CN101710609B - Organic white light device - Google Patents
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- CN101710609B CN101710609B CN2009101943420A CN200910194342A CN101710609B CN 101710609 B CN101710609 B CN 101710609B CN 2009101943420 A CN2009101943420 A CN 2009101943420A CN 200910194342 A CN200910194342 A CN 200910194342A CN 101710609 B CN101710609 B CN 101710609B
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Abstract
The invention relates to an organic white light device, which comprises a color conversion layer (1) for emitting red light, a substrate (2) for playing a role in supporting, a bottom electrode (3) for injecting and contacting current carriers, a first current carrier transmission layer or an exciton barrier layer (4) for injecting or transmitting or blocking the current carriers or excitons, an organic material light-emitting layer (5) for emitting blue light and green light simultaneously, a second current carrier transmission layer or an exciton barrier layer (6) for injecting or transmitting or blocking the current carriers or the excitons, and an upper electrode (7) for injecting and contacting the current carriers. The invention discloses an organic white light device which consists of the color conversion layer for emitting the red light and an organic electroluminescent device for emitting the blue light and the green light simultaneously, and can be applied to full color display and illumination.
Description
Technical field
The present invention relates to a kind of white organic light emitting diode, belong to technical field of organic electroluminescence.
Background technology
Organic electroluminescence device (Organic Light Emitting Diode; Organic Light-emitting diodes; Be called for short OLEDs) as a kind of novel flat-panel monitor and light source; Have many advantages such as active illuminating, wide visual angle, full color, flexible, high efficiency, low-power consumption, low cost concurrently, this technical field major progress is following:
1,1987, people such as Tang reported adopt the preparation of vacuum thermal evaporation film plating process, be hole transmission layer with the amine derivant, with oxine aluminium (Alq
3) be the double-decker micromolecule OLEDs (C.W.Tang and S.A.VanSlyke, Appl.Phys.Lett.51,913 (1987)) of luminescent layer;
2, nineteen ninety; People such as Burroughes have reported polymer electroluminescent device (the Polymer Light-emitting diodes of employing solution methods (solution process) preparation; Be called for short PLEDs) (H.Burroughes et al., Nature 347,539 (1990));
3,1998, people such as Baldo reported the method for utilizing the vacuum thermal evaporation plated film, the phosphorescent OLED s (M.A.Baldo et al., Nature 395,151 (1998)) that adopts the preparation of high efficiency organic phosphorescent material;
White organic light emitting diode (White OLEDs; Abbreviation WOLEDs) can be applicable to full-color demonstration and illumination; Receive people's extensive concern, realize that the method for WOLEDs is generally three looks (red, green, blue, RGB) mixing or two look (complementary colours; Like orange red, indigo plant) to mix, existing WOLEDs technical scheme mainly comprises:
A.1991 in year, people such as Tang disclose a kind of WOLEDs, constitute (United States Patent (USP) 5294870) by the organic electroluminescence device of emission blue light and the color conversion layer of transmitting green light and ruddiness;
B.1994 in year, people such as Kido have reported that luminescent layer is dispersed in the WOLEDs that electroluminescence constitutes in the polymer body material (J.Kido et al., Appl.Phys.Lett.64,815 (1994)) by three kinds of organic fluorescence materials of red, green, blue;
C.1995 in year, people such as Kido have reported the WOLEDs with three luminescent layers, and wherein each luminescent layer is launched red, green, blue electroluminescent fluorescent mixing realization white light (J.Kido et al., Science 267,1332 (1995)) respectively;
D.2002 year, people such as D ' Andrade have reported and have had bluish-green and red electroluminescent phosphorescence multi-luminescent layer WOLEDs (B.W.D ' Andrade et al., Adv.Mater.12,147 (2002));
E.2002 in year, people such as Duggal have reported a kind of WOLEDs, and yellow, orange by the polymer electroluminescent device of launching blue light and emission, as to reach ruddiness color conversion layer constitutes; Wherein the polymer light-emitting layer adopts solution methods preparation (A.Duggal et al.; Appl.Phys.Lett.80,3470 (2002), A.Duggal et al.; SID Int.Symp.Digest Tech.Papers 28 (2005)); People such as Duggal also disclose a kind of WOLEDs, constitute (Chinese invention patent application number 200310123726.6, publication number CN1520237) by launching the blue light and the organic electroluminescence device of ruddiness and the color conversion layer of transmitting green light;
F.2004 year, people such as D ' Andrade have reported that luminescent layer is entrained in the material of main part electroluminescent phosphorescence by three kinds of organic phosphorescent materials of red, green, blue and mixes and form WOLEDs (B.W.D ' Andrade et al., Adv.Mater.16,624 (2004));
G.2006 in year, people such as Sun have reported to have blue electroluminescent fluorescent and multi-luminescent layer WOLEDs (Y.R.Sun et al., Nature.440,908 (2006)) red, green electroluminescent phosphorescence;
H.2006 year; People such as Krummacher have reported that the organic electroluminescence device of emission blue light and the color conversion layer of emission gold-tinted constitute; Electroluminescence layer is dispersed in employing solution methods preparation (B.C.Krummacher in the polymer body material by the organic molecule phosphor material of blue light-emitting; Et al., Appl.Phys.Lett.88,113506 (2006));
I.2007 in year, people such as Qiu Yong disclose the WOLEDs that comprises the color conversion transport layer, and wherein the color conversion transport layer has the function (Chinese invention patent application number 200610137754.7, publication number CN1937277A) of color conversion and carrier transport concurrently.
J.2009 year; People such as Yuan Yongbo have reported a kind of micromolecule WOLEDs; Be made up of the organic electroluminescence device of emission blue light and the color conversion layer of the orange red light of emission, electroluminescence layer is entrained in the preparation of employing vacuum thermal evaporation method (Y.B.Yuan, et al. in the organic molecule material of main part by the organic molecule phosphor material of blue light-emitting; Optics Express 17,1577 (2009));
Above-mentioned WOLEDs technical scheme A, E, H, I, J utilize the method for color conversion to realize WOLEDs.
Summary of the invention
The present invention proposes a kind ofly by the color conversion layer of red-emitting with launch the novel white organic light emitting diode that the organic electroluminescence device of blue light and green glow constitutes simultaneously, can be applicable to full-color demonstration and illumination.
The white organic light emitting diode that the present invention proposes is by the color conversion layer that is used for red-emitting (1); Be used for passive substrate (2); Being used for charge carrier injects and the hearth electrode that contacts (3); Be used to inject or transmit or stop charge carrier or stop first carrier blocking layers or the exciton barrier-layer (4) of exciton; Be used for launching simultaneously the organic material luminescent layer (5) of blue light and green glow; Be used to inject or transmit or stop charge carrier or stop second carrier blocking layers or the exciton barrier-layer (6) of exciton; Being used for the charge carrier injection constitutes with the top electrode that contacts (7) successively.
The white organic light emitting diode that the present invention proposes, its color conversion layer (1) thickness are 0.1 nanometer-1 centimetre; Can absorb blue light or green glow and red-emitting; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can be rigidity or flexibility; Can constitute by inorganic or organic material; The composite material that glass, plastics, organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or the above-mentioned material that mixes including, but not limited to the inorganic or organic fluorescence of various red-emittings or phosphor material constitutes, the mass percent of doping is greater than 0.01%.
The white organic light emitting diode that the present invention proposes, its substrate (2) thickness is 1 micron-1 centimetre; In visible-range, has high permeability; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can be rigidity or flexibility; Can constitute by inorganic material or organic material, including, but not limited to the composite material of glass, plastics, organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
The white organic light emitting diode that the present invention proposes, its hearth electrode (3) thickness are 0.1 nanometer-1 micron; Conduction is also transparent in visible-range; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the polymer of the organic molecule of the chalcogenide of indium tin oxide (ITO), other conductive, transparent, conductive, transparent, conductive, transparent, conduct electricity the composite material that translucent metal or above-mentioned material constitute.
The white organic light emitting diode that the present invention proposes, its first carrier blocking layers or exciton barrier-layer (4) thickness are 0.1 nanometer-1 micron; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the composite material of organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
The white organic light emitting diode that the present invention proposes, its organic material luminescent layer (5) thickness are 0.1 nanometer-1 micron; Can constitute by the organic fluorescence or the phosphor material of emission blue light and green glow; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Be made up of organic material, including, but not limited to organic fluorescence or organic molecule, the polymer of phosphor material doping or the composite material that both constitute of various emission blue lights and green glow, the mass percent of doping is greater than 0.01%.
The white organic light emitting diode that the present invention proposes, its second carrier blocking layers or exciton barrier-layer (6) thickness are 0.1 nanometer-1 micron; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the composite material of organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
The white organic light emitting diode that the present invention proposes, its top electrode (7) thickness are 0.1 nanometer-1 micron; Conduction also has high reflectance in visible-range; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the chalcogenide of metal, conduction, the organic molecule of conduction, the polymer of conduction or the composite material that above-mentioned material constitutes.
The white organic light emitting diode that the present invention proposes is launched blue light and green glow simultaneously by the electroluminescent device that substrate (2), hearth electrode (3), first carrier blocking layers or exciton barrier-layer (4), organic material luminescent layer (5), second carrier blocking layers or exciton barrier-layer (6), top electrode (7) constitute successively under the driving of additional power source.
The white organic light emitting diode that the present invention proposes; Constitute by the color conversion layer of red-emitting and the organic electroluminescence device of launching blue light and green glow simultaneously; Blue light and the green glow that color conversion layer (1) absorption portion organic electroluminescence device is launched simultaneously also converts it to red emission, and this red emission forms white light with another part blue light that sees through color conversion layer (1) and green glow three mixture of colours.
The white organic light emitting diode that the present invention proposes; Its color conversion layer (1), hearth electrode (3), carrier blocking layers or exciton barrier-layer (4), organic material luminescent layer (5), carrier blocking layers or exciton barrier-layer (6), top electrode (7); Can adopt but be not limited to film such as vacuum thermal evaporation, electron beam evaporation, laser flash distillation, sputter or molecular beam epitaxy or the preparation of thin layer dry preparation process; Also can adopt but be not limited to spin coating, cast, lift, print, film or the preparation of thin layer wet method preparation process such as deposition, maybe can adopt other film known in those skilled in the art or thin layer preparation technology preparation.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, and the technological means that it is detailed can be implemented according to the content of specification.In order to let the characteristic of the present invention can be more obviously understandable, below specially lift embodiment, and conjunction with figs. be elaborated, as follows.
Description of drawings
Fig. 1 is the structural representation of white organic light emitting diode of the present invention.
1: color conversion layer
2: substrate
3: hearth electrode
4: the first carrier blocking layers or exciton barrier-layer
5: the organic material luminescent layer
6: the second carrier blocking layers or exciton barrier-layer
7: top electrode
Among Fig. 1, white organic light emitting diode of the present invention by the color conversion layer that is used for red-emitting (1), be used for passive substrate (2), be used for charge carrier inject with the hearth electrode that contact (3), be used to inject or transmit or stop charge carrier or stop exciton first carrier blocking layers or exciton barrier-layer (4), be used for launching simultaneously blue light and green glow organic material luminescent layer (5), be used to inject or transmit or stop charge carrier or stop exciton second carrier blocking layers or exciton barrier-layer (6), be used for the charge carrier injection and constitute successively with the top electrode that contacts (7).
Among Fig. 1, color conversion layer (1) thickness is 0.1 nanometer-1 centimetre; Can absorb blue light or green glow and red-emitting; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can be rigidity or flexibility; Can constitute by inorganic or organic material; The composite material that glass, plastics, organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or the above-mentioned material that mixes including, but not limited to the inorganic or organic fluorescence of various red-emittings or phosphor material constitutes, the mass percent of doping is greater than 0.01%.
Among Fig. 1, substrate (2) thickness is 1 micron-1 centimetre; In visible-range, has high permeability; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can be rigidity or flexibility; Can constitute by inorganic material or organic material, including, but not limited to the composite material of glass, plastics, organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
Among Fig. 1, hearth electrode (3) thickness is 0.1 nanometer-1 micron; Conduction is also transparent in visible-range; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the polymer of the organic molecule of the chalcogenide of indium tin oxide (ITO), other conductive, transparent, conductive, transparent, conductive, transparent, conduct electricity the composite material that translucent metal or above-mentioned material constitute.
Among Fig. 1, first carrier blocking layers or exciton barrier-layer (4) thickness is 0.1 nanometer-1 micron; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the composite material of organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
Among Fig. 1, organic material luminescent layer (5) thickness is 0.1 nanometer-1 micron; Can constitute by the organic fluorescence or the phosphor material of emission blue light and green glow; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Be made up of organic material, including, but not limited to organic fluorescence or organic molecule, the polymer of phosphor material doping or the composite material that both constitute of various emission blue lights and green glow, the mass percent of doping is greater than 0.01%.
Among Fig. 1, second carrier blocking layers or exciton barrier-layer (6) thickness is 0.1 nanometer-1 micron; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the composite material of organic molecule, polymer, halogen compound, chalcogenide, nitrogen group compound, carbon group compound or above-mentioned material formation.
Among Fig. 1, top electrode (7) thickness is 0.1 nanometer-1 micron; Conduction also has high reflectance in visible-range; Can be the single or multiple lift structure, wherein every layer can be made up of one-component or multicomponent; Can constitute by inorganic material or organic material, including, but not limited to the chalcogenide of metal, conduction, the organic molecule of conduction, the polymer of conduction or the composite material that above-mentioned material constitutes.
Fig. 2 is the structural representation of white organic light emitting diode in the embodiment of the invention.
Among Fig. 2, color conversion layer (1) is made up of the organic fluorescence materials DCJTB doped polymer PMMA material film of red-emitting, can absorb blue light or green glow and red-emitting.
Among Fig. 2, substrate (2) is made up of glass, in visible-range, has high permeability.
Among Fig. 2, hearth electrode (3) is made up of electrically conducting transparent indium tin oxide (ITO), in visible-range, has high permeability.
Among Fig. 2, first carrier blocking layers or exciton barrier-layer (4) are made up of NPB, TCTA bilayer film.
Among Fig. 2, organic material luminescent layer (5) is by blue-light emitting layer, the TPBi film separator of organic molecule phosphor material (FIrpic) the doping organic molecule material of main part (TCTA) of emission blue light, the organic molecule phosphor material (Ir (ppy) of transmitting green light
3) the green emission layer of doping organic molecule material of main part (TPBi) constitutes.
Among Fig. 2, second carrier blocking layers or exciton barrier-layer (6) are by TPBi, Cs
2CO
3Bilayer film constitutes.
Among Fig. 2, top electrode (7) is made up of conduction and the metal A l film that in visible-range, has a high reflectance.
Fig. 3 is the output spectrum figure of white organic light emitting diode in the embodiment of the invention.
Among Fig. 3; The output spectrum of white organic light emitting diode is made up of blue light (peak wavelength is about 470nm), green glow (peak wavelength is about 510nm) and ruddiness (peak wavelength is about 600nm) respectively; Blue, green, red trichromatism blend forms white light; Wherein blue light and green emission are from the electroluminescence of the organic material luminescent layer (5) in the organic electroluminescence device; And red emission is from blue light and the green glow of color conversion layer (1) absorption portion organic material luminescent layer (5) emission and convert it to red emission, this red emission and another part blue light that sees through color conversion layer (1) and green glow three mixture of colours formation white light.
Embodiment
At first; The organic fluorescence materials (DCJTB) of red-emitting is dispersed in the chloroformic solution of polymer (PMMA) by certain mass percent (0.5%); Subsequently it is spin-coated on cover glass (thickness is about 150 microns) surface, at room temperature forming thickness naturally is the color conversion layer (1) of micron dimension (about 1-10 micron).
Secondly, going up the method that adopts the vacuum thermal evaporation plated film at substrate of glass (2) (thickness is about 1 millimeter), electrically conducting transparent indium tin oxide (ITO) (thickness is about 40 nanometers) hearth electrode (3) prepares NPB that thickness is nanometer scale, TCTA film continuously and is used for injection and transporting holes, block electrons as sandwich construction first carrier blocking layers or exciton barrier-layer (4); Adopt then the method for coevaporation plated film prepare thickness be nanometer scale, by the blue-light emitting layer of organic molecule phosphor material (FIrpic) the doping organic molecule material of main part (TCTA) of emission blue light; Adopt the method for thermal evaporation plated film to prepare the TPBi film separator that thickness is nanometer scale again, adopt then the method for coevaporation plated film prepare thickness be nanometer scale, by the organic molecule phosphor material (Ir (ppy) of transmitting green light
3) the green emission layer of doping organic molecule material of main part (TPBi), above-mentioned blue-light emitting layer, separator, green emission layer constitute sandwich construction organic material luminescent layer (5); Adopt the method for thermal evaporation plated film to prepare TPBi, the Cs that thickness is nanometer scale subsequently
2CO
3Film is used for injection and transmission electronic, blocking hole as sandwich construction second carrier blocking layers or exciton barrier-layer (6); Utilize at last the method for vacuum thermal evaporation plated film prepare thickness for the height reflection conduction Al film of nanometer scale as top electrode (7).
Finally; Utilize index-matching fluid bonding the color conversion layer (1) of red-emitting and the organic electroluminescence device exiting surface of launching blue light and green glow simultaneously; The white organic light emitting diode structure is as shown in Figure 2 in the embodiment of the invention; Color conversion layer/Glass/ITO (40nm)/NPB (40nm)/TCTA (5nm)/FIrpic:TCTA (10%, 30nm)/TPBi (2nm)/Ir (ppy)
3: TPBi (7%, 10nm)/TPBi (30nm)/Cs
2CO
3(1nm)/Al (100nm).
As shown in Figure 3; Be the output spectrum figure of embodiment of the invention white organic light emitting diode; The output spectrum of white organic light emitting diode is made up of blue light (peak wavelength is about 470nm), green glow (peak wavelength is about 510nm) and ruddiness (peak wavelength is about 600nm) respectively; Blue, green, red trichromatism blend forms white light; Wherein blue light and green emission are from the electroluminescence of the organic material luminescent layer (5) in the organic electroluminescence device; And red emission is from blue light and the green glow of color conversion layer (1) absorption portion organic material luminescent layer (5) emission and convert it to red emission, this red emission and another part blue light that sees through color conversion layer (1) and green glow three mixture of colours formation white light.
The performance of the white organic light emitting diode that obtains according to above-mentioned preparation method in the embodiment of the invention is as shown in table 1:
The white organic light emitting diode performance of table 1 embodiment of the invention
| High-high brightness (cd/m 2) | 6000 |
| Maximal efficiency (lm/W) | 11 |
| The CIE chromaticity coordinates | (0.33，0.42) |
| Color rendering index | 70 |
| Colour temperature (K) | 5420 |
The technical term of mentioning among the present invention is conventionally known to one of skill in the art; Material of mentioning in the embodiment of the invention and english abbreviation thereof and preparation method are for conventionally known to one of skill in the art; But those skilled in the art are to be understood that; The present invention is not limited by described material of present embodiment and preparation method, and claim of the present invention and summary of the invention have been summarized scope of the present invention and spirit.
Claims (2)
1. white organic light emitting diode; By the color conversion layer that is used for red-emitting (1), be used for passive substrate (2), be used for charge carrier inject with the hearth electrode that contact (3), be used to inject or transmit or stop charge carrier or stop exciton first carrier blocking layers or exciton barrier-layer (4), be used for electricity simultaneously cause the organic material luminescent layer (5) of launching blue light and green glow, be used to inject or transmit or stop charge carrier or stop exciton second carrier blocking layers or exciton barrier-layer (6), be used for the charge carrier injection and constitute successively with the top electrode that contacts (7); It is characterized in that: organic material luminescent layer (5) comprises blue light-emitting, separator, green luminescence layer simultaneously, and being used for simultaneously, electricity causes emission blue light and green glow.
2. white organic light emitting diode according to claim 1; It is characterized in that: color conversion layer (1) absorption portion organic electroluminescence device electricity simultaneously causes the blue light and the green glow of emission and converts it to ruddiness, and this ruddiness forms white light with the blue light and green glow three mixture of colours that another part electricity that sees through color conversion layer (1) causes emission.
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| CN2009101943420A CN101710609B (en) | 2009-12-01 | 2009-12-01 | Organic white light device |
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| CN101710609A CN101710609A (en) | 2010-05-19 |
| CN101710609B true CN101710609B (en) | 2012-08-08 |
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Non-Patent Citations (2)
| Title |
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