CN101635334A - Red organic electroluminescence device and preparation method thereof - Google Patents
Red organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN101635334A CN101635334A CN200910060387A CN200910060387A CN101635334A CN 101635334 A CN101635334 A CN 101635334A CN 200910060387 A CN200910060387 A CN 200910060387A CN 200910060387 A CN200910060387 A CN 200910060387A CN 101635334 A CN101635334 A CN 101635334A
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Abstract
The invention discloses a red organic electroluminescence device, comprising a substrate, an anode layer, a cathode layer and an organic function layer arranged between the anode layer and the cathode layer, wherein the organic function layer comprises a luminescent layer. The red organic electroluminescence device is characterized in that: 1, the luminescent layer comprises main materials and dopant materials, the dopant materials are yellow phosphor dye and red fluorescent dye, the doping intensity of the yellow phosphor dye is 1-15wt% while the doping intensity of the red fluorescent dye is 0.1-5wt%; 2, excition energy is transferred from main materials to the yellow phosphor dye and the red fluorescent dye when the luminescent layer is driven by an external power supply, phosphor photosensitization of the yellow phosphor dye on the red fluorescent dye is utilized to improve energy transfer efficiency of phosphor triple state excition to fluorescent single state excition and improve utilization rate of radiation luminescence of fluorescent excition, so as to cause the device to give out red light.
Description
Technical field
The present invention relates to the organic electroluminescence device technical field, be specifically related to a kind of red organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent is meant luminous organic material luminous phenomenon under the excitation of electric current or electric field.1963, people such as the Pope of New York Univ USA (J.Chem.Phys., 1963,38,2042) reported first the electro optical phenomenon of organic material monocrystalline anthracene, opened the prelude of organic electroluminescent research.Nineteen eighty-two, Vincett research group (Thin Solid Films, 1982,94,171) adopts vacuum vapour deposition to prepare the anthracene single crystal film that successful thickness is 0.6 μ m, and the operating voltage of organic electroluminescent is dropped in the 30V.By 1987, C.W.Tang of Kodak and S.A.Vanslyke (Appl.Phys.lett., 1987,51,913) invented the device of sandwich structure on the basis of summing up forefathers' research, and successfully having prepared quantum efficiency is 1%, and brightness is greater than 1000cd/m
2Organic electroluminescence device (Organic light-emitting devices, OLEDs).This breakthrough has excited the research enthusiasm of people for OLEDs, makes OLEDs become worldwide popular research topic rapidly.The OLEDs technology has that all solid state active surface is luminous, ultra-thin, light, power consumption is little, response speed is fast, flexible, a series of advantage such as operating temperature range is wide, and processing and forming is easy, free from environmental pollution, has broad application prospects.A plurality of in the world famous laboratory, research institute, display device manufacturer, lighting apparatus manufacturer and chemical companies all in the input of the research field of OLEDs material, components and parts, manufacturing process and production equipment huge manpower and fund.Therefore, through short 20 years development, OLEDs has finished the transition from the basic research to the finished commercial prod substantially, at field of information display and lighting field in occupation of consequence.
In the development and utilization to OLEDs, the research of the colorize of OLEDs is a very important link.Because three primary colors (red, green, blue) combinations can obtain colors all in the chromatogram, be focus in the research therefore based on trichromatic organic electroluminescence device.1989, people such as C.W.Tang (J.Appl.Phys., 1989,65,3610) adopted red fluorescence dyestuff DCM and green fluorescence dyestuff C540 to be doped to Alq respectively
3In, obtain quantum efficiency and be～2.5% Chinese red and green organic electroluminescence device, started the beginning of OLEDs colorize.From then on, fluorescent dye is used in preparation three primary colors organic electroluminescence device widely.But because fluorescent material is subjected to the restriction of electron spin, its electroluminescence has only utilized the energy (25%) of singlet excited, and all the other energy that are in triplet excited state all are not utilized (75%).Therefore, the internal quantum efficiency of fluorescent material is subject to 25%, and it is inevitably sorry that this becomes further raising device efficiency.1998, (the Nature of Forrest team of Princeton university, 1998,395,151 or United States Patent (USP) 6645645) reported first a kind of red organic electroluminescence device based on red phosphorescent dyestuff PtOEP, its internal quantum efficiency has been opened up the frontier of organic electromechanical phosphorescent material up to 23%.Calendar year 2001, Forrest team (J.Appl.Phys., 2001,90,5048) has reported once more based on green phosphorescent dye (ppy)
2The OLEDs of Ir (acac), having obtained external quantum efficiency is 19.0 ± 1.0%, internal quantum efficiency has been broken the electroluminescent organic material internal quantum efficiency and has been lower than 25% restriction near 100% green device.2003, people such as Y.J.Su (Adv.Mater.2003,15,884) reported based on phosphorescent coloring (piq)
2The red phosphorescent device of Ir (acac) is 100mA/cm in current density
2The time external quantum efficiency reach 9.21%.2006, Kodak company reported that in the ICEL-6 meeting a kind of green folds string data phosphorescence device, and its current efficiency is up to 350cd/A.2008, the Frank So of University of Florida (Appl.Phys.lett., 2008,93,143307) reported a series of blue organic electroluminescent devices based on phosphorescent coloring FIrpic, and external quantum efficiency is 23%, and current efficiency is 49cd/A.
As can be seen, because the exploitation and the introducing of phosphorescent coloring, the luminous efficiency of red green blue tricolor OLEDs is greatly improved.Yet, compare green and blue phosphorescent dyestuff, the kind of red phosphorescent dyestuff is considerably less, has only (btp) at present
2Ir (acac), (piq)
3Ir, (piq)
2Ir (Adv.Func.Mater.2009,19,420) several more stable red phosphorescent dyestuffs such as (acac) are in the news and use.The patented technology of these dyestuffs is grasped in the fewer companies hand, and the cost costliness has limited the development of red organic electro phosphorescent device to a certain extent.In addition, when red organic electro phosphorescent device was worked under high current density, triplet-triplet usually can take place its phosphorescent coloring buried in oblivion phenomenon, seriously reduces the luminous efficiency of device.Opposite, many red fluorescence dyestuffs such as DCM series, DCJTB, DCDDC just do not have triplet-triplet to bury in oblivion effect, and their characteristics of luminescence is stable, and technology maturation also is beneficial to application.Therefore, in order to promote the development of red organic electroluminescence fluorescent device, and make full use of the energy of triplet excited state, 2000, people such as M.A.Baldo (Nature, 2000,403,750) notion of phosphor-sensitized fluorescent has been proposed, being intended to the phosphorescent coloring that certain is suitable (phosphorescence sensitizer) is doped in macromolecule or the micromolecule material of main part jointly with red fluorescence dyestuff, make the triplet excited state energy of phosphorescent coloring pass to the singlet excited of fluorescent dye as much as possible, thereby all energy all are utilized effectively, reach the purpose that improves the fluorescent dye quantum efficiency.
In the sensitization doped system of material of main part-phosphorescent coloring-fluorescent dye, mainly contain the mode of two kinds of energy delivery, a kind of Dexter energy delivery that is based on the adjacent molecule Orbital Overlap, another kind is based on dipole-dipole resonance (molecular excitation)
Energy delivery.The energy transfer process of having described the phosphor-sensitized fluorescent system (Nature, 2000,403,750) that Fig. 1 is detailed, wherein solid line is represented
Energy delivery, dotted line are represented Dexter energy delivery, S
0, S
*And T
*Ground state, singlet excited and the triplet excited state of representing luminescent material respectively.As can be seen, the available energy of fluorescent dye is mainly by following approach transmission:
1. S
*(main body) → S
*(fluorescence) → S
0(fluorescence)
2. S
*(main body) → S
*(phosphorescence) → S
*(fluorescence) → S
0(fluorescence)
3. S
*(main body) → S
*(phosphorescence) → T
*(phosphorescence) → S
*(fluorescence) → S
0(fluorescence)
4. T
*(main body) → T
*(phosphorescence) → S
*(fluorescence) → S
0(fluorescence)
In energy transfer process, 1. and 2. approach is singlet excited (S
*)-singlet excited (S
*)
Energy delivery, and 3. and 4. approach relates to triplet excited state (T
*)-singlet excited (S
*) energy delivery.That is to say, to have only and improve T as far as possible in order to make full use of 75% triplet excited state energy
* Phosphorescence-S
* FluorescenceEnergy transfer efficiency, just can reach the purpose that improves the device internal quantum efficiency.
As seen from the above analysis, the selection of phosphorescence sensitizer is to realizing high efficiency T
* Phosphorescence-S
* FluorescenceEnergy delivery is extremely important.Because the ladder of energy delivery, require the triplet energy state of material of main part to be higher than the energy of phosphorescence sensitizer usually, the triplet energy state of phosphorescence sensitizer is higher than the energy of fluorescent dye, and this has limited the range of choice of phosphorescence sensitizer to a certain extent.The phosphor-sensitized fluorescent system of report all adopts green phosphorescent dye and red fluorescence dyestuff to be doped to jointly in the material of main part at present, finally realizes red fluorescence efficiently.For example, calendar year 2001, people (Appl.Phys.lett., 2001,79,1045) such as D ' Andrade have reported that with CBP as material of main part, Ir (ppy) simultaneously mixes
3The phosphor-sensitized fluorescent device of green phosphorescent dye and DCM2 red fluorescence dyestuff, its external quantum efficiency are 9 ± 1%, and luminous efficiency is 17 ± 2lm/W (0.01mA/cm
2).But the glow color of device is yellow partially, and spectrum spectrum peak is about 580nm, and this is because Ir (ppy)
3Excitation state is to the T of DCM2 excitation state
* Phosphorescence-S
* FluorescenceEnergy delivery is incomplete, Ir (ppy)
3The triplet excitons radioluminescence is obvious, thereby has influenced the red emission colorimetric purity of device.2003, people such as G.Cheng (Appl.Phys.lett., 2003,82,4224) reported based on CBP:Ir (ppy)
3: the white light OLED s of DCJTB, the emitting red light spectrum peak of its doping system is also only about 580-590nm.After this, focus mostly in the development of white light OLED s, the research of red OLEDs is not deeply gone down about the report of micromolecule phosphor-sensitized fluorescent device.
From the existing result who utilizes phosphor-sensitized fluorescent to obtain ruddiness, generally all be to adopt green phosphorescent dye sensitization red fluorescence dyestuff.Although green phosphorescent dye doping red fluorescence dyestuff system has successfully improved the internal quantum efficiency of device, because the energy delivery of this system is incomplete, mainly be T
* Phosphorescence-S
* FluorescenceThe efficient of energy delivery is not high, causes not eliminating fully the luminous of phosphorescent coloring, and then has influenced the colorimetric purity of device.The problem that the colorimetric purity of the red OLEDs of this class is not high does not solve, and just can not satisfy the requirement of harsh day by day chromatogram color, is unfavorable for further developing of phosphor-sensitized fluorescent device yet.
Summary of the invention
Problem to be solved by this invention is: how a kind of red organic electroluminescence device and preparation method thereof is provided, and this device has overcome existing defective in the prior art, has improved the luminous efficiency of device, has improved the red light color purity of device.
Technical problem proposed by the invention is to solve like this: a kind of red organic electroluminescence device is provided, comprise substrate, anode layer, cathode layer, be arranged on the organic function layer between anode layer and the cathode layer, organic function layer comprises luminescent layer, it is characterized in that:
1. described luminescent layer comprises material of main part and dopant material, and described dopant material is yellow phosphorescence dyestuff and red fluorescence dyestuff, and the doping content of yellow phosphorescence dyestuff is 1～15wt%, and the doping content of red phosphorescent dyestuff is 0.1～5wt%;
2. described luminescent layer is under the driving of additional power source, exciton energy is shifted to red fluorescence dyestuff to the yellow phosphorescence dyestuff by material of main part, utilize of the phosphorescence sensibilization of yellow phosphorescence dyestuff to red fluorescence dyestuff, improve the energy transfer efficiency of phosphorescence triplet excitons to the fluorescence singlet exciton, increase the utilance of fluorescence exciton radioluminescence, make device send ruddiness
According to red organic electroluminescence device provided by the present invention, it is characterized in that, described material of main part is a carbazole compound, comprise 4,4 '-two (biphenyl (CBP), 4,4 '-two of carbazole-9-yl) (carbazole-9-yl)-2,2 '-dimethyl diphenyl (CDBP), 4,4 ', 4 "-three (triphenylamine (TCTA) and 1 of carbazole-9-yl), and 3-two (carbazole-9-yl)-benzene (mCP).
According to red organic electroluminescence device provided by the present invention, it is characterized in that described yellow phosphorescence dyestuff is iridium metals organic coordination compound two [2-(4-tertiary amine-butyl phenyl) benzo thiazolato-N, a C2 '] iridium (acetylacetonate compound) ((t-bt)
2Ir (acac)).
According to red organic electroluminescence device provided by the present invention, it is characterized in that, described red fluorescence dyestuff comprises 4-(dicyano methylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyrans (DCM2), 4-(dicyano methylene)-2-specific base-6 (1,1,7,7-tetramethyl-julolidine-4-yl-vinyl)-and 4H-pyrans (DCJTB), 3-(dicyano methylene)-5,5-dimethyl-1-(4-dimethylamino-styryl) encircles second rare (DCDDC).
According to red organic electroluminescence device provided by the present invention, it is characterized in that described organic function layer also comprises one or more of hole transmission layer, electron transfer layer, hole injection layer, electron injecting layer.
According to red organic electroluminescence device provided by the present invention, it is characterized in that, described hole transport layer material is aromatic diamine compounds or aromatic triamine compounds, wherein the aromatic diamine compounds is N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine (NPB) or N, N '-two (3-aminomethyl phenyl)-N, N '-two (phenyl)-benzidine (TPD) or N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-2,2 '-dimethylbenzidine (a-NPD), the aromatic triamine compounds is two-[4-(N, N-ditolyl-amino)-phenyl] cyclohexanes (TAPC).
According to red organic electroluminescence device provided by the present invention, it is characterized in that, described electric transmission layer material and electron injecting layer material are a kind of materials in metal organic complex, pyridines, o-phenanthroline class, oxadiazole class or the glyoxaline compound material, and wherein metal organic complex comprises oxine aluminium (Alq
3) or two (2-methyl-8-quino)-4-(phenylphenol) aluminium (BAlq), pyridine compounds and their comprises three [2,4,6-trimethyl-3-(phenyl of pyridine-3-yl)]-borine (3TPYMB), the o-phenanthroline compounds comprises 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 4,7-biphenyl-1,10-phenanthrolene (BPhen) oxadiazole electron-like transferring material is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole (PBD) or 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene (OXD-7), the imidazoles electron transport material is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBI).
According to red organic electroluminescence device provided by the present invention, it is characterized in that, described hole injection layer material comprises poly-(3, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or CuPc (CuPc) or 4,4 ', 4 " class in (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine compounds such as (m-MTDATA)-three.
According to red organic electroluminescence device provided by the present invention, it is characterized in that described substrate is glass or flexible substrate or sheet metal, wherein flexible substrate is ultra-thin solid-state thin slice, polyesters or poly-phthalimide compounds; Described anode layer is inorganic, metal oxide film or metallic film, and wherein the inorganic, metal oxide film is tin indium oxide (ITO) film or zinc oxide (ZnO) film or zinc tin oxide film, and metallic film is the metallic film of gold, copper, silver; Described anode layer material also can be the organic conductive polymer of PEDOT:PSS or PANI class; Described cathode layer is metallic film or alloy firm, comprises the alloy firm of metallic film that work functions such as lithium, magnesium, calcium, strontium, aluminium, indium are lower or they and copper, gold, silver.
Second technical problem proposed by the invention is to solve like this: a kind of preparation method of organic electroluminescence device, it is characterized in that, and may further comprise the steps:
1. utilize acetone, ethanolic solution and deionized water that substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. substrate is carried out the preparation of electrode layer in the vacuum evaporation chamber, described electrode comprises anode layer or cathode layer;
The substrate that 3. will prepare electrode moves in the vacuum chamber, carries out preliminary treatment under oxygen pressure ring border;
4. above-mentioned cleaning is dried up and place in the vacuum chamber through pretreated substrate, vacuumize, evaporation organic function layer on above-mentioned conductive substrates then, described organic function layer comprises luminescent layer, also comprise hole transmission layer, electron transfer layer, hole injection layer, in the electron injecting layer one or more, wherein, when the evaporation organic luminous layer, adopt the method for three source evaporations to carry out grade doping, respectively with material of main part, the yellow phosphorescence dyestuff places different evaporation sources with red fluorescence dyestuff, by controlling the evaporation speed of three evaporation sources, make yellow phosphorescence dyestuff and the red fluorescence dyestuff doping content in material of main part be respectively 1～15wt% and 0.1～5wt%;
5. keep above-mentioned vacuum chamber internal pressure constant, carry out the preparation of another electrode after the organic function layer evaporation finishes, described electrode is as the cathode layer or the anode layer of device;
6. ready-made device is sent to glove box and encapsulates, glove box is a nitrogen atmosphere.
The red organic electroluminescence device that the present invention proposes, have the following advantages: propose to adopt yellow phosphorescence dyestuff and red fluorescence dyestuff to be doped in the material of main part jointly for the first time, by utilizing of the phosphorescence sensibilization of yellow phosphorescence dyestuff, improved the phosphorescence triplet excitons effectively to fluorescence singlet exciton (T to red fluorescence dyestuff
* Phosphorescence-S
* Fluorescence) energy transfer efficiency, increased the utilance of fluorescence exciton radioluminescence, the luminous efficiency of device is improved, also eliminated the luminous of material of main part and phosphorescent coloring substantially, make the red light color purity of device obtain tangible improvement.
Description of drawings
Fig. 1 is the energy transfer process figure of phosphor-sensitized fluorescent system;
Fig. 2 is an organic electroluminescence device structural representation provided by the present invention;
Fig. 3 is the structural representation of embodiment 1-3 provided by the present invention;
Fig. 4 is the structural representation of embodiment 4-6 provided by the present invention;
Fig. 5 is the current density-voltage-brightness curve of the OLEDs of embodiment 1 among the present invention;
Fig. 6 is luminous efficiency-current density curve of the OLEDs of embodiment 1 among the present invention;
Fig. 7 is luminescent spectrum and the CIE coordinate of OLEDs under different voltages of embodiment 1 among the present invention.
Wherein, 1, substrate, 2, anode layer, 3, organic function layer, 30, hole injection layer, 31, hole transmission layer, 32, luminescent layer, 33, electron transfer layer, 4, cathode layer, 5, power supply.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
The invention provides a kind of red organic electroluminescence device, as Fig. 2, shown in Figure 3, the structure of device comprises substrate 1, anode layer 2, organic function layer 3, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, and organic function layer 3 is between anode layer 2 and cathode layer 4, and organic function layer 3 comprises hole transmission layer 31, luminescent layer 32 and electron transfer layer 33, device is luminous under the driving of additional power source 5.
As shown in Figure 4, the structure of device comprises substrate 1, anode layer 2, organic function layer 3, cathode layer 4, wherein anode layer 2 is positioned at substrate 1 surface, organic function layer 3 is between anode layer 2 and cathode layer 4, and organic function layer 3 comprises hole injection layer 30, hole transmission layer 31, luminescent layer 32 and electron transfer layer 33, device is luminous under the driving of additional power source 5.
Some the organic material title materials that relate in this specification and the abbreviation of molecular formula and full name list as following table:
Hole injection layer 30 is for the inorganic molecules compound or have the organic compound of low the highest occupied energy level (HOMO) energy level in the organic electroluminescence device among the present invention, a kind of as in the compounds such as CuPc, PEDOT:PSS, m-MTDATA.
Hole transmitting layer 31 is aromatic diamine compounds or aromatic triamine compounds in the organic electroluminescence device among the present invention, a kind of as in the materials such as NPB, TPD, a-NPD, TAPC, and the present invention is preferably NPB.
Organic luminous layer 32 is the mixed layer of doping yellow phosphorescence dyestuff, red fluorescence dyestuff in material of main part in the organic electroluminescence device among the present invention.Material of main part has higher triplet, can give phosphorescent coloring with energy delivery effectively, makes phosphorescent coloring luminous, and material of main part generally uses a kind of material of carbazole compound (as CBP, CDBP, TCTA, mCP).The phosphorescent coloring that is entrained in the material of main part is the metal organic complex of jaundice light, as (t-bt)
2Ir (acac) etc., its doping content is 1～15wt%, preferred doping content is 5～10wt%.The red fluorescence dyestuff that is entrained in simultaneously in the material of main part with phosphorescent coloring comprises DCM2, DCJTB, DCDDC etc., and its doping content is 0.1～5wt%, preferred doping content 0.6～1.5wt%.
The preferred structure of red organic electroluminescence device of the present invention is as follows:
Substrate/ITO/ hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Substrate/ITO/ hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/cathode layer
Embodiment 1:
As shown in Figure 2, hole transmission layer 31 materials of device are NPB, and the material of main part in the luminescent layer is CBP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCDDC, and electron transfer layer 33 materials are BPhen, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/NPB(50nm)/CBP:((t-bt)
2Ir(acac)8wt％):(DCDDC?1wt％)(15nm)/Bphen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation method is as follows:
1. utilize washing agent, deionized water, acetone soln and ethanolic solution to glass substrate and on transparent conductive film ITO carry out ultrasonic cleaning, clean the back and dry up with high pure nitrogen.Wherein the ito thin film on the glass substrate is as the anode layer of device, and the square resistance of ito thin film is 10 Ω/, and thickness is 180nm.
2. the substrate after the cleaning and drying is moved in the vacuum chamber, under oxygen is pressed to the environment of 25Pa ito glass is carried out low energy oxygen plasma preliminary treatment 5 minutes, sputtering power is～20W.
3. will after 15 minutes, move down in organic chamber through pretreated substrate cooling, be evacuated to 2 * 10 in vacuum environment
-4Below the Pa, evaporation one deck NPB is as hole transmission layer on above-mentioned ito thin film then, and the evaporation speed of NPB material is 0.1～0.2nm/s, and thickness is 50nm;
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned NPB hole transmission layer, continue evaporation doping yellow phosphorescence dyestuff (t-bt)
2The organic luminous layer of Ir (acac) and red fluorescence dyestuff DCDDC adopts the method for three source evaporations to mix, respectively with material of main part CBP, phosphorescent coloring (t-bt)
2Ir (acac), fluorescent dye DCDDC place different evaporation sources, with three film thickness monitoring instrument probes the evaporation speed of three evaporation sources is monitored respectively simultaneously at evaporation, by controlling the evaporation speed of three evaporation sources, make phosphorescent coloring, the fluorescent dye doping content in material of main part meet technological requirement.Wherein, (t-bt)
2The doping content of Ir (acac) in CBP is 8wt%, and the doping content of DCDDC in CBP is 1wt%.Total film thickness is 15nm;
5. keep above-mentioned vacuum chamber internal pressure constant, continue evaporation one deck BPhen as electron transfer layer on above-mentioned organic luminous layer, the evaporation speed of BPhen is 0.1～0.2nm/s, and thickness is 30nm;
6. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned BPhen electron transfer layer successively evaporation Mg:Ag alloy-layer, Ag layer as the cathode layer of device, wherein alloy adopts the method for double source evaporation to mix, Mg in the alloy-layer, Ag evaporation speed ratio are 10: 1, the total speed of evaporation is 1nm/s, the evaporation gross thickness is 200nm, and the evaporation speed of Ag layer is 0.1nm/s, and thickness is 10nm.
Current density-the voltage of device-brightness curve sees that the luminous efficiency-current density curve of Fig. 5, device sees Fig. 6, and luminescent spectrum and the CIE coordinate of device under different voltages seen Fig. 7.As can be seen, the bright voltage that opens of device is 3.8V, reaches high-high brightness 14163cd/m when 16.4V
2, the maximum of power efficiency is 8.2lm/W, the maximum of current efficiency is 12.6cd/A.The glow color of device is that colourity is red preferably, and the peak wavelength of luminescent spectrum is 620nm, and CIE coordinate (0.62,0.37) (0.57,0.38) when moving to 11V during by 5V is all well remaining on ruddiness chromatogram zone in big voltage range.
Embodiment 2:
As shown in Figure 3, hole transmission layer 31 materials of device are NPB, and the material of main part in the luminescent layer 32 is CBP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCJTB, and electron transfer layer 33 materials are BPhen, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/NPB(50nm)/CBP:((t-bt)
2Ir(acac)8wt％):(DCJTB?1.2wt％)(15nm)/Bphen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 3:
As shown in Figure 3, hole transmission layer 31 materials of device are NPB, and the material of main part in the luminescent layer 32 is CBP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCM2, and electron transfer layer 33 materials are BPhen, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/NPB(50nm)/CBP:((t-bt)
2Ir(acac)8wt％):(DCM2?1.5wt％)(15nm)/Bphen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 4:
As shown in Figure 4, hole injection layer 30 materials of device are CuPc, and hole transmission layer 31 materials are NPB, and the material of main part in the luminescent layer 32 is mCP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCDDC, and electron transfer layer 33 materials are TPBI, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/CuPc(10nm)/NPB(40nm)/mCP:((t-bt)
2Ir(acac)8wt％):(DCDDC?1wt％)(15nm)/TPBI(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 5:
As shown in Figure 4, hole injection layer 30 materials of device are CuPc, and hole transmission layer 31 materials are NPB, and the material of main part in the luminescent layer 32 is mCP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCJTB, and electron transfer layer 33 materials are TPBI, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass substrate/ITO/CuPc (10nm)/NPB (40nm)/mCP:((t-bt)
2Ir (acac) 8wt%): (DCJTB 1.2wt%) (15nm)/TPBI (30nm)/Mg:Ag (200nm)/Ag (10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 6:
As shown in Figure 4, hole injection layer 30 materials of device are CuPc, and hole transmission layer 31 materials are NPB, and the material of main part in the luminescent layer 32 is mCP, and phosphorescent coloring is (t-bt)
2Ir (acac), red fluorescence dyestuff are DCM2, and electron transfer layer 33 materials are TPBI, and cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass substrate/ITO/CuPc (10nm)/NPB (40nm)/mCP:((t-bt)
2Ir (acac) 8wt%): (DCM2 1.5wt%) (15nm)/TPBI (30nm)/Mg:Ag (200nm)/Ag (10nm)
The preparation of devices flow process is similar to embodiment 1.
Claims (9)
1, a kind of red organic electroluminescence device comprises substrate, anode layer, cathode layer, is arranged on the organic function layer between anode layer and the cathode layer, and organic function layer comprises luminescent layer, it is characterized in that:
1. described luminescent layer comprises material of main part and dopant material, and described dopant material is yellow phosphorescence dyestuff and red fluorescence dyestuff, and the doping content of yellow phosphorescence dyestuff is 1～15wt%, and the doping content of red phosphorescent dyestuff is 0.1～5wt%;
2. described luminescent layer is under the driving of additional power source, exciton energy is shifted to red fluorescence dyestuff to the yellow phosphorescence dyestuff by material of main part, utilize of the phosphorescence sensibilization of yellow phosphorescence dyestuff to red fluorescence dyestuff, improve the energy transfer efficiency of phosphorescence triplet excitons to the fluorescence singlet exciton, increase the utilance of fluorescence exciton radioluminescence, make device send ruddiness.
2, red organic electroluminescence device according to claim 1, it is characterized in that, described material of main part is a carbazole compound, comprise 4,4 '-two (biphenyl, 4 of carbazole-9-yl), 4 '-two (carbazole-9-yl)-2,2 '-dimethyl diphenyl, 4,4 ', 4 "-three (triphenylamine and 1 of carbazole-9-yl), and 3-two (carbazole-9-yl)-benzene.
3, red organic electroluminescence device according to claim 1 is characterized in that, described yellow phosphorescence dyestuff is iridium metals organic coordination compound two [2-(4-tertiary amine-butyl phenyl) benzo thiazolato-N, a C2 '] iridium (acetylacetonate compound).
4, red organic electroluminescence device according to claim 1, it is characterized in that, described red fluorescence dyestuff comprises 4-(dicyano methylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyrans, 4-(dicyano methylene)-2-specific base-6 (1,1,7,7-tetramethyl-julolidine-4-yl-vinyl)-and 4H-pyrans, 3-(dicyano methylene)-5,5-dimethyl-1-(4-dimethylamino-styryl) ring second is rare.
5, red organic electroluminescence device according to claim 1 is characterized in that, described organic function layer also comprises one or more of hole transmission layer, electron transfer layer, hole injection layer, electron injecting layer.
6, red organic electroluminescence device according to claim 5, it is characterized in that, described hole transport layer material is aromatic diamine compounds or aromatic triamine compounds, wherein the aromatic diamine compounds is N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine or N, N '-two (3-aminomethyl phenyl)-N, N '-two (phenyl)-benzidine or N, N '-two (naphthal-1-yl)-N, N '-two (phenyl)-2,2 '-dimethylbenzidine, the aromatic triamine compounds is two-[4-(N, N-ditolyl-amino)-phenyl] cyclohexanes.
7, red organic electroluminescence device according to claim 5, it is characterized in that, described electric transmission layer material and electron injecting layer material are metal organic complexes, pyridines, a kind of material in o-phenanthroline class oxadiazole class or the glyoxaline compound material, wherein metal organic complex comprises oxine aluminium or two (2-methyl-8-quino)-4-(phenylphenol) aluminium, pyridine compounds and their comprises three [2,4,6-trimethyl-3-(phenyl of pyridine-3-yl)]-borine, the o-phenanthroline compounds comprises 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 4,7-biphenyl-1,10-phenanthrolene ， oxadiazole electron-like transferring material is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1,3,4-oxadiazole or 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene, the imidazoles electron transport material is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene.
8, red organic electroluminescence device according to claim 5, it is characterized in that, described hole injection layer material comprises poly-(3, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid or CuPc or 4,4 ', 4 " class in (N-3-aminomethyl phenyl-N-phenyl-amino) triphenyl amine compound-three.
9, a kind of preparation method of organic electroluminescence device is characterized in that, may further comprise the steps:
1. utilize acetone, ethanolic solution and deionized water that substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. substrate is carried out the preparation of electrode layer in the vacuum evaporation chamber, described electrode comprises anode layer or cathode layer;
The substrate that 3. will prepare electrode moves in the vacuum chamber, carries out preliminary treatment under oxygen pressure ring border;
4. above-mentioned cleaning is dried up and place in the vacuum chamber through pretreated substrate, vacuumize, evaporation organic function layer on above-mentioned conductive substrates then, described organic function layer comprises luminescent layer, also comprise hole transmission layer, electron transfer layer, hole injection layer, in the electron injecting layer one or more, wherein, when the evaporation organic luminous layer, adopt the method for three source evaporations to carry out grade doping, respectively with material of main part, the yellow phosphorescence dyestuff places different evaporation sources with red fluorescence dyestuff, by controlling the evaporation speed of three evaporation sources, make yellow phosphorescence dyestuff and the red fluorescence dyestuff doping content in material of main part be respectively 1～15wt% and 0.1～5wt%;
5. keep above-mentioned vacuum chamber internal pressure constant, carry out the preparation of another electrode after the organic function layer evaporation finishes, described electrode is as the cathode layer or the anode layer of device;
6. ready-made device is sent to glove box and encapsulates, glove box is a nitrogen atmosphere.
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