CN102208552A - White-light organic electroluminescent device and preparation method thereof - Google Patents
White-light organic electroluminescent device and preparation 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 arranged between the anode layer and the cathode layer, wherein the organic functional layer comprises a luminous layer; a blue phosphorescence dye is doped in the wide band gap main body matrix with hole transmission property, and a complementary phosphorescence dye is doped in the main body matrix with electron transmission and hole blocking properties, so that the hole and electrode resonance is transmitted onto the blue phosphorescence dye molecules to directly form excitonic composite luminescence; according to the hole blocking property of the complementary phosphorescence dye main body matrix, the complementary phosphorescence dye is prevented from trapping excessive hole current carriers, the luminous strength of the blue light dye is enhanced, and annihilation of excitons and polarons in the complementary phosphorescence luminous layer is inhibited at the same time, so that uniform and stable white light emission is obtained; and relatively weak blue light emission and even total quenching in the conventional white light device are solved, and the obtained phosphorescence white light device has simple structure, is easily controlled and efficient.
Description
Technical field
The present invention relates to the organic electroluminescence device technical field, be specifically related to white light organic electroluminescent device and preparation method thereof.
Background technology
With respect to monochrome devices, white light need cover whole visible region because of the width of its emission spectrum, thereby more complicated on the device architecture, so the research of white color organic electroluminescence device (WOLED) is more late than the starting of monochromatic light device.But since people (Appl.Phys.lett., 1994,64,815) such as J.Kido in 1994 have reported after the WOLED that WOLED has just caused people's extensive interest.At present, begin attracting the attention of whole world industrial circle and scientific circles as the white color organic electroluminescence device that is most widely used, development prospect is the most optimistic.The energy is saved the energy and will be become particularly important as the focus of 21 century countries in the world contention.About 2,300 hundred million dollars electric energy is arranged according to statistics now owing to illumination loses every year, therefore just more and more higher for energy-conservation requirement.Their efficient of traditional lighting source, especially incandescent lamp is very low, energy consumption is big, makes people have to seek a kind of lighting source of novel energy-conserving.White color organic electroluminescence device progresses into people's the visual field as the lighting source of a new generation, and input ratio is more in the world at present for its research.The numerous and confused semiconductor lighting engineering that proposes of a lot of countries, China also started the semiconductor lighting engineering in 2003.Because the characteristics of making of OLED device, the lighting system that some traditional lighting light fixtures (comprising inorganic LED) are difficult for realizing also becomes possibility, for example white light flat head lamp source, large tracts of land even flexibility illumination, this makes WOLED have more special advantage as the development of solid-state illumination light source.This device not only can be applied to lighting field, and can be applied to liquid crystal background light source, realize aspect such as panchromatic demonstration.Traditional LCD backlight mainly adopts cold-cathode fluorescence lamp (CCFL), though cold-cathode fluorescence lamp has good characteristic, easily cause environmental pollution because of mercurous, and color saturation is also not enough.OLED is pollution-free, the advantage of high colour gamut makes it become the first-selection of LCD product backlight of future generation.
WOLEDs commonly used generally is by the collocation of red, green, blue three primary colors or utilizes blue light and light another complementation or two kinds of long wavelengths, mixes the generation white light mutually as in gold-tinted, ruddiness, the green glow one or both.No matter adopt the sort of mode to prepare WOLEDs, the blue light composition all is indispensable.And in the full phosphorescence WOLEDs that receives much concern,, limited further developing of full phosphorescence WOLEDs because of the life-span of blue phosphorescent material itself is wanted much shorter than green and red phosphorescence material.Also there is a certain distance in present blue phosphorescent material luminous efficiency with respect to other color phosphor materials simultaneously.In currently used single-shot photosphere structure, normally red, green, blue or indigo plant, complementary dyestuff are mixed in the same host matrix altogether, owing to exist energy to shift between different dyes, shift to energy red, green dye as the blue light dyestuff, the green glow dyestuff shifts to the energy of red dye, therefore need the careful concentration of various dyestuffs of regulating to reach versicolor balance, the outgoing of ability synthesize white light, strengthened the difficulty of making, parasitic simultaneously energy loss has reduced the efficient of blue light ingredient and entire device.In the multi-luminescent layer structure, because long wavelength's dyestuff has stronger carrier capture ability with respect to the blue light dyestuff, cause recombination region mainly to concentrate in the luminescent layer of long wavelength's dyestuff, the emission that the energy delivery between the two can the cancellation blue light simultaneously, therefore in spectrum, have only very weak even do not have blue emission, finally be difficult to obtain white light.Therefore people such as Forrest (Nature 2006,440,908) by between luminescent layer, inserting electronics or hole blocking layer, to avoid the energy delivery between the luminescent layer to obtain white light, but the use of exciton barrier-layer material, be unfavorable for the transmission of charge carrier, cause the cut-in voltage of device higher, power efficiency is lower.
The quality of white light parts performance, a part are decided by selected material, are decided by the structure of device on the other hand.Therefore, in present stage blue light phosphor material progress slowly under the situation, if can design a kind of simple device architecture, do not avoid unnecessary energy delivery between blue light dyestuff and other long wavelength's dyestuffs by introducing electronics or hole blocking layer, guarantee the luminous intensity and the efficient of blue light dyestuff simultaneously, will help obtaining the phosphorescence white light organic electroluminescent device of efficient stable.Given this, the present invention is dye adulterated in having the broad-band gap host matrix of hole transport characteristic with blue phosphorescent, complementary phosphorescent coloring is entrained in has electric transmission and hold concurrently in the host matrix of hole barrier characteristic, hole, electronics are transmitted in by resonance directly form the exciton recombination luminescence on the blue phosphorescent dye molecule, avoid having improved the luminous efficiency of blue light dyestuff and entire device by the energy delivery loss of main body to the blue light dyestuff; The hole barrier characteristic of complementary phosphorescent coloring host matrix avoids complementary phosphorescent coloring to capture too much holoe carrier, helps strengthening the luminous intensity of blue light dyestuff, suppresses burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer simultaneously; The present invention obtain device architecture simple, be easy to control, efficient, stable phosphorescence white light parts.
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, the luminous efficiency and the color stability of device 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, be arranged on the organic function layer between anode layer and the cathode layer, organic function layer comprises luminescent layer, luminescent layer by the blue phosphorescent luminescent layer and can and the blue phosphorescent luminescent layer cooperation complementary phosphorescence luminescent layer that sends white light constitute, described blue phosphorescent luminescent layer comprises host matrix and blue phosphorescent dyestuff, described complementary phosphorescence luminescent layer comprises complementary host matrix and complementary phosphorescent coloring, it is characterized in that:
1. in the described blue phosphorescent luminescent layer, blue phosphorescent dyestuff the highest occupied the highest molecular orbital energy level that occupied that molecular orbital energy level is lower than host matrix, its lowest unoccupied molecular orbital energy level is not less than the lowest unoccupied molecular orbital energy level of the complementary host matrix in the complementary phosphorescence luminescent layer, hole, electronics are transmitted in by resonance directly form the exciton recombination luminescence on the blue phosphorescent dye molecule, improve the luminous efficiency of blue light dyestuff and entire device;
2. the triplet of host matrix is higher than the triplet of blue phosphorescent dyestuff in the described blue phosphorescent luminescent layer, triplet excitons can be limited on the molecule of blue phosphorescent dyestuff, avoids object to arrive the energy passback loss of main body;
3. the complementary host matrix in the described complementary phosphorescence luminescent layer has the hole barrier characteristic, can avoid complementary phosphorescent coloring to capture too much holoe carrier, can strengthen the luminous intensity of blue light dyestuff, and suppress burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer, improved the color stability and the efficient of device.
According to white light organic electroluminescent device provided by the present invention, it is characterized in that the host matrix in the described blue phosphorescent luminescent layer comprises carbazole compound 4,4 '-two (carbazole-9-yl)-2,2 '-dimethyl diphenyl (CDBP), 9,9 '-(1, the 3-phenyl) two-9H-carbazole (mCP); The blue light phosphorescent coloring is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium (Firpic), two (2,4-two fluorobenzene pyridines) four (1-pyrazoles) boric acid complex of iridium (FIr6), three ((3,5-two fluoro-4-benzene nitriles) 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, complementary host matrix in the described complementary phosphorescence luminescent layer is a pyridines, o-phenanthroline class oxadiazole class or glyoxaline compound, a kind of in the organosilicon 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), organosilicon compound is 1,4-two (triphenylsilyl) benzene (UGH2), 1,3-two (triphenylsilyl) benzene (UGH3); Described complementary phosphorescent coloring 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 the novel iridium metals organic coordination compound two of green phosphorescent dye (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)] or red phosphorescent dyestuff two-(2-benzene quinoline-N, C2 ') (acetylacetone,2,4-pentanedione) complex of iridium (PQIr).
According to white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of described hole transmission layer 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 white light organic electroluminescent device provided by the present invention, it is characterized in that, the material of described electron transfer layer is a pyridines, o-phenanthroline class oxadiazole class or glyoxaline compound, a kind of in the organosilicon 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 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; 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 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 multiple solvent, 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, evaporation organic function layer successively on above-mentioned conductive substrates then, organic function layer comprises luminescent layer, luminescent layer by the blue phosphorescent luminescent layer and can and the blue phosphorescent luminescent layer cooperation complementary phosphorescence luminescent layer that sends white light constitute, described blue phosphorescent luminescent layer comprises host matrix and blue phosphorescent dyestuff, described complementary phosphorescence luminescent layer comprises complementary host matrix and complementary phosphorescent coloring, in the described blue phosphorescent luminescent layer, blue phosphorescent dyestuff the highest occupied the highest molecular orbital energy level that occupied that molecular orbital energy level is lower than host matrix, its lowest unoccupied molecular orbital energy level is not less than the lowest unoccupied molecular orbital energy level of the complementary host matrix in the complementary phosphorescence luminescent layer, can make the hole, electronics is transmitted in by resonance and directly forms the exciton recombination luminescence on the blue phosphorescent dye molecule, improves the luminous efficiency of blue light dyestuff and entire device; The triplet of host matrix is higher than the triplet of blue phosphorescent dyestuff in the described blue phosphorescent luminescent layer, triplet excitons can be limited on the molecule of blue phosphorescent dyestuff, avoids object to arrive the energy passback loss of main body; Complementary host matrix in the described complementary phosphorescence luminescent layer has the hole barrier characteristic, can avoid complementary phosphorescent coloring to capture too much holoe carrier, can strengthen the luminous intensity of blue light dyestuff, and suppress burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer, improved the color stability and the efficient of device.
5. after the organic function layer evaporation finishes, carry out the preparation of another electrode layer, described electrode layer is as the cathode layer or the anode layer of device;
6. the device for preparing is sent to after glove box encapsulates, carries out performance test.
The white light organic electroluminescent device that the present invention proposes has the following advantages:
The present invention is dye adulterated in having the broad-band gap host matrix of hole transport characteristic with blue phosphorescent, complementary phosphorescent coloring is entrained in have electric transmission and hold concurrently in the host matrix of hole barrier characteristic, makes hole, electronics by the resonance transmission
Directly form the exciton recombination luminescence on the blue phosphorescent dye molecule, avoid having improved the luminous efficiency of blue light dyestuff and entire device by the energy delivery loss of main body to the blue light dyestuff; The hole barrier characteristic of complementary phosphorescent coloring host matrix avoids complementary phosphorescent coloring to capture too much holoe carrier, help strengthening the luminous intensity of blue light dyestuff, suppress burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer simultaneously, thereby obtain uniform and stable white light emission; The invention solves the phenomenon of the more weak relatively even complete quencher of blue light emitting in the current white light parts, so obtain device architecture simple, be easy to control, efficient, stable phosphorescence white light parts.
Description of drawings
Fig. 1 is an organic electroluminescence device structural representation provided by the present invention;
Fig. 2 is the structural representation of embodiment 1,2,3,7,8,9 provided by the present invention;
Fig. 3 is the structural representation of embodiment 4,5,6,10,11,12 provided by the present invention;
Fig. 4 is the luminescent spectrum figure of embodiment 4 among the present invention;
Fig. 5 is the current density-voltage-brightness curve of embodiment 4 among the present invention;
Fig. 6 is the efficient-brightness curve of embodiment 4 among the present invention;
Wherein, 1, substrate, 2, anode layer, 3, organic function layer, 30, hole transmission layer, 31 blue phosphorescent luminescent layers, 32, complementary phosphorescence 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 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, and organic function layer 3 is between anode layer 2 and cathode layer 4, organic function layer 3 comprises blue phosphorescent luminescent layer 31, complementary phosphorescence luminescent layer 32, electron transfer layer 33, 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, and organic function layer 3 is between anode layer 2 and cathode layer 4, and organic function layer 3 comprises hole transmission layer 30, blue phosphorescent luminescent layer 31, complementary phosphorescence luminescent layer 32, 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:
The blue phosphorescent dye selection of the white light organic electroluminescent device Smalt phosphorescence luminescent layer 31 among the present invention two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium (Firpic) or two (2,4-two fluorobenzene pyridines) four (1-pyrazoles) boric acid complex of iridium (FIr6).
The material of main part of the white light organic electroluminescent device Smalt phosphorescence luminescent layer 31 among the present invention is carbazole compound CDBP, mCP.The present invention is preferably mCP.
The material of the complementary phosphorescence luminescent layer 32 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 the novel iridium metals organic coordination compound two of green phosphorescent dye (4-tertiary amine-butyl-1-phenyl-1H-benzimidazolato-N, C2 ')
2Ir (acac)], perhaps red phosphorescent dyestuff two-(2-benzene quinoline-N, C2 ') (acetylacetone,2,4-pentanedione) complex of iridium (PQIr).
The material of main part of the complementary phosphorescence luminescent layer 32 of white light organic electroluminescent device among the present invention has stronger electric transmission and hole barrier ability, for pyridines (as 3TPYMB), o-phenanthroline class (as a kind of material in BPhen), oxadiazole class (as OXD-7), silicone based (UGH2) or imidazoles (as the TPBI) compound-material.
The material of electron transfer layer 33 is that pyridines (as 3TPYMB), o-phenanthroline class are (as a kind of material in BCP, BPhen), oxadiazole class (as OXD-7) or imidazoles (as the TPBI) compound-material in the white light organic electroluminescent device among the present invention.
The material of cathode layer 4 can be the alloy firm of the lower metallic film of 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/ blue phosphorescent luminescent layer/complementary phosphorescence luminescent layer/electron transfer layer/cathode layer
Substrate/ITO/ hole transmission layer/blue phosphorescent luminescent layer/complementary phosphorescence luminescent layer/electron transfer layer/cathode layer
Embodiment 1:
As shown in Figure 2, the blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/mCP:Firpic(20nm)/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, 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/sq, 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 under high vacuum environment, carry out the evaporation of organic film through pretreated substrate, according to device architecture evaporation blue phosphorescence luminescent layer mCP:Firpic, 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 blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/mCP:Firpic(20nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 3:
As shown in Figure 2, the blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected red phosphorescent dyestuff PQIr doping BPhen, 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/mCP:Firpic(20nm)/BPhen:PQIr(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 4:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, and blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping BPhen, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/TAPC(10nm)/mCP:Firpic(20nm)/BPhen:(t-bt)
2Ir(acac)(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/sq, 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 under high vacuum environment, carry out the evaporation of organic film through pretreated substrate, according to hole transmission layer TAPC, blue phosphorescent luminescent layer mCP:Firpic, complementary phosphorescence luminescent layer BPhen:(t-bt on the device architecture evaporation)
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 5:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, and blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping BPhen, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/TAPC(10nm)/mCP:Firpic(20nm)/BPhen:(t-bt)
2Ir(acac)(15nm)/BPhen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 4.
Embodiment 6:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, complementary phosphorescence luminescent layer 32 is selected red phosphorescent dyestuff PQIr doping BPhen, 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/TAPC(10nm)/mCP:Firpic(20nm)/BPhen:PQIr(15nm)/BPhen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 4.
Embodiment 7:
As shown in Figure 2, the blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping UGH2, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/mCP:Firpic(20nm)/UGH2:(t-bt)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 8:
As shown in Figure 2, the blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping UGH2, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/mCP:Firpic(20nm)/UGH2:(tpbi)
2Ir(acac)(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 9:
As shown in Figure 2, the blue phosphorescent luminescent layer 31 of device is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected red phosphorescent dyestuff PQIr doping UGH2, 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/mCP:Firpic(20nm)/UGH2:PQIr(15nm)/BPhen(40nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 1.
Embodiment 10:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, and blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected yellow phosphorescence dyestuff (t-bt)
2Ir (acac) doping UGH2, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/TAPC(10nm)/mCP:Firpic(20nm)/UGH2:(t-bt)
2Ir(acac)(15nm)/BPhen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 4.
Embodiment 11:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, and blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, and complementary phosphorescence luminescent layer 32 is selected green phosphorescent dye (tpbi)
2Ir (acac) doping UGH2, electron transfer layer 33 materials are BPhen, cathode layer 4 adopts Mg:Ag alloy and Ag.The entire device structrual description is:
Glass/ITO/TAPC(10nm)/mCP:Firpic(20nm)/UGH2:(tpbi)
2Ir(acac)(15nm)/BPhen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 4.
Embodiment 12:
As shown in Figure 3, the material of the hole transmission layer 30 of device is TAPC, blue phosphorescent luminescent layer 31 is selected blue phosphorescent material Firpic doping mCP, complementary phosphorescence luminescent layer 32 is selected red phosphorescent dyestuff PQIr doping UGH2, 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/TAPC(10nm)/mCP:Firpic(20nm)/UGH2:PQIr(15nm)/BPhen(30nm)/Mg:Ag(200nm)/Ag(10nm)
The preparation of devices flow process is similar to embodiment 4.
Claims (5)
1. white light organic electroluminescent device, 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, luminescent layer by the blue phosphorescent luminescent layer and can and the blue phosphorescent luminescent layer cooperation complementary phosphorescence luminescent layer that sends white light constitute, described blue phosphorescent luminescent layer comprises host matrix and blue phosphorescent dyestuff, described complementary phosphorescence luminescent layer comprises complementary host matrix and complementary phosphorescent coloring, it is characterized in that:
1. in the described blue phosphorescent luminescent layer, blue phosphorescent dyestuff the highest occupied the highest molecular orbital energy level that occupied that molecular orbital energy level is lower than host matrix, its lowest unoccupied molecular orbital energy level is not less than the lowest unoccupied molecular orbital energy level of the complementary host matrix in the complementary phosphorescence luminescent layer, hole, electronics are transmitted in by resonance directly form the exciton recombination luminescence on the blue phosphorescent dye molecule, improve the luminous efficiency of blue light dyestuff and entire device;
2. the triplet of host matrix is higher than the triplet of blue phosphorescent dyestuff in the described blue phosphorescent luminescent layer, triplet excitons can be limited on the molecule of blue phosphorescent dyestuff, avoids object to arrive the energy passback loss of main body;
3. the complementary host matrix in the described complementary phosphorescence luminescent layer has the hole barrier characteristic, can avoid complementary phosphorescent coloring to capture too much holoe carrier, can strengthen the luminous intensity of blue light dyestuff, and suppresses burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer.
2. white light organic electroluminescent device according to claim 1 is characterized in that, the host matrix in the described blue phosphorescent luminescent layer comprises carbazole compound 4,4 '-two (carbazole-9-yl)-2,2 '-dimethyl diphenyl or 9,9 '-(1, the 3-phenyl) two-9H-carbazole; The blue light phosphorescent coloring is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium, two (2,4-two fluorobenzene pyridines) four (1-pyrazoles) boric acid complex of iridium, three ((3,5-two fluoro-4-benzene nitriles) complex of iridium pyridine), three (N-dibenzofurans-N '-methylimidazole) complex of iridium or two [3,5-two (2-pyridine)-1,2,4-triazole] one or more of platinum complex.
3. white light organic electroluminescent device according to claim 1, it is characterized in that, complementary host matrix in the described complementary phosphorescence luminescent layer is a pyridines, o-phenanthroline class oxadiazole class or glyoxaline compound, a kind of in the organosilicon compound material, wherein pyridine compounds and their comprises three [2,4,6-trimethyl-3-(phenyl of pyridine-3-yl)]-borine, the o-phenanthroline compounds is 4,7-biphenyl-1, and 10-phenanthrolene oxadiazole compounds is 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene, glyoxaline compound is 1,3,5-three (N-phenyl-benzimidazolyl-2 radicals) benzene, organosilicon compound is 1,4-two (triphenylsilyl) benzene or 1,3-two (triphenylsilyl) benzene; Described complementary phosphorescent coloring 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 (the novel iridium metals organic coordination compound two (1 of acetylacetonate compound or green phosphorescent dye, 2-biphenyl-1H-benzisoxa pyrazoles) iridium (acetylacetonate compound), two (4-tertiary amine-butyl-1-phenyl-1H-benzimidazolato-N, C2 ') iridium (acetylacetonate compound) or red phosphorescent dyestuff two-(2-benzene quinoline-N, C2 ') (acetylacetone,2,4-pentanedione) complex of iridium.
4. white light organic electroluminescent device according to claim 1 is characterized in that, the material of described hole transmission layer is aromatic diamine compounds or aromatic triamine compounds; The material of described electron transfer layer is a kind of in pyridines, o-phenanthroline Lei, oxadiazole class or glyoxaline compound, the organosilicon compound material.
5. the preparation method of a white light organic electroluminescent device is characterized in that, may further comprise the steps:
1. in multiple solvent, 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 layer 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, evaporation organic function layer successively on above-mentioned conductive substrates then, organic function layer comprises luminescent layer, luminescent layer by the blue phosphorescent luminescent layer and can and the blue phosphorescent luminescent layer cooperation complementary phosphorescence luminescent layer that sends white light constitute, described blue phosphorescent luminescent layer comprises host matrix and blue phosphorescent dyestuff, described complementary phosphorescence luminescent layer comprises complementary host matrix and complementary phosphorescent coloring, in the described blue phosphorescent luminescent layer, blue phosphorescent dyestuff the highest occupied the highest molecular orbital energy level that occupied that molecular orbital energy level is lower than host matrix, its lowest unoccupied molecular orbital energy level is not less than the lowest unoccupied molecular orbital energy level of the complementary host matrix in the complementary phosphorescence luminescent layer, can make the hole, electronics is transmitted in by resonance and directly forms the exciton recombination luminescence on the blue phosphorescent dye molecule, improves the luminous efficiency of blue light dyestuff and entire device; The triplet of host matrix is higher than the triplet of blue phosphorescent dyestuff in the described blue phosphorescent luminescent layer, triplet excitons can be limited on the molecule of blue phosphorescent dyestuff, avoids object to arrive the energy passback loss of main body; Complementary host matrix in the described complementary phosphorescence luminescent layer has the hole barrier characteristic, can avoid complementary phosphorescent coloring to capture too much holoe carrier, can strengthen the luminous intensity of blue light dyestuff, and suppresses burying in oblivion of exciton-polaron in the complementary phosphorescence luminescent layer;
5. after the organic function layer evaporation finishes, carry out the preparation of another electrode layer, described electrode layer is as the cathode layer or the anode layer of device;
6. the device for preparing is sent to after glove box encapsulates, carries out performance test.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394276A (en) * | 2011-11-25 | 2012-03-28 | 中国科学院长春应用化学研究所 | Red organic light emitting diode and preparation method thereof |
| CN102496682A (en) * | 2011-11-25 | 2012-06-13 | 中国科学院长春应用化学研究所 | Blue-green organic light-emitting device and manufacture method thereof |
| CN102969455A (en) * | 2012-12-18 | 2013-03-13 | 中国科学院长春应用化学研究所 | White organic electroluminescence device and preparation method thereof |
| CN103890992A (en) * | 2011-10-19 | 2014-06-25 | E.I.内穆尔杜邦公司 | Organic electronic device for lighting |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543282A (en) * | 2003-03-17 | 2004-11-03 | ��ʽ����뵼����Դ�о��� | Light emitting element and light emitting device |
| US20100033082A1 (en) * | 2008-08-07 | 2010-02-11 | General Electric Company | Method of Manufacture of a Multi-Layer Phosphorescent Organic Light Emitting Device, and Articles Thereof |
| WO2010062643A1 (en) * | 2008-10-28 | 2010-06-03 | The Regents Of The University Of Michigan | Stacked white oled having separate red, green and blue sub-elements |
| CN101789495A (en) * | 2009-01-21 | 2010-07-28 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
-
2011
- 2011-05-20 CN CN 201110132744 patent/CN102208552A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543282A (en) * | 2003-03-17 | 2004-11-03 | ��ʽ����뵼����Դ�о��� | Light emitting element and light emitting device |
| US20100033082A1 (en) * | 2008-08-07 | 2010-02-11 | General Electric Company | Method of Manufacture of a Multi-Layer Phosphorescent Organic Light Emitting Device, and Articles Thereof |
| WO2010062643A1 (en) * | 2008-10-28 | 2010-06-03 | The Regents Of The University Of Michigan | Stacked white oled having separate red, green and blue sub-elements |
| CN101789495A (en) * | 2009-01-21 | 2010-07-28 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890992A (en) * | 2011-10-19 | 2014-06-25 | E.I.内穆尔杜邦公司 | Organic electronic device for lighting |
| CN102394276A (en) * | 2011-11-25 | 2012-03-28 | 中国科学院长春应用化学研究所 | Red organic light emitting diode and preparation method thereof |
| CN102496682A (en) * | 2011-11-25 | 2012-06-13 | 中国科学院长春应用化学研究所 | Blue-green organic light-emitting device and manufacture method thereof |
| CN102394276B (en) * | 2011-11-25 | 2014-08-27 | 中国科学院长春应用化学研究所 | Red organic light emitting diode and preparation method thereof |
| CN102496682B (en) * | 2011-11-25 | 2015-11-25 | 中国科学院长春应用化学研究所 | blue-green organic electroluminescent device and preparation method thereof |
| CN102969455A (en) * | 2012-12-18 | 2013-03-13 | 中国科学院长春应用化学研究所 | White organic electroluminescence device and preparation method thereof |
| CN102969455B (en) * | 2012-12-18 | 2015-08-05 | 中国科学院长春应用化学研究所 | White color organic electroluminescence device and preparation method thereof |
| CN108799859A (en) * | 2018-06-28 | 2018-11-13 | 镭米光学科技（宁波）有限公司 | All solid state high-brightness illuminating device |
| CN108799859B (en) * | 2018-06-28 | 2020-03-20 | 镭米光学科技（宁波）有限公司 | All-solid-state high-brightness lighting device |
| CN109192884A (en) * | 2018-08-17 | 2019-01-11 | 合肥工业大学 | The method for promoting the red phosphor OLED device service life |
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