CN102064282B - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
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- CN102064282B CN102064282B CN 200910234759 CN200910234759A CN102064282B CN 102064282 B CN102064282 B CN 102064282B CN 200910234759 CN200910234759 CN 200910234759 CN 200910234759 A CN200910234759 A CN 200910234759A CN 102064282 B CN102064282 B CN 102064282B
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Abstract
The invention relates to an organic electroluminescent device. In order to obtain the organic electroluminescent device with high efficiency and good color purity, an organic functional layer of the device comprises a blue luminescent layer and a phosphorescence luminescent layer, wherein the phosphorescence luminescent layer can be monolayer or multilayer; and in the blue luminescent layer, a blue light material with the high triplet-state energy level is adopted, and the blue light material can be used as a main material of a phosphorescence layer simultaneously, so that singlet-state excitons and triplet-state excitons of the blue light material can be utilized effectively. Therefore the efficiency of the device is improved, the material is saved and a process is simplified simultaneously.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device, relate in particular to a kind of structure of organic electroluminescent white light device.
Background technology
Incandescent lamp and fluorescent lamp are two kinds of light sources commonly used at present, but its energy utilization efficiency is all not high.The efficient of incandescent lamp only has 13～20lm/W, and it has caused a large amount of energy dissipations with most of electric energy energy transform into heat energy.Fluorescent lamp plays an important role the human lives with in producing, and its efficient is about 90lm/W.But fluorescent lamp also exists a series of defectives, and is as low in luminous efficiency, useful life is short, contain a large amount of ultraviolet radiations in light, thereby contains a large amount of mercury and the plumbous heavy metal that waits causes environmental pollution.So people's needs are a kind of efficiently, the new type light source of energy-saving and environmental protection.
Organic electroluminescence device (Organic Light Emitting Diode is hereinafter to be referred as OLED) is by on-load voltage between two electrodes, makes the electric field excitation light-emitting material, thereby converts electrical energy into the device of luminous energy.White OLED is because the advantage of himself uniqueness becomes planar light source of new generation.White OLED is area source, and is luminous even, do not glimmer; Lightweight, ultra-thin, can deposit on multiple substrate, as glass, plastics etc.; Have good chromaticity coordinates, can realize the high color rendering index (CRI) (CRI) etc. near 100, so White OLED has attracted people more and more to pay close attention to holding out broad prospects aspect illumination and plane display backlight.
White OLED is divided according to luminescence center, can be divided into two luminescence centers and three luminescence centers, and the former realizes by mixing two complementary colours, and as blue and yellow, orange red and sky blue, the latter often realizes by mixing red, green, blue three primary colors.White OLED is divided according to structure, can be divided into that single compound emits white light, single-shot photosphere white light, multi-luminescent layer white light, the white light of laminated construction etc.In this various structures, especially ripe with multi-luminescent layer white light structure.In multi-luminescent layer white light structure, often use red, green, blue three luminescent layers, this structure can reach higher efficient, colourity and higher color rendering index preferably.The luminescent layer of OLED device adopts the structure of material of main part dopant dye usually, and the inventor has proposed a kind of new thinking through concentrating on studies, and device efficiency is higher, the material category of use still less, cost is lower.
Certainly, be not limited to send white light after two or more blend of colors, in the situation that blend other colors, the present invention can reduce the kind of the material of use equally, raises the efficiency.
Summary of the invention
The purpose of this invention is to provide that a kind of material category is few, cost is low, the OLED device of efficient stable.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of organic electroluminescence device, comprise anode layer, cathode layer and the organic function layer between anode layer and cathode layer, organic function layer comprises blue light-emitting layer, comprise the first phosphorescent layer of material of main part and the first phosphor material, comprise the second phosphorescent layer of material of main part and the second phosphor material, and the triplet of the luminescent material of blue light-emitting layer is higher than the triplet of the first phosphorescent coloring and the second phosphorescent coloring.
The material of main part of the second phosphorescent layer is identical with the luminescent material of blue light-emitting layer.The luminescent material of blue light-emitting layer can for the complex of Be, Al, Ga, In, Zn, be preferably Bepp
2, AlmND
3, AlmmND
3, GamND
3, InmND
3, 4CzPBP.
Blue light-emitting layer also comprises the material of transport property, and its triplet can be hole transport ability matter, electric transmission character or double carriers transport property higher than the triplet of the first phosphorescent coloring and the second phosphorescent coloring.
Blue light-emitting layer is between the first phosphorescent layer and the second phosphorescent layer, and thickness is preferably 2～20nm.
Organic function layer can also comprise electron transfer layer, and the material of electron transfer layer can be identical with the material of blue light-emitting layer.
The first phosphorescent coloring can be Ir (piq)
3, Ir (piq)
2(acac), Btp
2Ir (acac), Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac), Ir (bt)
2(acac) or PtOEP.The second phosphorescent coloring can be Ir (ppy)
3, Ir (ppy)
2(acac) or Ir (mppy)
3The material of main part of the first phosphorescent layer can be NPB, TCTA, TPD, TAPC, Bepp
2, Bebq
2, BAlq, MCP or CBP.The material of main part of the second phosphorescent layer can be Bepp
2, TCTA, TAZ, TPBI or CBP.
Organic electroluminescence device produces white light.
Purpose of the present invention can also be achieved through the following technical solutions:
A kind of organic electroluminescence device, comprise anode layer, cathode layer and the organic function layer between anode layer and cathode layer, organic function layer comprises blue light-emitting layer, comprises the phosphorescent layer of material of main part and phosphorescent coloring, and the triplet of the luminescent material of blue light-emitting layer is higher than the triplet of phosphorescent coloring.
The material of main part of phosphorescent layer is identical with the luminescent material of blue light-emitting layer.The luminescent material of blue light-emitting layer is the complex of Be, Al, Ga, In, Zn, is preferably Bepp
2, AlmND
3, AlmmND
3, GamND
3, InmND
3, 4CzPBP.
Blue light-emitting layer also comprises the material of transport property, and its triplet can be hole transport ability matter, electric transmission character or double carriers transport property higher than the triplet of phosphorescent coloring.
Blue light-emitting layer is between the first phosphorescent layer and the second phosphorescent layer, and thickness is preferably 2～20nm.
Organic function layer can also comprise electron transfer layer, and the material of electron transfer layer can be identical with the material of blue light-emitting layer.
Phosphorescent coloring is selected from Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac) or Ir (bt)
2(acac).The material of main part of phosphorescent layer can be NPB, TCTA, Bepp
2, Bebq
2, BAlq, MCP or CBP.
Organic electroluminescence device produces white light.
The compound tense on the blu-ray layer material when electronics and hole, existing singlet exciton has again triplet excitons, and singlet exciton is used for radiation and sends blue-fluorescence, and triplet excitons is invalid compound in the ordinary course of things, can not be utilized.But can effectively utilize the triplet excitons of blu-ray layer in the present invention, because the triplet of the blu-ray layer material that the present invention adopts is higher than the triplet of phosphorescent coloring, so the energy of the triplet excitons of blu-ray layer can pass to phosphorescent coloring, produce radiation transistion or compound in phosphorescent coloring, make the singlet exciton of blu-ray layer and the energy of triplet excitons be fully used.Therefore, the efficient of device is higher.
The material of blue light-emitting layer can simultaneously as material of main part or the electron transport material of other luminescent layers, reduce the kind of material requested in this case.
Description of drawings
Fig. 1 is the structural representation of organic electroluminescence device.
Wherein, description of reference numerals is as follows:
The 01-substrate, 02-anode layer, 03-cathode layer, 04-hole transmission layer, 05,06, the 07-luminescent layer, 08-electron transfer layer.
Embodiment
The structural formula of the main chemical substance of the present invention is described as follows:
Table 8
Basic structure in the organic electroluminescence device that the present invention proposes as shown in Figure 1, wherein 01 be substrate, can be glass or flexible substrate, a kind of material in flexible substrate employing polyesters, polyimides compounds; 02 is anode layer, can adopt inorganic material or organic conductive polymer.Inorganic material is generally tin indium oxide (be called for short ITO), the higher metals of work function such as the metal oxide such as zinc oxide, zinc tin oxide or gold, copper, silver, preferably ITO; The organic conductive polymer is preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOTPSS), polyaniline (hereinafter to be referred as PANI); 03 is cathode layer, generally adopts the alloy of the lower metal of the work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver, or the electrode layer that alternately forms of metal and metal fluoride, and the present invention is preferably LiF layer, Al layer successively.
In Fig. 1 04 is hole transmission layer, material for example, have amino substituting group De oxadiazole compound, have amino substituent triphenyl methane compound, three grades of compounds, hydrazone compound, pyrazoline compounds, enamine compound, compound of styryl, 1,2-diphenyl ethene compounds or carbazole compound.Can also adopt the halide of bismuth metal or the oxide of bismuth metal to adulterate.
05,06,07 is three luminescent layers, can certainly be the structure of two luminescent layers.Material of main part and dyestuff to phosphorescent layer are not particularly limited.For example, Ir (ppy)
3, Ir (ppy)
2(acac) or Ir (mppy)
3Can be used as the green glow dyestuff; Ir (piq)
3, Ir (piq)
2(acac), Btp
2Ir (acac), Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac), Ir (bt)
2(acac) or PtOEP can be used as red dye; Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac) or Ir (bt)
2(acac) can be used as the gold-tinted dyestuff.
08 is electron transfer layer (nonessential), and material can be anthracene compound, phenanthrene compound, fluoranthene compound, benzo (9,10) phenanthrene compound, diazole compounds or vinylidene compound.
The below will provide some embodiment, and specific explanations technical scheme of the present invention by reference to the accompanying drawings.Should be noted that the following examples only are used for helping to understand invention, rather than limitation of the present invention.
(1) embodiment 1-7
Embodiment 1 provides a kind of White OLED device of three luminescence centers.Three luminescent layers are respectively red, blue, green light emitting layer, and the red phosphorescent luminescent layer adopts hole transport ability material of main part NPB, doping red dye Ir (piq)
3The blue luminescence layer adopts Bepp
2The main body of green phosphorescent luminescent layer adopts the material B epp identical with the blue luminescence layer
2, doping green dyestuff Ir (ppy)
3The device architecture of the present embodiment is as follows:
ITO/NPB/NPB：Ir(piq)
3/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (1)
The concrete preparation method who prepares the OLED device with above structure (1) is as follows:
1. utilize ultrasonic detergent and the ultrasonic method of deionized water boil that glass substrate 01 is cleaned, and be placed under infrared lamp and dry.As anode 02, thickness is 180nm at evaporation one deck ITO on glass;
2. above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10
-5Pa continues evaporation one deck NPB film as hole transmission layer 04 on above-mentioned anode tunic, speed is 0.1nm/s, and the evaporation thickness is 20nm;
3. the method that adopts again double source to steam is altogether carried out the evaporation doping of red phosphorescent luminescent layer 05, Ir (piq)
3Doping content in NPB is 0.7wt%, and the evaporation thickness is 15nm;
4. evaporation Bepp on the red phosphorescent luminescent layer
2Material is as blue light-emitting layer 06, and single source evaporation, thickness are 2nm; 5. evaporation green phosphorescent luminescent layer 07 on blue light-emitting layer 06, the method that adopts double source to steam is altogether carried out, Ir (ppy)
3At Bepp
2In doping content be 15wt%, the evaporation thickness is 35nm;
6. on the green phosphorescent luminescent layer, continue evaporation one deck Bepp
2Material is as electron transfer layer 08, and its evaporation speed is 0.2nm/s, and the evaporation total film thickness is 25nm;
7. last, evaporation LiF layer and Al layer are as the cathode layer 03 of device successively on above-mentioned luminescent layer, and wherein the evaporation speed of LiF layer is 0.01～0.02nm/s, and thickness is 0.7nm, and the evaporation speed of Al layer is 2.0nm/s, and thickness is 150nm.
Device architecture and the preparation method of embodiment 2-embodiment 7 are substantially the same manner as Example 1, distinguish part and are, the thickness of the blue light-emitting layer of embodiment 2-embodiment 7 is respectively 4nm, 6nm, 8nm, 10nm, 15nm, 20nm.
The OLED device architecture performance of above-described embodiment 1-embodiment 7 is as shown in table 1, and wherein, x% represents the doping percentage by weight of red light emitting layer dyestuff in material of main part, and y% represents the doping percentage by weight of green light emitting layer dyestuff in material of main part.
Table 1
| Ruddiness | Green glow | Luminous | Chromaticity coordinates |
| Device | The luminescent layer device architecture | Layer x% | Layer y% | Efficient (cd/A) | (x，y) |
| Embodiment 1 | NPB：Ir(piq) 3(15nm)/Bepp 2(2nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 21.2 | (0.44，0.45) |
| Embodiment 2 | NPB：Ir(piq) 3(15nm)/Bepp 2(4nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 20.4 | (0.43，0.44) |
| Embodiment 3 | NPB：Ir(piq) 3(15nm)/Bepp 2(6nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 19.5 | (0.40，0.42) |
| Embodiment 4 | NPB：Ir(piq) 3(15nm)/Bepp 2(8nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 19.1 | (0.39，0.39) |
| Embodiment 5 | NPB：Ir(piq) 3(15nm)/Bepp 2(10nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 18.7 | (0.37，0.37) |
| Embodiment 6 | NPB：Ir(piq) 3(15nm)/Bepp 2(15nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 18.1 | (0.36，0.36) |
| Embodiment 7 | NPB：Ir(piq) 3(15nm)/Bepp 2(20nm)/Bepp 2： Ir(ppy) 3(35nm) | 0.7 | 15 | 17.8 | (0.34，0.35) |
Comparative Examples 1
Device architecture is as follows:
ITO/NPB/NPB：Ir(piq)
3/NPB/Bepp
2：BD/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (2)
The concrete preparation method of OLED device with above structure (2) is as follows:
1. utilize ultrasonic detergent and the ultrasonic method of deionized water boil that glass substrate is cleaned, and be placed under infrared lamp and dry, as anode, thickness is 180nm at evaporation one deck ITO on glass;
2. above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10
-5Pa, evaporation one deck NPB film is as hole transmission layer on above-mentioned anode tunic, and speed is 0.1nm/s, and the evaporation thickness is 20nm;
3. the method that adopts again double source to steam is altogether carried out the evaporation doping of red phosphorescent luminescent layer, Ir (piq)
3Doping content in NPB is 0.7wt%, and the evaporation thickness is 15nm;
4. evaporation one deck NPB film is as the first barrier layer on the red phosphorescent luminescent layer, and speed is 0.1nm/s, and the evaporation thickness is 2nm;
5. the method evaporation blue light-emitting layer that adopts double source to steam altogether, BD is at Bepp
2In doping content be 5wt%, thickness is 10nm;
6. evaporation Bepp on blue light-emitting layer
2Material is as the second barrier layer, and thickness is 2nm;
7. evaporation green phosphorescent luminescent layer on blue light-emitting layer 07, the method that adopts double source to steam is altogether carried out, Ir (ppy)
3At Bepp
2In doping content be 15wt%, the evaporation thickness is 35nm;
8. on the green phosphorescent luminescent layer, continue evaporation one deck Bepp
2Material is as electron transfer layer, and its evaporation speed is 0.2nm/s, and the evaporation total film thickness is 25nm;
9. last, evaporation LiF layer and Al layer are as the cathode layer of device successively on above-mentioned luminescent layer, and wherein the evaporation speed of LiF layer is 0.01～0.02nm/s, and thickness is 0.7nm, and the evaporation speed of Al layer is 2.0nm/s, and thickness is 150nm.
Compare with embodiment 1-embodiment 7, the blue light-emitting layer of Comparative Examples 1 adopts the structure of main body dopant dye, and material of main part is Bepp
2, dyestuff is referred to as BD (structural formula is as shown in table 8).Comparative Examples 2 is identical with the device architecture of Comparative Examples 1, and 3. difference is step, the Ir of Comparative Examples 2 (piq)
3Doping content in NPB is 5wt%.The device performance of Comparative Examples 1 and Comparative Examples 2 is as shown in table 2:
Table 2
| The luminescent layer device architecture | Ruddiness layer x% | Green glow layer y% | Luminous efficiency (cd/A) | Chromaticity coordinates (x, y) | |
| Comparative Examples 1 | NPB：Ir(piq) 3(15nm)/NPB(2 nm)/Bepp 2：BD(10nm，5％)/Bepp 2(2 nm)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 5.5 | (0.18，0.27) |
| Comparative Examples 2 | NPB：Ir(piq) 3(15nm)/NPB(2 nm)/Bepp 2：BD(10nm，5％)/Bepp 2(2 nm)/Bepp 2：Ir(ppy) 3(35nm) | 5 | 15 | 8.5 | (0.34，0.38) |
As can be seen from Table 2, the device of Comparative Examples 1 is blue.The analysis reason is as follows: if with the form of blue light-emitting layer with the material of main part dopant dye, need to add the barrier layer between fluorescence coating and phosphorescent layer, this is for the singlet exciton of the material of main part of the block blue luminescent layer dyestuff transferring energy to phosphorescent layer, but pass to the blue light dyestuff, be used for launching blue-fluorescence; Allow simultaneously triplet excitons to the phosphorescent layer transferring energy as far as possible.But in Comparative Examples 1, the transport property due to the material of main part of the first phosphorescent layer and the second phosphorescent layer makes electronics and hole be easy in blue fluorescent body compound, the relative intensity of ruddiness composition and green glow composition is very weak, the device glow color is partially blue, and chromaticity coordinates is bad, and efficient is not high yet.Comparative Examples 2 has increased the concentration of red dye doping, makes the relative intensity of ruddiness composition increase, and improved chromaticity coordinates, but the relative intensity of green composition is still very weak, so whole efficiency is still very low.And the thickness on barrier layer also is not easy to control.
This structure of the present invention: the red phosphorescent luminescent layer is near anode, its main body is the hole transport ability material, and the green phosphorescent luminescent layer is near negative electrode, and its main body is the electron-transporting material, the centre is the blue fluorescent body of single compound, and blue fluorescent body need not doping.The result of above embodiment and Comparative Examples shows, this structure can access higher efficient and colorimetric purity preferably, because:
the material of main part of red phosphorescent luminescent layer is hole transport character, the material of main part of green phosphorescent luminescent material is electric transmission character, so the hole is easy to be transferred to red phosphorescent layer/blue-fluorescence bed boundary, electronics is easy to be transferred to green phosphorescent layer/blue-fluorescence bed boundary, commaterial due to the material of blue fluorescent body and the material of main part of green phosphorescent luminescent layer again, be also electric transmission character, be transferred to red phosphorescent layer/blue-fluorescence bed boundary so have portions of electronics, at the interface hole-recombination therewith, again due to the blue fluorescent body thinner thickness, the singlet exciton that electronics and hole-recombination form, cause the emission of blue-fluorescence, the triplet excitons that electronics and hole-recombination form can partly be transferred to the red phosphorescent layer that closes on, strengthen the emission of ruddiness, part is transferred to the green phosphorescent layer that closes on, strengthen the emission of green glow, make like this singlet exciton and the triplet excitons of blue fluorescent body all be fully used, finally make the efficient of white light of RGB three luminescence centers higher, color is purer.
(2) embodiment 8-14
Compare with embodiment 1-7, embodiment 8-14 has increased hole injection layer, and material of main part and the phosphorescent coloring of hole mobile material, red phosphorescent layer are also different.
The device architecture of embodiment 8-11:
ITO/HIL：HD/TAPC/TCTA：Ir(mdq)
2(acac)/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (3)
The device architecture of embodiment 12-14 is respectively:
ITO/HIL：HD/TAPC/TAPC：Ir(mdq)
2(acac)/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (4)
ITO/HIL：HD/TAPC/TPD：Ir(mdq)
2(acac)/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (5)
ITO/HIL：HD/TAPC/NPB：Ir(mdq)
2(acac)/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (6)
The device architecture of Comparative Examples 3-4:
ITO/HIL：HD/TAPC/TCTA：Ir(mdq)
2(acac)/TCTA/Bepp
2：BD/Bepp
2/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (7)
Table 3
| The luminescent layer device architecture | Orange red photosphere x% | Green glow layer y% | Luminous efficiency (cd/ A) | Chromaticity coordinates (x, y) | |
| Embodiment 8 | TCTA： Ir(mdq) 2(acac)(15nm)/Bepp 2(2nm)/Be pp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 54.4 | (0.44，0.49) |
| Embodiment 9 | TCTA： Ir(mdq) 2(acac)(15nm)/Bepp 2(6nm)/Be pp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 51.0 | (0.43，0.46) |
| Embodiment 10 | TCTA： Ir(mdq) 2(acac)(15nm)/Bepp 2(10nm)/B epp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 45.2 | (0.40，0.41) |
| Embodiment 11 | TCTA：Ir(mdq) 2(acac)(15nm)/Bepp 2(1 5nm)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 42.3 | (0.36，0.39) |
| Embodiment 12 | TAPC：Ir(mdq) 2(acac)(15nm)/Bepp 2(2n m)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 53.2 | (0.43，0.47) |
| Embodiment 13 | TPD：Ir(mdq) 2(acac)(15nm)/Bepp 2(6n m)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 48.2 | (0.42，0.44) |
| Embodiment 14 | NPB：Ir(mdq) 2(acac)(15nm)/Bepp 2(10n m)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 32.5 | (0.37，0.39) |
| Comparative Examples 3 | TCTA：Ir(mdq) 2(acac)(15nm)/TCTA(2 nm)/Bepp 2：BD(10nm，5％)/Bepp 2(2 nm)/Bepp 2：Ir(ppy) 3(35nm) | 0.7 | 15 | 9.5 | (0.18，0.27) |
| Comparative Examples 4 | TCTA：Ir(mdq) 2(acac)(15nm)/TCTA(2 nm)/Bepp 2：BD(10nm，5％)/Bepp 2(2 nm)/Bepp 2：Ir(ppy) 3(35nm) | 5 | 15 | 14.0 | (0.34，0.36) |
(3) embodiment 15-20
Embodiment 15-20 has adopted different blue light-emitting layers and electric transmission layer material, and device architecture is as follows:
ITO/HIL:HD/TAPC/TCTA:Ir (mdq)
2(acac)/blu-ray layer/Bepp
2: Ir (ppy)
3/ electron transfer layer/LiF/Al (8)
Table 4
| Device | Blu-ray layer | Electron transfer layer | Luminous efficiency (cd/A) | Chromaticity coordinates (x, y) |
| Embodiment 15 | Bepp 2(6nm) | Bebq 2(25nm) | 49 | (0.42，0.46) |
| Embodiment 16 | AlmND 3(6nm) | AlmND3(25nm) | 47 | (0.41，0.42) |
| Embodiment 17 | AlmmND 3(6nm) | AlmND3(25nm) | 45.5 | (0.40，0.42) |
| Embodiment 18 | GamND 3(6nm) | GamND3(25nm) | 43 | (0.42，0.43) |
| Embodiment 19 | InmND 3(6nm) | InmND3(25nm) | 42 | (0.43，0.43) |
| Embodiment 20 | 4CzPBP(6nm) | Bepp 2(25nm) | 41.2 | (0.41，0.42) |
(4) embodiment 21-25
Embodiment 21-23 has increased the material of transport property at blue light-emitting layer, device architecture is:
ITO/HIL：HD/TAPC/TCTA：Ir(mdq)
2(acac)/Bepp
2：TCTA/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (9)
The device architecture of embodiment 24:
ITO/HIL：HD/TAPC/TCTA：Ir(mdq)
2(acac)/Bepp
2：TAPC/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (10)
The device architecture of embodiment 25:
ITO/HIL：HD/TAPC/TCTA：Ir(mdq)
2(acac)/Bepp
2：CBP/Bepp
2：Ir(ppy)
3/Bepp
2/LiF/Al (11)
Table 5
| The blu-ray layer device architecture | Ruddiness layer x % | Green glow layer y% | Luminous efficiency (cd/ A) | Chromaticity coordinates (x, y) | |
| Embodiment 21 | TCTA：Ir(mdq) 2(acac)/Bepp 2：5％TCT A(6nm)/Bepp 2：Ir(ppy) 3 | 0.7 | 15 | 52.4 | (0.41，0.41) |
| Embodiment 22 | TCTA：Ir(mdq) 2(acac)/Bepp 2：10％TC TA(6nm)/Bepp 2：Ir(ppy) 3 | 0.7 | 15 | 52.0 | (0.40，0.41) |
| Embodiment 23 | TCTA：Ir(mdq) 2(acac)/Bepp 2：20％TC TA(6nm)/Bepp 2：Ir(ppy) 3 | 0.7 | 15 | 50.2 | (0.40，0.41) |
| Embodiment 24 | TCTA：Ir(mdq) 2(acac)/Bepp 2：10％TA | 0.7 | 15 | 52.3 | (0.39，0.42) |
| PC(6nm)/Bepp 2：Ir(ppy) 3 | |||||
| Embodiment 25 | TCTA：Ir(mdq) 2(acac)/Bepp 2：10％CB P(6nm)/Bepp 2：Ir(ppy) 3 | 0.7 | 15 | 53.1 | (0.39，0.39) |
If blu-ray layer is electric transmission character, as embodiment 8-14, Bepp
2Itself be electric transmission character, electronics and hole major part are compound at red/blue edge face.Embodiment 21-25 has increased the material TCTA of hole transport character or the CBP of TAPC or double carriers transport property in blu-ray layer, the zone of electronics and hole-recombination can be widened, blue/as greenly to have at the interface more electron-hole recombinations luminous, compound probability can be improved, the efficient of resulting devices is improved, and the stability of color can be better.
Simultaneously, after blu-ray layer added the material of transport property, exciton was not only at Bepp
2Upper formation, also can form on transferring material, because transferring material does not participate in luminous, and the triplet of transferring material is higher than ruddiness phosphorescent coloring and green glow phosphorescent coloring, so ruddiness phosphorescent coloring and green glow phosphorescent coloring around the exciton that forms on transferring material can pass to energy make the energy transmission more effective.
In order to reach the balance of both hole and electron transmission, can add according to the position of the transport property of blue light material and blu-ray layer the material of different transport properties.
(5) embodiment 26-28
Embodiment 26-embodiment 28 is with Bepp
2As the material of main part of ruddiness layer, the green glow layer is near anode simultaneously; The ruddiness layer is near negative electrode; Blu-ray layer is positioned at the centre of three luminescent layers.The device architecture of embodiment 26-embodiment 28 is all formula (12), and the thickness of blue light-emitting layer is followed successively by 2nm, 6nm, 10nm.
ITO/NPB/TCTA：Ir(ppy)
3/Bepp
2/Bepp
2：Ir(piq)
3/Bepp
2/LiF/Al (12)
Table 6
| The luminescent layer device architecture | Ruddiness layer x % | Green glow layer y% | Luminous efficiency (cd/A) | Chromaticity coordinates (x, y) | |
| Embodiment 26 | TCTA：Ir(ppy) 3(12nm)/Bepp 2(2nm)/Bepp 2： Ir(piq) 3(18nm) | 1 | 10 | 19.0 | (0.42，0.43) |
| Embodiment 27 | TCTA：Ir(ppy) 3(12nm)/Bepp 2(6nm)/Bepp 2： Ir(piq) 3(18nm) | 1 | 10 | 18.0 | (0.39，0.40) |
| Embodiment 28 | TCTA：Ir(ppy) 3(12nm)/Bepp 2(10nm)/Bepp 2： Ir(piq) 3(18nm) | 1 | 10 | 17.5 | (0.37，0.38) |
As can be seen from Table 6, Bepp
2Can do the material of main part of ruddiness layer equally, and the green glow layer can be positioned at also near anode one side.
(6) embodiment 29-32
Embodiment 29-32 is the white light parts of two luminescence centers.The device architecture of embodiment 29-31 is all formula (13), and the device architecture of embodiment 32 is formula (14), performance of devices such as table 7.
ITO/NPB/Bepp
2/Bepp
2：Ir(bt)
2(acac)(35nm)/Bepp
2/LiF/Al (13)
ITO/NPB/Bepp
2/Bebq
2：Ir(bt)
2(acac)(35nm)/Bepp
2/LiF/Al (14)
Table 7
| The luminescent layer device architecture | Blu-ray layer thickness | Gold-tinted layer doping content y% | Luminous efficiency (cd/ A) | Chromaticity coordinates (x, y) | |
| Embodiment 29 | Bepp 2(4nm)/Bepp 2：Ir(bt) 2(acac)(35nm) | 4nm | 0.7 | 23.0 | (0.36，0.37) |
| Embodiment 30 | Bepp 2(6nm)/Bepp 2：Ir(bt) 2(acac)(35nm) | 6nm | 0.7 | 22.5 | (0.34，0.36) |
| Embodiment 31 | Bepp 2(10nm)/Bepp 2：Ir(bt) 2(acac)(35nm) | 10nm | 0.7 | 22.0 | (0.34，0.35) |
| Embodiment 32 | Bepp 2(6nm)/Bebq 2：Ir(bt) 2(acac)(35nm) | 6nm | 0.7 | 21.1 | (0.35，0.36) |
Although the present invention discloses as above with preferred embodiment; yet it is not to limit the present invention; anyly be familiar with this technology personage; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations; therefore, protection scope of the present invention is as the criterion when the scope of the claims with application defines.
Claims (19)
1. an organic electroluminescence device, comprise anode layer, cathode layer and the organic function layer between anode layer and cathode layer, and organic function layer comprises:
(1) blue light-emitting layer;
(2) first phosphorescent layer comprise material of main part and the first phosphorescent coloring;
(3) second phosphorescent layer comprise material of main part and the second phosphorescent coloring;
It is characterized in that,
(1) triplet of the luminescent material of blue light-emitting layer is higher than the triplet of the first phosphorescent coloring and the second phosphorescent coloring;
(2) luminescent material of described blue light-emitting layer is the complex of Al, Ga, In, Zn; Or described blue light-emitting layer also comprises the material of transport property, and the triplet of the material of described transport property is higher than the triplet of the first phosphorescent coloring and the second phosphorescent coloring.
2. organic electroluminescence device according to claim 1, is characterized in that, the luminescent material of described blue light-emitting layer is AlmND
3, AlmmND
3, GamND
3, InmND
3, 4CzPBP.
3. organic electroluminescence device according to claim 1, is characterized in that, the material of described transport property is hole transport character, electric transmission character or double carriers transport property.
4. organic electroluminescence device according to claim 1, is characterized in that, described blue light-emitting layer is between the first phosphorescent layer and the second phosphorescent layer.
5. organic electroluminescence device according to claim 4, is characterized in that, the thickness of described blue light-emitting layer is 2 ~ 20nm.
6. organic electroluminescence device according to claim 1, is characterized in that, described organic function layer also comprises electron transfer layer, and the material of electron transfer layer is identical with the material of blue light-emitting layer.
7. organic electroluminescence device according to claim 1, is characterized in that, described the first phosphorescent coloring is selected from Ir (piq)
3, Ir (piq)
2(acac), Btp
2Ir (acac), Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac), Ir (bt)
2(acac) or PtOEP.
8. organic electroluminescence device according to claim 1, is characterized in that, described the second phosphorescent coloring is selected from Ir (ppy)
3, Ir (ppy)
2(acac) or Ir (mppy)
3
9. organic electroluminescence device according to claim 1, is characterized in that, the material of main part of described the first phosphorescent layer is selected from NPB, TCTA, TPD, TAPC, Bepp
2, Bebq
2, BAlq, MCP or CBP.
10. organic electroluminescence device according to claim 1, is characterized in that, the material of main part of described the second phosphorescent layer is selected from Bepp
2, TCTA, TAZ, TPBI or CBP.
11. organic electroluminescence device according to claim 1 is characterized in that, described organic electroluminescence device produces white light.
12. an organic electroluminescence device comprises anode layer, cathode layer and the organic function layer between anode layer and cathode layer, and organic function layer comprises:
(1) blue light-emitting layer;
(2) phosphorescent layer comprises material of main part and phosphorescent coloring;
It is characterized in that,
(1) triplet of the luminescent material of blue light-emitting layer is higher than the triplet of phosphorescent coloring;
(2) luminescent material of described blue light-emitting layer is the complex of Al, Ga, In, Zn; Or described blue light-emitting layer also comprises the material of transport property, and the triplet of the material of described transport property is higher than the triplet of phosphorescent coloring.
13. organic electroluminescence device according to claim 12 is characterized in that, the luminescent material of described blue light-emitting layer is AlmND
3, AlmmND
3, GamND
3, InmND
3, 4CzPBP.
14. organic electroluminescence device according to claim 12 is characterized in that, the material of described transport property is hole transport character, electric transmission character or double carriers transport property.
15. organic electroluminescence device according to claim 12 is characterized in that, the thickness of described blue light-emitting layer is 2nm ~ 20nm.
16. organic electroluminescence device according to claim 12 is characterized in that, described organic function layer also comprises electron transfer layer, and the material of electron transfer layer is identical with the material of blue light-emitting layer.
17. organic electroluminescence device according to claim 12 is characterized in that, the phosphorescent coloring of described phosphorescent layer is selected from Ir (MDQ)
2(acac), Ir (DBQ)
2(acac), Ir (fbi)
2(acac), Ir (2-phq)
3, Ir (2-phq)
2(acac) or Ir (bt)
2(acac).
18. organic electroluminescence device according to claim 12 is characterized in that, the material of main part of described phosphorescence luminescent layer is selected from NPB, TCTA, Bepp
2, Bebq
2, BAlq, MCP or CBP.
19. organic electroluminescence device according to claim 12 is characterized in that, described organic electroluminescence device produces white light.
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| CN108288678B (en) * | 2018-03-29 | 2023-12-01 | 佛山科学技术学院 | Double blue light layer hybridization white light organic electroluminescent device |
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