CN103579521B - A kind of top radiation organic EL part and manufacture method thereof - Google Patents
A kind of top radiation organic EL part and manufacture method thereof Download PDFInfo
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Abstract
The invention discloses a kind of top radiation organic EL part, on the cathode layer of described top radiation organic EL part, plating has cover layer, wherein, described cover layer is that refractive index is greater than 1.8 in wavelength 450nm to 650nm scope, and energy gap Eg is greater than the organic material of 3.0eV. The invention also discloses the preparation method of top radiation organic EL part. Top radiation organic EL part of the present invention can ensure the light transmittance of negative electrode, can avoid display screen to change with visual angle simultaneously.
Description
Technical field
The invention belongs to organic electroluminescence device field, relate to a kind of top radiation organic EL part andIts manufacture method.
Background technology
Organic Light Emitting Diode, claims again organic electroluminescence device (OLED) to be divided into end transmitting according to bright dipping modeOrganic electroluminescence device and top radiation organic EL part. End radiation organic EL part(BEOLED), its transparent anode indium tin oxide ITO (or indium-zinc oxide IZO) is raw by the mode of sputterLong in glass substrate, the light that device inside sends passes through ITO (or IZO) in succession, glass substrate penetrates. AdoptThe display screen of making in this way, because drive circuit and viewing area will be produced on above glass simultaneously, is ledCause viewing area area and relatively reduce, the aperture opening ratio of display screen reduces. Compared with common end ballistic device,Top radiation organic EL part (TEOLED) is due to the design feature of itself, and light can be from top electrodesPenetrate, in active driving OLED, pixel-driving circuit, bus etc. can be produced on viewing area underSide, thus drive circuit and the viewing area problem of competition mutually avoided, make the aperture opening ratio of device greatlyImprove. Top radiation organic EL part can also be produced in silicon-based substrate, thereby can be made on silicon micro-Display. Because the display screen of top ballistic device making also has, resolution ratio is high, information content advantages of higher,This all makes top radiation organic EL part receive over the past two years more and more people's concern, and becomes oneIndividual study hotspot.
In top radiation organic EL part, generally use transparent ITO (or IZO) or translucentMetal is as top negative electrode. Need to use the method for sputter owing to making ITO (or IZO), high energy ITO (orIZO) particle is very strong for the organic layer destructiveness of bottom, and therefore better replacement scheme is that employing is translucentMetal substitutes ITO (or IZO) as top negative electrode. Its advantage is easy growth, destructive little; Shortcoming isThe light transmission of metal is poor, is unfavorable for the coupling output of light, and microcavity effect is comparatively obvious, at displayIn application, luminous intensity and color are maximum shortcomings with the change at visual angle. Therefore we need to be translucentMetal level on prepare one deck cover layer, reduce luminous energy in the reflection of optical element surface, increase transmitted lightLuminous flux. Equally, introducing cover layer on the metallic cathode surface of top radiation organic EL part can changeBecome the distribution of reflection of light and transmission potential. The conventional cover layer using is high temperature inorganic material, conventionally adoptsSputtering method or chemical gaseous phase depositing process preparation. But these modes all can damage organic film.
Triamine derivative, arlydene diamine derivative, CBP, Alq in Samsung patent 101944570, are used3As organic coating layer, to increase the efficiency of emergent light, and the thickness that limits this organic layer is 30nm-90nm.Although this scheme has obtained maximum emergent light intensity, does not consider the visual angle change causing due to microcavity effect.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides top radiation organic EL part, this top is sent outPenetrating plating on the cathode layer of organic electroluminescence device has cover layer,
Wherein, described cover layer is that refractive index is greater than 1.8, energy gap in wavelength 450nm to 650nm scopeEg is greater than the organic material of 3.0eV.
Preferably, described cover layer is the organic material that has the organic material of formula 1 structure or have formula 2 structures,
Formula 1
In formula 1, R1-R4、R5-R8、R5’-R8' respectively independently selected from protium, halogen, CN,NO2, amino, sub-fused ring aryl, sub-condensed hetero ring aryl, alkyl or alcohol radical; A and B be choosing independently respectivelyFrom phenyl, naphthyl or anilino-; R9、R10、R9' and R10' respectively independently selected from aryl;
Formula 2
In formula 2, A and B are respectively independently selected from phenyl, naphthyl or anilino-, R1And R2、R1' and R2’Respectively independently selected from aryl.
Preferably, in formula 1, described sub-fused ring aryl is that carbon number is 6 to 30 sub-fused ring aryl, instituteStating sub-condensed hetero ring aryl is that carbon number is 6 to 30 sub-condensed hetero ring aryl, and described alkyl is that carbon number is6 to 20 alkyl, described alcohol radical is that carbon number is 6 to 30 alcohol radical, R9、R10、R9' and R10' pointIt is not 6 to 30 aryl independently selected from carbon number. In formula 2, R1And R2、R1' and R2' respectively solelyOn the spot be selected from carbon number and be 6 to 30 aryl.
The organic material preferably, with formula 1 structure is following compound:
Formula 1-1
Formula 1-2
Formula 1-3
Formula 1-4
Formula 1-5
The organic material preferably, with formula 2 structures is following compound:
Formula 2-1
Formula 2-2
Formula 2-3
Formula 2-4
Formula 2-5
Preferably, above-mentioned top radiation organic EL part, comprising: substrate, and on substrate successivelyReflecting layer, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer that plating forms,Electron injecting layer, cathode layer and described cover layer.
Preferably, described cathode layer is silver or silver alloy, and thickness is 15 ~ 25nm; Described cover layer, thicknessBe 30 ~ 70nm.
More preferably, cathode layer is silver or silver alloy, and thickness is 15 ~ 18nm; Cover layer, thickness is 30 ~ 70nm.
More preferably, cathode layer is silver or silver alloy, thickness 18 ~ 25nm; Cover layer, thickness is 30 ~ 50nm.
Wherein, described silver alloy is the silver-colored magnesium alloy of weight ratio 1:10 ~ 10:1 or the silver of weight ratio 1:10-10:1Lithium alloy.
The invention provides the manufacture method of above-mentioned top radiation organic EL part, sink by physical vaporLong-pending method or chemical gaseous phase depositing process are prepared reflecting layer and anode layer on substrate, then by thermal evaporation sideFormula deposits hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the moon successivelyUtmost point layer and cover layer.
Top radiation organic EL part of the present invention can ensure the light transmittance of negative electrode, can avoid aobvious simultaneouslyShow that screen changes with visual angle.
Brief description of the drawings
The structural representation of Fig. 1 top radiation organic EL part of the present invention.
The refractive index of the tectal organic material of Fig. 2 the present invention is with wavelength variations schematic diagram.
Description of reference numerals:
Substrate 1; Reflecting layer 2; Anode layer 3; Hole injection layer 4; Hole transmission layer 5; Luminescent layer 6; ElectricitySub-transport layer 7; Electron injecting layer 8; Cathode layer 9; Cover layer 10.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, so that those skilled in the art canBetter understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention.
The invention provides a kind of top radiation organic EL part, can improve top radiation organic ELDevice visual angle.
As shown in Figure 1, top radiation organic EL part structure comprises: substrate 1, and on substrate 1Plating forms successively reflecting layer 2, anode layer 3, hole injection layer (HIL) 4, hole transmission layer (HTL) 5,Luminescent layer (EML) 6, electron transfer layer (ETL) 7, electron injecting layer (EIL) 8, cathode layer 9 andCover layer 10.
Wherein, substrate 1 is glass or polymer (plastics or polyimides etc.).
Reflecting layer 2 can be argent or silver alloy, metal aluminum or aluminum alloy.
Anode layer 3 can be ITO(tin indium oxide), IZO(indium zinc oxide).
Hole injection layer 4 is 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (MTDATA)With the mixture of 2,3,5,6-tetrafluoro four cyano Kui bismethane (F4TCNQ), both mass ratios are 25:1,The molecular structural formula of MTDATA and F4TCNQ is as follows:
Hole transmission layer 5 is N, N '-bis--(1-naphthyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamines(NPB), its molecular structural formula is
Luminescent layer 6 can be ruddiness, green glow or blue light. Wherein,
The main body RH of ruddiness is Bebq2(two (10-hydroxy benzo [h] quinoline) beryllium), dyestuff RD areIr(piq)2(acac), molecular structural formula is respectively:
The main body GH of green glow is CBP(4,4 '-Bis (9H-carbazol-9-yl) biphenyl), dyestuff GD isIr(ppy)3, molecular structural formula is respectively:
Blue light main body BH is AND(9,10-Di (naphtha-2-yl) anthracene), dyestuff BD is DPAVB(4-(di-p-tolylamino)-4 '-[(di-p-tolylamino) styryl] stilbene), molecular structural formula is respectively:
Electron transfer layer 7 is Bphen, and its molecular structural formula is:
In specific implementation process, can utilize following formula (1), make in organic layer each layer (to comprise HILLayer, htl layer, luminescent layer and ETL layer) and the thickness of anode layer meet:
Wherein, the peak value that λ is luminescent spectrum, the phase angle that Φ 1 is reflecting layer, Φ 2 is phase places of negative electrodeAngle, dmThe thickness that is each layer and ITO layer in organic layer (be between reflecting layer and transparent cathode each layer) is (totalThickness d=Σ dm），nmFor each layer of corresponding refractive index, θ0Be each layer of corresponding emergent light angle, k is normalNumber.
Electron injecting layer 8 can be alkali metal, inorganic base metal compound or organic alkali metal complex. PreferablyAlkali metal is lithium metal, metallic potassium, and inorganic base metal compound is LiF, and organic alkali metal complex is eightOxyquinoline lithium.
Cathode layer 9 can be Ag, silver-colored magnesium alloy (Mg:Ag weight ratio=1:10 ~ 10:1), silver-colored lithium alloy (Li:AgWeight ratio=1:10 ~ 10:1), cathode layer thickness is 15nm-25nm.
Cover layer 10 is that refractive index is greater than 1.8 in wavelength 450nm to 650nm scope, and energy gap Eg is greater thanThe organic material of 3.0eV.
For top radiation organic EL part, should obtain the visual angle that high efficiency obtains again, firstNeed covering layer material to there is appropriate refractive index and suitable energy gap, require its refractive index at visible wavelengthIn scope, (450nm-650nm) is greater than 1.8, to increase the light transmittance of negative electrode; Energy gap Eg > 3.0eV, withEven if ensure that dark blue coloured light does not have light absorption phenomenon by cover layer yet and occurs. 450nm's to 650nmOptical band, particularly wavelength are greater than the red spectral band of 600nm, and the refractive index of organic material only has 1.7 left and right.And the higher organic material of some refractive indexes is owing to having larger conjugated system, therefore its bandwidth is less than3.0eV, likely absorbs the blue light of OLED outgoing.
The organic material after measured with formula 1 structure exists with the organic material with formula 2 structuresRefractive index within the scope of 450nm-650nm is greater than 1.8, if Fig. 2 is formula 1-1 compound and formula 2-1 compoundRefractive index with the schematic diagram of wavelength variations. There is the organic material of formula 1 structure and there is having of formula 2 structuresMachine material energy level adopts cyclic voltammetry test, is respectively 3.0eV-3.3eV and 3.15eV-3.45eV.
The optional use of cover layer 10 has the organic material of formula 1 molecular structure:
Formula 1
In formula 1, R1-R4、R5-R8、R5’-R8' respectively independently selected from protium, halogen ,-CN,-NO2, amino, sub-fused ring aryl, sub-condensed hetero ring aryl, alkyl and alcohol radical, described sub-fused ring aryl is preferredFor carbon number is 6 to 30 sub-fused ring aryl, it is 6 that described sub-condensed hetero ring aryl is preferably carbon numberTo 30 sub-condensed hetero ring aryl, it is 6 to 20 alkyl that described alkyl is preferably carbon number, described alcohol radicalBe preferably carbon number and be 6 to 30 alcohol radical. A and B are selected from respectively phenyl, naphthyl and anilino-. R9、R10、R9' and R10' respectively independently selected from aryl, be preferably carbon number and be 6 to 30 aryl.The organic material with formula 1 structure can be:
Formula 1-1
Formula 1-2
Formula 1-3
Formula 1-4
Formula 1-5
Formula 1-1 ~ formula 1-5 compound can be prepared according to the disclosed mode of US6586120.
Cover layer also can be the organic material with formula 2 structures:
Formula 2
Wherein, A and B are respectively independently selected from phenyl, naphthyl and anilino-. R1And R2、R1' and R2' point, independently selected from aryl, preferably carbon number is not 6 to 30 aryl.
The organic material with formula 2 structures can be:
Formula 2-1
Formula 2-2
Formula 2-3
Formula 2-4
Formula 2-5
The preparation method of formula 2-1 ~ 2-5 compound is as follows:
Under nitrogen protection, by 7.4 gram of two (o-bromophenyl) dimethylsilane, (synthetic method is referring to J.Organomet.Chem.1984,271,319-326) (20mmol) join in 500ml there-necked flask, addEntering 150ml absolute ether dissolves. Reaction system is cooled to-80 DEG C, slowly drips 1.5M tert-butyl lithium(59ml, 88mmol) keeps reaction mixture at-80 DEG C in dropping process, dropwises, and continuesAt this temperature, stir 1 hour. Then add 3.65g benzophenone (20mmol), stir at low temperaturesMix 30 minutes, then remove cryostat, make reaction system naturally be warmed up to room temperature, and at room temperature continueStir 3 hours. Add saturated ammonium chloride solution cancellation reaction, product is extracted with ethyl acetate, organic phaseUse anhydrous magnesium sulfate drying. Product separates and obtains white solid II4.67g, yield 67% through column chromatography.
4.67 grams of white solids (12.4mmol) that upper step is obtained are dissolved in the carrene that 10ml is dry,To 0-5 DEG C, slowly drip bromine (4.4g, 27mmol) with ice-water bath cooling reaction system, drip completelyAfter be raised to room temperature, and continue to stir 5 hours, TLC monitoring raw material disappears. Add sodium hydrogensulfite water-solubleLiquid cancellation is reacted and is removed excessive bromine. Post processing also separates and obtains white solid III through silica gel column chromatography4.92g, yield 83%.
Above-mentioned 4.92g bis-bromo-derivatives (10.3mmol) are joined to 250ml there-necked flask under nitrogen protectionIn, add the 1:1 mixture of 100ml absolute ether and THF, system is cooled to-80 DEG C with cryostat,Slowly drip 1.5M tert-butyl lithium (30ml, 45mmol), in dropping process, keep temperature-resistant,After dripping completely, continue at this temperature, to stir 1 hour. Then add 3.4g bis-(4-bromophenyl) ketone(10mmol), continue to remain on this temperature lower 30 minutes, then remove cryostat, make reaction system natureBe warmed up to room temperature, and at room temperature continue to stir 4 hours. Add saturated ammonium chloride solution cancellation reaction,Product is extracted with ethyl acetate, organic phase anhydrous magnesium sulfate drying. Product obtains white through column chromatography separationLook solid IV3.6g, yield 56%.
At N2Under protection, add successively 150ml toluene to being equipped with in the 250ml there-necked flask of magnetic agitation,6.4g9,9-bis-(to bromophenyl)-10,10-diphenyl dihydroanthracene IV (10mmol), 6.1g phenyl-(4-xenyl)Amine (25mmol), under agitation, adds 2.9g sodium tert-butoxide (30mmol), can not dissolve completely, then addEnter 86mgPd (dba)2(0.15mmol), darken, then add 0.6g10% tri-butyl phosphine just ownAlkane solution (0.3mmol), adds hot reflux, and reactant liquor becomes yellow green, refluxes and puts plate after 5 hours, basicWithout raw material, be cooled to 45 DEG C when following, add the mixed solution of 5ml concentrated hydrochloric acid and 100ml water, separatory,150ml toluene extraction for water, merging is spin-dried for and obtains thick product, and thick product is through petrol ether/ethyl acetate (bodyLong-pending than 5:1) system column chromatography for separation obtains white solid 7.1g, is formula 2-1 compound, yield 73%.
Product MS(m/e): 970, elementary analysis (C74H54N2): theoretical value C:91.51%, H:5.60%, N:2.88%; Measured value C:91.38%, H:5.55%, N:2.72%.
At N2Under protection, add successively 150ml toluene to being equipped with in the 250ml there-necked flask of magnetic agitation,6.4g9,9-bis-(to bromophenyl)-10,10-diphenyl dihydroanthracene IV (10mmol), 8.0g bis-(4-xenyl)Amine (25mmol), under agitation, adds 2.9g sodium tert-butoxide (30mmol), can not dissolve completely, then addEnter 86mgPd (dba)2(0.15mmol), darken, then add 0.6g10% tri-butyl phosphine just ownAlkane solution (0.3mmol), adds hot reflux, and reactant liquor becomes green, reflux and put plate after 5 hours, substantially withoutRaw material, is cooled to 45 DEG C when following, adds the mixed solution of 5ml concentrated hydrochloric acid and 100ml water, separatory,150ml toluene extraction for water, merging is spin-dried for and obtains thick product, and thick product is through petrol ether/ethyl acetate (bodyLong-pending than 6:1) system column chromatography for separation obtains white solid 7.75g, is formula 2-2 compound, yield69%。
Product MS(m/e): 1122, elementary analysis (C86H62N2): theoretical value C:91.94%, H:5.56%, N:2.49%; Measured value C:91.79%, H:5.63%, N:2.31%.
At N2Under protection, add successively 150ml toluene to being equipped with in the 250ml there-necked flask of magnetic agitation,6.4g9,9-bis-(to bromophenyl)-10,10-diphenyl dihydroanthracene IV (10mmol), 4.3g diphenylamine(25mmol), under agitation, add 2.9g sodium tert-butoxide (30mmol), can not dissolve completely, then add86mgPd(dba)2(0.15mmol), darken, then add 0.6g10% tri-butyl phosphine n-hexane moltenLiquid (0.3mmol), adds hot reflux, and reactant liquor becomes green, and reflux and put plate after 5 hours, substantially without raw material,Below being cooled to 45 DEG C time, add the mixed solution of 5ml concentrated hydrochloric acid and 100ml water, separatory, water is usedThe extraction of 150ml toluene, merging is spin-dried for and obtains thick product, and thick product is through petrol ether/ethyl acetate (volume ratio6:1) system column chromatography for separation obtains white solid 6.6g, is formula 2-3 compound, yield 81%.
Product MS(m/e): 818, elementary analysis (C62H46N2): theoretical value C:90.92%, H:5.66%, N:3.42%; Measured value C:90.84%, H:5.60%, N:3.51%.
At N2Under protection, add successively 150ml toluene to being equipped with in the 250ml there-necked flask of magnetic agitation,6.4g9,9-bis-(to bromophenyl)-10,10-diphenyl dihydroanthracene IV (10mmol), 5.5g phenyl-(2-naphthyl)Amine (25mmol), under agitation, adds 2.9g sodium tert-butoxide (30mmol), can not dissolve completely, then addEnter 86mgPd (dba)2(0.15mmol), darken, then add 0.6g10% tri-butyl phosphine just ownAlkane solution (0.3mmol), adds hot reflux, and reactant liquor becomes green, reflux and put plate after 5 hours, substantially withoutRaw material, is cooled to 45 DEG C when following, adds the mixed solution of 5ml concentrated hydrochloric acid and 100ml water, separatory,150ml toluene extraction for water, merging is spin-dried for and obtains thick product, and thick product is through petrol ether/ethyl acetate (bodyLong-pending than 6:1) system column chromatography for separation obtains white solid 7.2g, is formula 2-4 compound, yield 78%.
Product MS(m/e): 918, elementary analysis (C70H50N2): theoretical value C:91.47%, H:5.48%, N:3.05%; Measured value C:91.55%, H:5.39%, N:3.11%.
At N2Under protection, add successively 150ml toluene to being equipped with in the 250ml there-necked flask of magnetic agitation,6.4g9,9-bis-(to bromophenyl)-10,10-diphenyl dihydroanthracene IV (10mmol), 5.5g phenyl-(1-naphthyl)Amine (25mmol), under agitation, adds 2.9g sodium tert-butoxide (30mmol), can not dissolve completely, then addEnter 86mgPd (dba)2(0.15mmol), darken, then add 0.6g10% tri-butyl phosphine just ownAlkane solution (0.3mmol), adds hot reflux, and reactant liquor becomes green, reflux and put plate after 5 hours, substantially withoutRaw material, is cooled to 45 DEG C when following, adds the mixed solution of 5ml concentrated hydrochloric acid and 100ml water, separatory,150ml toluene extraction for water, merging is spin-dried for and obtains thick product, and thick product is through petrol ether/ethyl acetate (bodyLong-pending than 6:1) system column chromatography for separation obtains white solid 5.1g, is formula 2-5 compound, yield 56%.
Product MS(m/e): 918, elementary analysis (C70H50N2): theoretical value C:91.47%, H:5.48%, N:3.05%; Measured value C:91.41%, H:5.52%, N:3.16%.
In the present invention, the efficiency that top light-emitting organic electroluminescent device will obtain and viewing angle characteristic, require cloudyHas the light extraction efficiency of specific light transmittance or specific wavelength, therefore the thickness of negative electrode Ag and tectalThickness preferably has certain corresponding relation. In the time that the thickness of Ag is 15-18nm, tectal thickness exists30nm-70nm; In the time that the thickness of Ag is 18-25nm, tectal thickness is 30-50nm.For example, in the time that cathode layer selects Ag to be 15nm, on it, plating has cover layer (the organic material of formula 1-1 of different-thicknessMaterial), when overburden cover is respectively 0nm, 30nm, 40nm, 50nm, 60nm, 70nm, at 458nmWavelength under plating have tectal cathode layer light transmittance as shown in table 1.
Table 1
As can be seen from Table 1, cover layer has the effect that increases light transmittance, and plating has tectal cathode construction,Compare and while thering is no cover layer, improved light transmittance.
In the time that cathode layer selects Ag to be 20nm, on it, be coated with cover layer (the organic material of formula 2-1 of different-thicknessMaterial), when overburden cover is respectively 0nm, 30nm, 40nm, 50nm, under the wavelength of 458nmPlating has tectal cathode layer light transmittance as shown in table 2.
Table 2
Plating has tectal cathode construction, compares and while thering is no cover layer, has improved light transmittance.
Below enumerate specific embodiment so that the present invention is further described
Embodiment 1
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 130nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein F4TCNQ weight is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again the deposition ADN of 30nm and the mixing of DPAVBThing is as luminescent layer, and wherein DPAVB weight is 5% of AND weight. Then deposit the Bphen of 20nmAs electron transfer layer (ETL). Keep the vacuum constant, pass through Li3N is (temperature 600 in evaporate processDEG C) Li of mode evaporation 1nm that decomposes is as electron injecting layer (EIL), the Ag conduct of deposition 20nmNegative electrode, the organic material that deposition 40nm has formula 1-1 structure is as cover layer.
The emergent light of device prepared by the present embodiment is blue light, luminescent spectrum peak value with visual angle change as table 3Show
Table 3
As can be seen from Table 3, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 2
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 170nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein F4TCNQ weight is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again the deposition CBP of 30nm and the mixing of Ir (ppy) 3Thing is as luminescent layer, wherein Ir (ppy)3Weight is 5% of CBP weight. Then deposit the Bphen of 20nmAs electron transfer layer (ETL). Keep the vacuum constant, pass through KBH4(temperature 400 in evaporate processDEG C) K of mode evaporation 1nm that decomposes is as electron injecting layer (EIL), the Ag conduct of deposition 20nmNegative electrode, the organic material that deposition 40nm has formula 1-3 structure is as cover layer.
Device prepared by the present embodiment is green glow, and luminescent spectrum peak value is as shown in table 4 with visual angle change
Table 4
As can be seen from Table 4, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 3
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 60nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein F4TCNQ weight is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again the BeBq of deposition 30nm2And Ir (piq)2(acac)Mixture as luminescent layer, wherein Ir (piq)2(acac) weight is BeBq25% of weight. Then depositionThe Bphen of 20nm is as electron transfer layer (ETL). Keep the vacuum constant, pass through KBH4At evaporationThe K of the mode evaporation 1nm that in process, (400 DEG C of temperature) decomposes, as electron injecting layer (EIL), depositsThe Ag of 25nm is as negative electrode, and the organic material that deposition 30nm has formula 1-5 structure is as cover layer.
Device prepared by the present embodiment is ruddiness, and luminescent spectrum peak value is as shown in table 5 with visual angle change:
Table 5
As can be seen from Table 5, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 4
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 130nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein the weight of F4TCNQ is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again the deposition ADN of 30nm and the mixing of DPAVBThing is as luminescent layer, and wherein the weight of DPAVB is 5% of ADN weight. Then deposit the Bphen of 20nmAs electron transfer layer (ETL). Keep the vacuum constant, pass through Li3N is (temperature 600 in evaporate processDEG C) Li of mode evaporation 1nm that decomposes is as electron injecting layer (EIL), the Ag conduct of deposition 15nmNegative electrode, the organic material that deposition 70nm has formula 2-1 structure is as cover layer.
Device prepared by the present embodiment is blue-light device, and luminescent spectrum peak value is as shown in table 6 with visual angle change
Table 6
As can be seen from Table 6, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 5
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 170nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein the weight of F4TCNQ is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again CBP and the Ir (ppy) of deposition 30nm3MixingThing is as luminescent layer, wherein Ir (ppy)3Weight be 5% of CBP weight. Then deposit the Bphen of 20nmAs electron transfer layer (ETL). Keep the vacuum constant, pass through KBH4In evaporate process, (temperature approximately400 DEG C) K of mode evaporation 1nm that decomposes is as electron injecting layer (EIL), the Ag of deposition 25nmAs negative electrode, the organic material that deposition 50nm has formula 2-2 structure is as cover layer.
Device prepared by the present embodiment is green device, and luminescent spectrum peak value is as shown in table 7 with visual angle change
Table 7
As can be seen from Table 7, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 6
On glass substrate, sputtering sedimentation Ag is as reflecting layer, and thickness is 150nm, the ITO of sputter 10nmAs the anode of device, and etch required figure, use O2Plasma treatment 3 minutes. By gained basePlate is placed in vacuum, by the common steaming deposition MTDATA of 60nm and the mixture of F4TCNQ as skyCave implanted layer (HIL), wherein the weight of F4TCNQ is 4% of MTDATA weight. Then deposit 10nmNPB as hole transmission layer (HTL). Steam altogether again the BeBq of deposition 30nm2And Ir (piq)2(acac)Mixture as luminescent layer, wherein Ir (piq)2(acac) weight is BeBq25% of weight. Then depositionThe Bphen of 20nm is as electron transfer layer (ETL). Keep the vacuum constant, pass through KBH4At evaporationThe K of the mode evaporation 1nm that in process, (approximately 400 DEG C of temperature) decomposes is as electron injecting layer (EIL), heavyThe Ag of long-pending 22nm is as negative electrode, and the organic material that deposition 45nm has formula 2-4 structure is as cover layer.
The prepared device of the present embodiment is ruddiness device, and luminescent spectrum peak value is as shown in table 8 with visual angle change
Table 8
As can be seen from Table 8, the luminescent spectrum peak change of the top radiation organic EL part of the present embodimentScope is very little, has avoided display screen to change with visual angle.
Embodiment 7
The preparation method of the top radiation organic EL part of the present embodiment is with embodiment 1, and difference is to sinkAmass the metal complex LiQ of 1nm as electron injecting layer, silver-colored magnesium alloy (the Mg:Ag weight ratio of 18nm=1:10) as negative electrode, cover layer is the organic material with formula 1-2 structure of thickness 40nm.
The prepared device of the present embodiment is blue-light device, and luminescent spectrum peak value is as shown in table 9 with visual angle change
Table 9
Embodiment 8
The preparation method of the top radiation organic EL part of the present embodiment is with embodiment 2, and difference is to coverCap rock is the organic material with formula 1-4 structure of thickness 40nm.
The prepared device of the present embodiment is green device, luminescent spectrum peak value with visual angle change as table 10Show:
Table 10
Embodiment 9
The preparation method of the top radiation organic EL part of the present embodiment is with embodiment 4, and difference is to coverCap rock is the organic material with formula 2-3 structure of thickness 45nm.
The prepared device of the present embodiment is blue-light device, luminescent spectrum peak value with visual angle change as table 11Show:
Table 11
Embodiment 10
The preparation method of the top radiation organic EL part of the present embodiment is with embodiment 6, and difference is to coverCap rock is the organic material with formula 2-5 structure of thickness 40nm.
The prepared device of the present embodiment is ruddiness device, and luminescent spectrum peak value is as shown in table 12 with visual angle change
Table 12
The above embodiment is only the preferred embodiment for absolutely proving that the present invention lifts, of the present inventionProtection domain is not limited to this. What those skilled in the art did on basis of the present invention be equal to substitute orConversion, all within protection scope of the present invention. Protection scope of the present invention is as the criterion with claims.
Claims (9)
1. a top radiation organic EL part, is characterized in that, on the cathode layer of described top radiation organic EL part, plating has cover layer,
Described cover layer is that refractive index is greater than 1.8 in wavelength 450nm to 650nm scope, and energy gap Eg is greater than the organic material of 3.0eV;
Wherein, described cover layer is the organic material with formula 2 structures,
Formula 2
In formula 2, A and B are respectively independently selected from phenyl, naphthyl or anilino-, R1And R2、R1' and R2' respectively independently selected from aryl.
2. top radiation organic EL part according to claim 1, is characterized in that,
In formula 2, R1And R2、R1' and R2' be respectively 6 to 30 aryl independently selected from carbon number.
3. top radiation organic EL part according to claim 1, is characterized in that, described in there are formula 2 structures organic material be following compound:
Formula 2-1
Formula 2-2
Formula 2-3
Formula 2-4
Formula 2-5.
4. top radiation organic EL part according to claim 1, it is characterized in that, comprise: substrate, and reflecting layer, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer and described cover layer that on substrate, plating forms successively.
5. top radiation organic EL part according to claim 4, is characterized in that, described cathode layer is silver or silver alloy, and thickness is 15 ~ 25nm; Described overburden cover is 30 ~ 70nm.
6. top radiation organic EL part according to claim 4, is characterized in that, cathode layer is silver or silver alloy, and thickness is 15 ~ 18nm; Described overburden cover is 30 ~ 70nm.
7. top radiation organic EL part according to claim 4, is characterized in that, cathode layer is silver or silver alloy, thickness 18 ~ 25nm; Described overburden cover is 30 ~ 50nm.
8. according to the top radiation organic EL part described in claim 5-7 any one, it is characterized in that, described silver alloy is the silver-colored magnesium alloy of weight ratio 1:10 ~ 10:1 or the silver-colored lithium alloy of weight ratio 1:10-10:1.
9. the manufacture method of the top radiation organic EL part described in claim 1 ~ 8 any one, it is characterized in that, on substrate, prepare reflecting layer and anode layer by physical gas-phase deposite method or chemical gaseous phase depositing process, then deposit successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer and cover layer by thermal evaporation mode.
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