CN102214798B - White light organic electroluminescent device and manufacturing method thereof - Google Patents
White light organic electroluminescent device and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a white light organic electroluminescent device which comprises a substrate, an anode layer, a cathode layer and an organic functional layer which is arranged between the anode layer and a cathode layer; the organic functional layer comprises a hole injection layer, a hole transmission and exciton blocking layer, a blue phosphorescence luminescent layer, a spacing layer, acomplementary phosphorescence luminescent layer and an electronic transmission layer; and the triplet state energy level of the hole transmission and exciton blocking layer is not less than that of the main material in the blue phosphorescence luminescent layer, the lowest unoccupied molecular orbit energy level of the spacing layer is higher than that of a blue phosphorescence luminescent material, and the triplet state energy level of the spacing layer is not less than that of the main material in a blue light emitting layer. By using the device, defects in the prior art are overcome, the performances and color stability under high current density of the device are improved, an efficient, stable and phosphorescence white light device is obtained, the cost of raw materials is lowered, and the device is more suitable for industrial production in large scale.
Description
Technical field
The present invention relates to the organic electroluminescence device technical field, be specifically related to a kind of white light organic electroluminescent device and preparation method thereof.
Background technology
White light organic electroluminescent device is as solid light source, because preparation technology is simple, cost of manufacture is low, can realize large area light emitting, ultra-thin, flexible, material source extensively and the advantage such as environmental protection, showing and lighting field has obtained people's attention.Through the development of two more than ten years, organic electroluminescence device performance and theoretical research have all obtained considerable progress.Various monochromatic light emitters part technology reach its maturity, and device performance constantly is improved, and have had commercially produced product to come out.Because the demand to the panchromatic demonstration of organic electroluminescent and solid state lighting grows with each passing day, the performance that improves white organic light emitting diode has become one of the focus direction in organic light emission field with the research of satisfying application demand.
Divide from the angle of material, the preparation method of white light organic electroluminescent device comprises based on three kinds of methods such as full fluorescence, full phosphorescence, the mixing of phosphorescence fluorescence.White light organic electroluminescent device based on full phosphorescence can utilize excited singlet and triplet excitons simultaneously, and internal quantum efficiency can reach 100% in theory, therefore adopts the device of full phosphor material to be studied widely because having higher efficient.Luminescent layer in the present electrophosphorescence device has mostly adopted the Subjective and Objective structure, namely usually the phosphorescence luminescent substance is incorporated in the host matrix as object, forms the luminescent layer of Subjective and Objective structure.Because there is interaction in some organic dyestuff when high concentration, generate easily dimer or polymer and produce that concentration is broken goes out, also might make the dye molecule crystallization simultaneously, thereby luminous efficiency is sharply reduced.Therefore, it is entrained in the host material of higher exciton energy, the substrate molecule that available energy transmission realization is excited shifts to the energy of dye molecule, thereby realizes the luminous of dye molecule.But a significant deficiency of electrophosphorescence device is that how avoiding triplet state-triplet excitons quenching effect is one of ultimate challenge of phosphorescence device because the triplet excitons quenching effect makes device efficiency increase and reduce rapidly with current density.Simultaneously colourity variation also is a key factor that affects the white light parts luminescent properties, usually cause the reason of device chromaticity coordinates displacement to have following several: the firstth, the dyestuff of broad stopband is easier being excited under high operating voltage, then causes easily the device chromaticity coordinates to raise with operating voltage blue shift occurs; The secondth, it is saturated that the dyestuff of low concentration doping produces absorption easily; At last a kind of is the problem of multilayer device charge carrier compound interface displacement, and this mainly is because the different institutes of the mobility in electronics, hole cause that the displacement of charge carrier compound interface is the main cause that causes the displacement of multi-luminescent layer device chromaticity coordinates to occur.These factors have all directly caused device commercialization difficulty.
At present, the efficient of white light parts improves greatly, but in the research of white light electrophosphorescence, how to improve performance and the color stability of the device focus that be still research of device under high current density.And in the research work of having delivered, the work that can solve simultaneously these two aspects restraining factors rarely has report.Given this, the present invention is entrained in blue phosphorescent and complementary phosphorescent light-emitting materials respectively in the material of main part with different carrier transmission performances, injection with equilibrium carrier, widen Carrier composite, suppress the exciton cancellation, the higher triplet of host matrix can effectively be limited in exciton in the luminescent layer simultaneously, makes device can cause to effectively utilize electricity all excitons of generation, internal quantum efficiency reaches 100%, thereby obtains efficient white light emission; By between two luminescent layers, introducing the broad stopband wall to regulate charge carrier and the distribution of exciton between luminescent layer, effectively suppressed burying in oblivion of triplet state-triplet state, exciton-polaron, elimination is because of the radiationless energy composite energy loss that exciton diffusion causes, obtains under high current density almost negligible high efficiency phosphorescent white light parts of excellent performance and look drift.
Summary of the invention
Problem to be solved by this invention is: how a kind of white light organic electroluminescent device and preparation method thereof is provided, this device has overcome existing defective in the prior art, device performance and color stability under high current density have been improved, obtain efficient, stable phosphorescence white light parts, reduced cost of material, large-scale industrialized production preferably.
Technical problem proposed by the invention is to solve like this: a kind of white light organic electroluminescent device is provided, comprise substrate, anode layer, cathode layer and be arranged on anode layer and cathode layer between organic function layer, described organic function layer comprises hole injection layer, hole transport hold concurrently exciton barrier-layer, blue phosphorescent luminescent layer, wall, complementary phosphorescence luminescent layer and electron transfer layer, it is characterized in that:
1. the hold concurrently triplet of exciton barrier-layer of described hole transport is not less than the triplet of material of main part in the blue phosphorescent luminescent layer, makes exciton can effectively be limited in blue light-emitting layer, improves the utilance of exciton radiative recombination;
2. the lowest unoccupied molecular orbital energy level of described wall is higher than the lowest unoccupied molecular orbital energy level of blue phosphorescent luminescent material, perhaps described wall the highest is occupied the highest molecular orbital energy level that is occupied that molecular orbital energy level is higher than complementary phosphorescent light-emitting materials, be conducive to control charge carrier and the distribution of exciton between two luminescent layers, so that the exciton recombination zone territory does not change with the variation of voltage, guaranteed the color stability of device; Simultaneously effectively suppress burying in oblivion of triplet state-triplet state, exciton-polaron, improved the performance of device under high current density;
3. the triplet of described wall is not less than the triplet of material of main part in the blue light-emitting, avoids exciton to cause radiationless energy composite energy loss to Yellow luminous regional diffusion by blueness, has improved the efficient of device;
4. the material of main part of described blue phosphorescent luminescent layer has strong cavity transmission ability, the material of main part of complementary phosphorescence luminescent layer has strong electron transport ability, is conducive to the injection of equilibrium carrier, widens the recombination region of charge carrier, suppress the exciton cancellation, improve performance of devices.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of described hole injection layer is poly-(3, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or CuPc (CuPc) or 4,4 ', 4 " a kind of in the compound such as (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA)-three.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the hold concurrently material of exciton barrier-layer of described hole transport comprises carbazole compound or aromatic triamine compounds, wherein carbazole compound is 4,4 '; 4 "-three (triphenylamine (TCTA) of carbazole-9-yl), the aromatic triamine compounds is two-[4-(N, N-ditolyl-amino)-phenyl] cyclohexanes (TAPC).
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, blue light dyestuff in the described blue phosphorescent luminescent layer is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium (Firpic), two (2,4-difluorobenzene pyridine) four (1-pyrazoles) boric acid complex of iridium (FIr6), three ((3,5-, two fluoro-4-cyanophenyls) pyridine) complex of iridium (FCNIr), three (N-dibenzofurans-N '-methylimidazole) complex of iridium [Ir (dbfmi)], two [3,5-two (2-pyridine)-1,2, the 4-triazole] platinum complex [Pt (ptp)
2] one or more.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of main part of described blue phosphorescent luminescent layer is carbazole compound 4,4 '-two (carbazole-9-yl)-2,2 '-dimethyl diphenyl (CDBP), 9,9 '-(1,3-phenyl)-9H-carbazole (mCP), 4,4 ', 4 " (the triphenylamine (TCTA) of carbazole-9-yl)-three.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of described wall comprises carbazole compound or organosilicon compound, wherein carbazole compound is 4,4 '; 4 "-three (triphenylamines (TCTA) of carbazole-9-yl), 9,9 '-(1, the 3-phenyl)-and 9H-carbazole (mCP), organosilicon compound is Isosorbide-5-Nitrae-two (triphenylsilyl) benzene (UGH2), 1,3-two (triphenylsilyl) benzene (UGH3) etc.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, luminescent material in the described complementary phosphorescence luminescent layer comprises yellow phosphorescence dyestuff iridium metals organic coordination compound two [2-(4-tertiary amine-butyl phenyl) benzo thiazolato-N, C2 '], and iridium (acetylacetonate compound) [(t-bt)
2Ir (acac)], iridium (acetylacetonate compound) is [(bt) for two (2-phenyl benzo thiazolato-N, C2 ')
2Ir (acac)] or green phosphorescent dye Novel iridium metal organic complex two (1,2-biphenyl-1H-benzisoxa pyrazoles) iridium (acetylacetonate compound) [(pbi)
2Ir (acac)], iridium (acetylacetonate compound) is [(tpbi) for two (4-tertiary amine-butyl-1-phenyl-1H-benzimidazolato-N, C2 ')
2Ir (acac)].
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, material of main part in the described complementary phosphorescence luminescent layer is pyridines, a kind of in o-phenanthroline class oxadiazole class or the glyoxaline compound material, wherein pyridine compounds and their comprises three [2,4,6-trimethyl-3-(phenyl of pyridine-3-yl)]-borine (3TPYMB), the o-phenanthroline compounds is 4,7-biphenyl-1,10-phenanthrolene (BPhen) oxadiazole compounds is 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene (OXD-7), glyoxaline compound is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBI).
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of described electron transfer layer is a kind of material in metal organic complex, pyridines, o-phenanthroline Lei, 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 compounds 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), glyoxaline compound is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene (TPBI).
According to white light organic electroluminescent 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, 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; The material of described anode layer 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 the 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 white light organic electroluminescent device is provided, it is characterized in that, may further comprise the steps:
1. in multi-solvents, substrate is cleaned;
2. substrate is carried out the preparation of electrode layer in the vacuum evaporation chamber, described electrode layer comprises anode layer or cathode layer;
The substrate that 3. will prepare electrode moves in the vacuum chamber, carries out preliminary treatment;
4. above-mentioned cleaning is dried up and place in the vacuum chamber through pretreated substrate, vacuumize, then evaporation organic function layer successively on above-mentioned conductive substrates, described organic function layer comprises hole injection layer, hole transport hold concurrently exciton barrier-layer, blue phosphorescent luminescent layer, wall, complementary phosphorescence luminescent layer and electron transfer layer, wherein: the hold concurrently triplet of exciton barrier-layer of described hole transport is not less than the triplet of material of main part in the blue phosphorescent luminescent layer, makes exciton can effectively be limited in blue light-emitting layer; The lowest unoccupied molecular orbital energy level of described wall is higher than the lowest unoccupied molecular orbital energy level of blue phosphorescent luminescent material, perhaps described wall the highest is occupied the highest molecular orbital energy level that is occupied that molecular orbital energy level is higher than complementary phosphorescent light-emitting materials, can control the distribution between two luminescent layers of charge carrier and exciton, so that the exciton recombination zone territory does not change with the variation of voltage, suppress simultaneously burying in oblivion of triplet state-triplet state, exciton-polaron; The triplet of described wall is not less than the triplet of material of main part in the blue light-emitting, can avoid exciton to cause radiationless compound by blueness to Yellow luminous regional diffusion; The material of main part of described blue phosphorescent luminescent layer has strong cavity transmission ability, the material of main part of complementary phosphorescence luminescent layer has the strong electronic transmission performance hole barrier ability of holding concurrently, the recombination region of charge carrier is widened in injection that can equilibrium carrier, suppresses the exciton cancellation;
5. after the organic function layer evaporation finishes, carry out the preparation of another electrode layer, described electrode layer is as cathode layer or the anode layer of device;
6. after the device for preparing being sent to glove box and encapsulating, carry out performance test.
The white light organic electroluminescent device that the present invention proposes has the following advantages:
The present invention is entrained in respectively in the material of main part with different carrier transmission performances injection with equilibrium carrier with blue phosphorescent and complementary phosphorescent light-emitting materials, widened the exciton recombination zone territory, the higher triplet of material of main part is limited in exciton in the luminescent layer simultaneously, make device can effectively utilize all excitons that electricity causes generation, improved the efficient of device; By between two luminescent layers, introducing the broad stopband wall with the distribution in luminescent layer of equilibrium carrier, exciton, effectively suppressed burying in oblivion of triplet state-triplet state, exciton-polaron, eliminate the radiationless energy composite energy loss that causes because of exciton diffusion, obtained under high current density almost negligible high-performance phosphorescence white light parts of excellent performance and look drift; Two large outstanding problems of the progress of current obstruction phosphorescence white-light electroluminescence device have been solved.
Description of drawings
Fig. 1 is organic electroluminescence device structural representation provided by the present invention;
Fig. 2 is embodiment 1 provided by the present invention, 2,3,4,5,7,9,11 structural representation;
Fig. 3 is embodiment 6 provided by the present invention, 8,10,12 structural representation;
Fig. 4 is the luminescent spectrum of OLEDs under different voltages of embodiment 1 among the present invention;
Fig. 5 is the OLEDs efficient-brightness curve of embodiment 1 among the present invention;
Wherein, 1, substrate, 2, anode layer, 3, organic function layer, 30, hole injection layer, the 31 hole transport exciton barrier-layer of holding concurrently, 32, the blue phosphorescent luminescent layer, 33, wall, 34, complementary phosphorescence luminescent layer, 35, electron transfer layer, 4, cathode layer, 5, power supply.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
The invention provides a kind of white light organic electroluminescent device, as shown in Figure 1 and Figure 2, 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 the hole transport exciton barrier-layer 31 of holding concurrently, blue phosphorescent luminescent layer 32, wall 33, complementary phosphorescence luminescent layer 34, electron transfer layer 35, device is luminous under the driving of additional power source 5.
As 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, organic function layer 3 is between anode layer 2 and cathode layer 4, organic function layer 3 comprises hole injection layer 30, the hole transport exciton barrier-layer 31 of holding concurrently, blue phosphorescent luminescent layer 32, wall 33, complementary phosphorescence luminescent layer 34, electron transfer layer 35, device is luminous under the driving of additional power source 5.
Some organic material title materials that relate in this specification and the abbreviation of molecular formula and full name list such as following table:
White light organic electroluminescent device Anodic layer 2 among the present invention adopts inorganic, metal oxide (such as ITO usually, ZnO etc.), organic conductive polymer (such as PEDOT:PSS, PANI etc.) or high-work-function metal material (such as gold, copper, silver, platinum etc.).
Hole transport exciton barrier-layer 31 materials of holding concurrently have stronger hole transport performance and higher triplet in the white light organic electroluminescent device among the present invention, exciton can be limited in the blue phosphorescent luminescent layer, comprise carbazole compound or aromatic triamine compounds, a kind of as in the materials such as TCTA, TAPC, the present invention is preferably TAPC.
The blue phosphorescent dye selection of blue phosphorescent luminescent layer 32 two (4 in the white light organic electroluminescent device among the present invention, 6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium (Firpic) or two (2,4-difluorobenzene pyridine) four (1-pyrazoles) boric acid complex of iridium (FIr6).
The material of main part of blue phosphorescent luminescent layer 32 is carbazole compound CDBP, mCP, TCTA in the white light organic electroluminescent device among the present invention.The present invention is preferably mCP.
The material of the white light organic electroluminescent device intermediate interlayer 33 among the present invention can be regulated charge carrier and the distribution of exciton in luminescent layer, its lowest unoccupied molecular orbital energy level is higher than the lowest unoccupied molecular orbital energy level of blue phosphorescent luminescent material, perhaps it the highlyest is occupied the highest molecular orbital energy level that is occupied that molecular orbital energy level is higher than complementary phosphorescent light-emitting materials, comprises carbazole compound mCP, TCTA or organosilicon compound UGH2, UGH3.
The material of the complementary phosphorescence luminescent layer 34 of the white light organic electroluminescent device among the present invention is selected yellow phosphorescence dyestuff iridium metals organic coordination compound two [2-(4-tertiary amine-butyl phenyl) benzo thiazolato-N, C2 '], and iridium (acetylacetonate compound) [(t-bt)
2Ir (acac)], perhaps iridium (acetylacetonate compound) is [(tpbi) for green phosphorescent dye Novel iridium metal organic complex two (4-tertiary amine-butyl-1-phenyl-1H-benzimidazolato-N, C2 ')
2Ir (acac)].
The material of main part of the complementary phosphorescence luminescent layer 34 of white light organic electroluminescent device among the present invention has stronger electron transport ability, for pyridines (such as 3TPYMB), o-phenanthroline class (such as a kind of material in BPhen), oxadiazole class (such as OXD-7) or imidazoles (such as the TPBI) compound-material.
The material of electron transfer layer 35 is that metal organic complex is (such as Alq in the white light organic electroluminescent device among the present invention
3, BAlq), pyridines (such as 3TPYMB), o-phenanthroline class be (such as a kind of material in BCP, BPhen), oxadiazole class (such as OXD-7) or imidazoles (such as the TPBI) compound-material.
The material of cathode layer 4 can be the alloy firm of the lower metallic film of the work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver in the white light organic electroluminescent device among the present invention, and the present invention is preferably Mg:Ag alloy-layer, Ag layer or LiF layer successively, Al layer successively.
The preferred structure of white light organic electroluminescent device of the present invention is as follows:
Substrate/ITO/ hole transport exciton barrier-layer/blue phosphorescent luminescent layer/wall/complementary phosphorescence luminescent layer/electron transfer layer/cathode layer of holding concurrently
Substrate/ITO/ hole injection layer/hole transport exciton barrier-layer/blue phosphorescent luminescent layer/wall/complementary phosphorescence luminescent layer/electron transfer layer/cathode layer of holding concurrently
Embodiment 1:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, and wall 33 is selected broad-band gap hole transport shaped material mCP, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:Firpic(20nm)/mCP(5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/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, dries up with high pure nitrogen after cleaning.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/sq, and thickness is 180nm.
2. the substrate after the cleaning and drying is moved in the vacuum chamber, under oxygen is pressed as the environment of 25Pa ito glass is carried out low energy oxygen plasma preliminary treatment 5 minutes, sputtering power is～20W.
3. will under high vacuum environment, carry out through pretreated substrate the evaporation of organic film, according to hole transport on the device architecture evaporation hold concurrently exciton barrier-layer TAPC, blue phosphorescent luminescent layer mCP:Firpic, wall mCP, complementary phosphorescence luminescent layer BPhen:(t-bt)
2Ir (acac), electron transfer layer BPhen, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
4. finish the preparation of laggard row metal electrode at the organic layer evaporation.Its air pressure is 3 * 10
-3Pa, evaporation speed is 1nm/s, Mg in the alloy: the Ag ratio is 10: 1, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 6. current-voltage-light characteristic of test component, and test component.
Embodiment 2:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, and wall 33 is selected broad-band gap hole transport shaped material mCP, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:Firpic(20nm)/mCP(5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 3:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, and wall 33 is selected broad-band gap hole transport shaped material mCP, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:FIr6(20nm)/mCP(5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 4:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, and wall 33 is selected broad-band gap hole transport shaped material mCP, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:FIr6(20nm)/mCP(5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 5:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, and wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:Firpic(20nm)/UGH2(0.5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 6:
As shown in Figure 3, the material of the hole injection layer 30 of device is m-MTDATA, the hold concurrently material of exciton barrier-layer 31 of hole transport is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, the material of electron transfer layer 35 is BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/m-MTDATA(10nm)/TAPC(20nm)/mCP:Firpic(20nm)/UGH2(0.5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/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, dries up with high pure nitrogen after cleaning.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/sq, and thickness is 180nm.
2. the substrate after the cleaning and drying is moved in the vacuum chamber, under oxygen is pressed as the environment of 25Pa ito glass is carried out low energy oxygen plasma preliminary treatment 5 minutes, sputtering power is～20W.
3. will under high vacuum environment, carry out through pretreated substrate the evaporation of organic film, according to hole injection layer m-MTDATA, hole transport on the device architecture evaporation hold concurrently exciton barrier-layer TAPC, blue phosphorescent luminescent layer mCP:Firpic, wall UGH2, complementary phosphorescence luminescent layer BPhen:(t-bt)
2Ir (acac), electron transfer layer BPhen, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
4. finish the preparation of laggard row metal electrode at the organic layer evaporation.Its air pressure is 3 * 10
-3Pa, evaporation speed is 1nm/s, Mg in the alloy: the Ag ratio is 10: 1, evaporation speed and thickness are by near the film thickness gauge monitoring that is installed in the substrate.
5. ready-made device is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The luminescent spectrum parameter of the 6. current-voltage-light characteristic of test component, and test component.
Embodiment 7:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, and wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, the material of electron transfer layer 35 is BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:Firpic(20nm)/UGH2(0.5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 8:
As shown in Figure 3, the material of the hole injection layer 30 of device is m-MTDATA, the hold concurrently material of exciton barrier-layer 31 of hole transport is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material Firpic doping mCP, wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/m-MTDATA(10nm)/TAPC(20nm)/mCP:Firpic(20nm)/UGH2(0.5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 6.
Embodiment 9:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, and wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, the material of electron transfer layer 35 is BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:FIr6(20nm)/UGH2(0.5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 10:
As shown in Figure 3, the material of the hole injection layer 30 of device is m-MTDATA, the hold concurrently material of exciton barrier-layer 31 of hole transport is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, the material of electron transfer layer 35 is BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/m-MTDATA(10nm)/TAPC(20nm)/mCP:FIr6(20nm)/UGH2(0.5nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 6.
Embodiment 11:
As shown in Figure 2, the hold concurrently material of exciton barrier-layer 31 of the hole transport of device is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, and wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 35 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/TAPC(30nm)/mCP:FIr6(20nm)/UGH2(0.5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 1.
Embodiment 12:
As shown in Figure 3, the material of the hole injection layer 30 of device is m-MTDATA, the hold concurrently material of exciton barrier-layer 31 of hole transport is TAPC, blue phosphorescent luminescent layer 32 is selected blue phosphorescent material FIr6 doping mCP, wall 33 is selected broad-band gap electric transmission shaped material UGH2, and complementary phosphorescence luminescent layer 34 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, the material of electron transfer layer 35 is BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.Whole device architecture is described as:
Glass/ITO/m-MTDATA(10nm)/TAPC(20nm)/mCP:FIr6(20nm)/UGH2(0.5nm)/BPhen:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation flow of device is similar to embodiment 6.
Claims (9)
1. white light organic electroluminescent device, comprise substrate, anode layer, cathode layer and be arranged on anode layer and cathode layer between organic function layer, described organic function layer comprises hole injection layer, hole transport hold concurrently exciton barrier-layer, blue phosphorescent luminescent layer, wall, complementary phosphorescence luminescent layer and electron transfer layer, it is characterized in that:
1. the hold concurrently triplet of exciton barrier-layer of described hole transport is higher than the triplet of material of main part in the blue phosphorescent luminescent layer, makes exciton can effectively be limited in blue light-emitting layer, improves the utilance of exciton radiative recombination;
2. the lowest unoccupied molecular orbital energy level of described wall is higher than the lowest unoccupied molecular orbital energy level of blue phosphorescent luminescent material, perhaps described wall the highest is occupied the highest molecular orbital energy level that is occupied that molecular orbital energy level is higher than complementary phosphorescent light-emitting materials, can control the distribution between two luminescent layers of charge carrier and exciton, so that the exciton recombination zone territory does not change with the variation of voltage, suppress simultaneously burying in oblivion of triplet state-triplet state, exciton-polaron;
3. the triplet of described wall is higher than the triplet of material of main part in the blue light-emitting, avoids exciton to cause radiationless energy composite energy loss to Yellow luminous regional diffusion by blueness;
4. the material of main part of described blue phosphorescent luminescent layer has strong cavity transmission ability, and the material of main part of complementary phosphorescence luminescent layer has strong electron transport ability, and the recombination region of charge carrier is widened in injection that can equilibrium carrier, suppresses the exciton cancellation.
2. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described hole injection layer is poly-(3, the inferior second dioxy thiophene of 4-): polystyrene-based benzene sulfonic acid or CuPc or 4,4 ', 4 " a kind of in (N-3-aminomethyl phenyl-N-phenyl-amino) triphenyl amine compound-three.
3. white light organic electroluminescent device according to claim 1, it is characterized in that, the hold concurrently material of exciton barrier-layer of described hole transport comprises carbazole compound or aromatic triamine compounds, wherein carbazole compound is 4,4 '; 4 "-three (triphenylamine of carbazole-9-yl), the aromatic triamine compounds is two-[4-(N, N-ditolyl-amino)-phenyl] cyclohexanes.
4. white light organic electroluminescent device according to claim 1, it is characterized in that, blue light dyestuff in the described blue phosphorescent luminescent layer is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium, two (2,4-difluorobenzene pyridine) four (1-pyrazoles) boric acid complex of iridium, three ((3,5-, two fluoro-4-cyanophenyls) pyridine) complex of iridium, three (N-dibenzofurans-N '-methylimidazole) complex of iridium, two [3,5-two (2-pyridine)-1,2,4-triazole] one or more of platinum complex.
5. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of main part of described blue phosphorescent luminescent layer is carbazole compound 4,4 '-two (carbazole-9-yl)-2,2 '-dimethyl diphenyl, 9,9 '-(1,3-phenyl) two-9H-carbazole or 4,4 ', 4 " (the triphenylamine of carbazole-9-yl)-three.
6. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described wall comprises carbazole compound or organosilicon compound, and wherein carbazole compound is 4,4 '; 4 "-three (triphenylamines or 9 of carbazole-9-yl), 9 '-(1,3-phenyl) two-9H-carbazole, organosilicon compound is 1,4-two (triphenylsilyl) benzene or 1,3-two (triphenylsilyl) benzene.
7. white light organic electroluminescent device according to claim 1, it is characterized in that, luminescent material in the described complementary phosphorescence luminescent layer comprises yellow phosphorescence dyestuff iridium metals organic coordination compound two [2-(4-tertiary amine-butyl phenyl) benzo thiazolato-N, C2 '] iridium (acetylacetonate compound), two (2-phenyl benzo thiazolato-N, C2 ') iridium (acetylacetonate compound) or green phosphorescent dye Novel iridium metal organic complex two (1,2-biphenyl-1H-benzisoxa pyrazoles) iridium (acetylacetonate compound) or two (4-tertiary amine-butyl-1-phenyl-1H-benzimidazolato-N, C2 ') iridium (acetylacetonate compound).
8. white light organic electroluminescent device according to claim 1 is characterized in that, the material of main part in the described complementary phosphorescence luminescent layer is a kind of in pyridines, o-phenanthroline Lei, oxadiazole class or the glyoxaline compound material; The material of described electron transfer layer is a kind of material in metal organic complex, pyridines, o-phenanthroline Lei, oxadiazole class or the glyoxaline compound material.
9. the preparation method of a white light organic electroluminescent device is characterized in that, may further comprise the steps:
1. in multi-solvents, substrate is cleaned;
2. substrate is carried out the preparation of electrode layer in the vacuum evaporation chamber, described electrode layer comprises anode layer or cathode layer;
The substrate that 3. will prepare electrode moves in the vacuum chamber, carries out preliminary treatment;
4. above-mentioned cleaning is dried up and place in the vacuum chamber through pretreated substrate, vacuumize, then at 3. evaporation organic function layer successively on the substrate of gained of step, described organic function layer comprises hole injection layer, hole transport hold concurrently exciton barrier-layer, blue phosphorescent luminescent layer, wall, complementary phosphorescence luminescent layer and electron transfer layer, wherein: the hold concurrently triplet of exciton barrier-layer of described hole transport is higher than the triplet of material of main part in the blue phosphorescent luminescent layer, make exciton can effectively be limited in blue light-emitting layer, improve the utilance of exciton radiative recombination; The lowest unoccupied molecular orbital energy level of described wall is higher than the lowest unoccupied molecular orbital energy level of blue phosphorescent luminescent material, perhaps described wall the highest is occupied the highest molecular orbital energy level that is occupied that molecular orbital energy level is higher than complementary phosphorescent light-emitting materials, can control the distribution between two luminescent layers of charge carrier and exciton, so that the exciton recombination zone territory does not change with the variation of voltage, suppress simultaneously burying in oblivion of triplet state-triplet state, exciton-polaron; The triplet of described wall is higher than the triplet of material of main part in the blue light-emitting, avoids exciton to cause radiationless energy composite energy loss to Yellow luminous regional diffusion by blueness; The material of main part of described blue phosphorescent luminescent layer has strong cavity transmission ability, and the material of main part of complementary phosphorescence luminescent layer has strong electron transport ability, and the recombination region of charge carrier is widened in injection that can equilibrium carrier, suppresses the exciton cancellation;
5. after the organic function layer evaporation finishes, carry out the preparation of another electrode layer, described electrode layer is as cathode layer or the anode layer of device;
6. after the device for preparing being sent to glove box and encapsulating, carry out performance test.
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| CN108666430A (en) * | 2017-06-23 | 2018-10-16 | 深圳市晶鸿电子有限公司 | A kind of high performance electroluminescent organic device |
| CN109309165B (en) * | 2017-07-28 | 2021-07-13 | 上海和辉光电股份有限公司 | Organic light emitting diode and organic light emitting device |
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