CN104576934A - White-light OLED (organic light emission diode) device and preparation method thereof - Google Patents
White-light OLED (organic light emission diode) device and preparation method thereof Download PDFInfo
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Abstract
The invention provides a white-light OLED (organic light emission diode) device. The device comprises a glass substrate as well as a red light color conversion layer, an anode, a hole-transmission layer, a blue light emitting layer, an electronic transmission layer and a cathode which are stacked sequentially, wherein a yellow light color conversion layer is arranged on one surface, facing air, of the glass substrate; the materials of the red light color conversion layer comprise a red light fluorescent material and a red light host material; the materials of the blue light emitting layer comprise a blue light fluorescent material and a blue light host material or comprise a blue light phosphor material and a phosphor host material; the materials of the yellow light emitting layer comprise yellow fluorescent powder and a photocuring adhesive; the light absorption wavelength peak of each of the red light fluorescent material and the yellow fluorescent powder ranges from 460 nm to 470 nm; the material of the anode adopts metal gold or silver. The white-light OLED device can realize emission of white light with stable light color. The invention further provides a preparation method of the white-light OLED device.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of white light organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter referred to as OLED, there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
The OLED light-emitting device of prior art, in order to form white light emission, has multiple luminescent layer compound mode, such as polychrome mixed luminescence, and multilayer is luminous.From integrated cost, technique, complexity, usual employing bi-material is luminous controls glow color than being easier to, and preparation technology is also fairly simple, as adopted the mode of blue light plus red light, but color rendering index is general, in order to strengthen color rendering index, usually can add Yellow light emitting layer, and between Yellow light emitting layer and blue light-emitting not easily produce power shift.But when adopting multilayer luminous, usually can, because of the change of driving voltage, cause the distribution of charge carrier to change, the distribution of charge carrier in multiple luminescent layer be changed, thus glow color is changed along with voltage, not easily form stable white light emission.
Summary of the invention
In view of this, the invention provides a kind of white light organic electroluminescence device and preparation method thereof.By luminescent layer is set to independent blue light-emitting, and red light color conversion layer is set between glass substrate and anode, at glass substrate, gold-tinted color converting layer is set towards the one side of air, and the absorbing wavelength of the emission wavelength of blue light-emitting and red light color conversion layer and gold-tinted color converting layer matches, finally obtain the white light organic electroluminescence device with stable white light emission.
On the one hand, the invention provides a kind of white light organic electroluminescence device, the anode, hole transmission layer, blue light-emitting, electron transfer layer and the negative electrode that comprise glass substrate and be cascading on described glass substrate one surface, between described glass substrate and described anode, be provided with red light color conversion layer, at described glass substrate, the one side of air be provided with gold-tinted color converting layer;
The material of described red light color conversion layer comprises red light flourescent material and ruddiness material of main part that mass ratio is 1 ~ 10:100, and the peak value of the light absorption wavelength of described red light flourescent material is between 460nm ~ 470nm; Described ruddiness material of main part is (oxine)-aluminium (Alq3) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi);
The material of described blue light-emitting comprises blue emitting phosphor material and the phosphorescent light body material that blue-light fluorescent material and Blue-light emitting host material that mass ratio is 1 ~ 10:100 or mass ratio are 5 ~ 20:100, the emission wavelength peak of described blue-light fluorescent material and described blue emitting phosphor material is all between 460nm ~ 470nm, described Blue-light emitting host material is the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene (MADN) or N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPD); Described phosphorescent light body material is 4,4'-bis-(9-carbazole) biphenyl (CBP);
The material of described gold-tinted color converting layer comprises yellow fluorescent powder and Photocurable adhesive that mass ratio is 1 ~ 20:100, and the peak value of the light absorption wavelength of described yellow fluorescent powder is between 460nm ~ 470nm;
The material of described anode is metallic gold or silver.
White light organic electroluminescence device provided by the invention, red light luminescent layer and Yellow light emitting layer are set to color converting layer, excite red light flourescent material and yellow fluorescent powder luminescence by the utilizing emitted light of blue-light fluorescent material, produce photoluminescence emission, then mix blue light and finally form white light emission; And in order to luminescence generated by light will be formed, need red light flourescent material identical with the emission peak of blue-light fluorescent material with the absorption peak of yellow fluorescent powder or close, luminescence generated by light could be produced, therefore the present invention have selected the luminescent material matched, red light flourescent material between 460nm ~ 470nm of the peak value of light absorption wavelength and yellow fluorescent powder and the blue-light fluorescent material of emission wavelength peak between 460nm ~ 470nm.Due to luminescent layer is set to independent blue light-emitting, only has the impact that blue light-emitting is regulated and controled by charge carrier, under single luminescent layer, injection and the transmission of charge carrier are less on the impact of glow color, therefore the white light emission that obtains of the present invention is photochromic stable, and owing to being red, yellow, blue three-colour light-emitting, its color rendering index can keep higher level.
Preferably, described red light flourescent material is 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl)-4H-pyrans (DCM).
Preferably, described blue-light fluorescent material is 2,5,8, the tertiary Ding Ji perylene (TBPe) of 11-tetra-, 4,4'-two [4-(diphenylamino) styryl] biphenyl (BDAVBi) or N-(4-((E)-2-(6-((E)-4-(diphenylamino) styryl) naphthalene-2-base) vinyl) phenyl)-N-phenylaniline (N-BDAVBi); Described blue emitting phosphor material is that two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium (FIr6).
Preferably, described yellow fluorescent powder is [Sr, Ba, Ca]
2si
5n
8: Eu
2+fluorescent material, the thickness of described gold-tinted color converting layer is 10 μm ~ 50 μm.Preferably, described Photocurable adhesive is light-solidifying poly acrylic resin.
Preferably, the thickness of described red light color conversion layer is 100nm ~ 400nm.
Preferably, the thickness of described blue light-emitting is 5nm ~ 20nm.
Preferably, the thickness of described anode is 18nm ~ 30nm.
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), the thickness of described hole transmission layer is 20 ~ 60nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), the thickness of described electron transfer layer is 20 ~ 60nm.
Preferably, described negative electrode is laminate electrode, comprise the first cathode layer being layered in described electron transfer layer surface and the second cathode layer being layered in described first cathode layer surface, the material of described first cathode layer is CsF or LiF, and the material of described second cathode layer is metal A g, Al, Mg-Al alloy or Mg-Ag alloy; The thickness of described first cathode layer is 0.5nm ~ 2nm, and the thickness of described second cathode layer is 70nm ~ 200nm.
On the other hand, the invention provides a kind of preparation method of white light organic electroluminescence device, comprise the following steps:
Clean glass substrate is provided, adopts the mode of silk screen printing to prepare gold-tinted color converting layer on the surface at one of described glass substrate: after 1 ~ 20:100 mixes in mass ratio with Photocurable adhesive by yellow fluorescent powder, to be coated in one of described glass substrate on the surface; The peak value of the light absorption wavelength of described yellow fluorescent powder is between 460nm ~ 470nm; The meshcount that described screen printing process adopts is 200 ~ 1000 orders;
Be 1 × 10 in vacuum degree
-5~ 1 × 10
-3in the vacuum coating system of Pa, adopt the mode of vacuum evaporation to prepare red light color conversion layer, anode, hole transmission layer, blue light-emitting, electron transfer layer and negative electrode successively on the surface at another of described glass substrate, obtain white light organic electroluminescence device;
The material of described red light color conversion layer comprises red light flourescent material and ruddiness material of main part that mass ratio is 1 ~ 10:100, and the peak value of the light absorption wavelength of described red light flourescent material is between 460nm ~ 470nm; Described ruddiness material of main part is (oxine)-aluminium or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; The evaporation rate of described red light color conversion layer is 0.01 ~ 2nm/s;
The material of described anode is metallic gold or silver, and evaporation rate is 0.01 ~ 1nm/s;
The material of described blue light-emitting comprises blue emitting phosphor material and the phosphorescent light body material that blue-light fluorescent material and Blue-light emitting host material that mass ratio is 1 ~ 10:100 or mass ratio are 5 ~ 20:100, the emission wavelength peak of described blue-light fluorescent material and described blue emitting phosphor material is all between 460nm ~ 470nm, described Blue-light emitting host material is the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene or N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines; Described phosphorescent light body material is 4,4'-bis-(9-carbazole) biphenyl (CBP); The evaporation rate of described blue light-emitting is 0.01 ~ 1nm/s.
Preferably, described red light flourescent material is 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl)-4H-pyrans (DCM).
Preferably, described blue-light fluorescent material is 2,5,8, the tertiary Ding Ji perylene (TBPe) of 11-tetra-, 4,4'-two [4-(diphenylamino) styryl] biphenyl (BDAVBi) or N-(4-((E)-2-(6-((E)-4-(diphenylamino) styryl) naphthalene-2-base) vinyl) phenyl)-N-phenylaniline (N-BDAVBi); Described blue emitting phosphor material is that two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium (FIr6).
Preferably, described yellow fluorescent powder is [Sr, Ba, Ca]
2si
5n
8: Eu
2+fluorescent material, the thickness of described gold-tinted color converting layer is 10 μm ~ 50 μm.Preferably, described Photocurable adhesive is light-solidifying poly acrylic resin.
Preferably, the thickness of described red light color conversion layer is 100nm ~ 400nm.
Preferably, the thickness of described blue light-emitting is 5nm ~ 20nm.
Preferably, the thickness of described anode is 18nm ~ 30nm.
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), the thickness of described hole transmission layer is 20 ~ 60nm.Preferably, the evaporation rate of described hole transmission layer is 0.1 ~ 1nm/s.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), the thickness of described electron transfer layer is 20 ~ 60nm.Preferably, the evaporation rate of described electron transfer layer is 0.1 ~ 1nm/s.
Preferably, described negative electrode is laminate electrode, comprise the first cathode layer being layered in described electron transfer layer surface and the second cathode layer being layered in described first cathode layer surface, the material of described first cathode layer is CsF or LiF, and the material of described second cathode layer is metal A g, Al, Mg-Al alloy or Mg-Ag alloy; The thickness of described first cathode layer is 0.5nm ~ 2nm, and the thickness of described second cathode layer is 70nm ~ 200nm.Preferably, the evaporation rate of described negative electrode is 0.01 ~ 1nm/s.
The invention provides a kind of white light organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) white light organic electroluminescence device provided by the invention, luminescent layer is set to independent blue light-emitting, therefore the transmitting of blue light can not be subject to the variable effect of driving voltage, red light luminescent layer is set to color converting layer, excite red light material luminous by the utilizing emitted light of blue light material, red light material produces photoluminescence emission, then arranges a gold-tinted color converting layer again in outside, formed multicolor luminous, thus realize white light emission; The white light emission that the present invention adopts look switch technology to obtain, due to the impact only having blue light-emitting regulated and controled by charge carrier, under single luminescent layer, injection and the transmission of charge carrier are less on the impact of glow color, therefore the white light emission that obtains of the present invention is photochromic stable, and owing to being multicolor luminous, its color rendering index can keep higher level;
(2) preparation technology of white light organic electroluminescence device of the present invention is simple, and easy large area preparation, is suitable for industrialization and uses on a large scale.
Accompanying drawing explanation
Fig. 1 is the structural representation of the white light organic electroluminescence device that the embodiment of the present invention 1 obtains;
Fig. 2 is the white light organic electroluminescence device color rendering index of the embodiment of the present invention 1 and comparative example and the change curve of driving voltage.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for white light organic electroluminescence device, comprises the following steps:
(1) provide glass substrate, and clean up, then adopt the mode of silk screen printing to prepare gold-tinted color converting layer on the surface at one of glass substrate, particularly, by yellow fluorescent powder [Sr, Ba, Ca]
2si
5n
8: Eu
2+with light curing agent polyacrylic resin in mass ratio 1:100 mix, be then coated in one of glass substrate on the surface, screen printing process adopt meshcount be 200 orders, the thickness of gold-tinted color converting layer is 50 μm;
(2) be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt thermal resistance evaporation technique to prepare red light color conversion layer, anode, hole transmission layer, blue light-emitting, electron transfer layer and negative electrode successively on the surface at another of glass substrate, obtain white light organic electroluminescence device;
Particularly, first prepare red light color conversion layer at glass baseplate surface, material comprises Alq3 and is entrained in the DCM in Alq3, wherein, the mass ratio of DCM and Alq3 is 1:100, and the thickness of red light color conversion layer is 400nm, the evaporation rate of DCM is the evaporation rate of 0.01nm/s, Alq3 is 1nm/s; Then prepare anode on red light color conversion layer surface, material is metallic gold, and thickness is 30nm, and evaporation rate is 1nm/s; Then prepare hole transmission layer at anode surface, material is NPB, and thickness is 20nm, and evaporation rate is 0.1nm/s;
Prepare blue light-emitting on hole transmission layer surface again, material comprises MADN and is entrained in the TBPe in MADN, and the mass ratio of TBPe and MADN is 1:100, and the thickness of blue light-emitting is 20nm.Wherein the evaporation rate of TBPe is the evaporation rate of 0.01nm/s, MADN is 1nm/s;
Prepare electron transfer layer on blue light-emitting surface again, material is TPBi, and thickness is 20nm, and evaporation rate is 0.1nm/s;
Finally prepare negative electrode on the electron transport layer, negative electrode comprises the first cathode layer, and material is LiF, and the second cathode layer, and material is metal A g, the laminated construction of composition LiF/Ag; The thickness of LiF is the thickness of 0.5nm, metal A g is 200nm; First on the electron transport layer prepare LiF, evaporation rate is 0.01nm/s, and the evaporation rate then preparing metal A g, metal A g is 0.01nm/s.
Fig. 1 is the structural representation of the white light organic electroluminescence device that the embodiment of the present invention 1 obtains.As shown in Figure 1, the present embodiment white light organic electroluminescence device, comprises glass substrate 10, red light color conversion layer 11, anode 12, hole transmission layer 13, blue light-emitting 14, electron transfer layer 15, negative electrode 16 and gold-tinted color converting layer 17.
Embodiment 2
A preparation method for white light organic electroluminescence device, comprises the following steps:
(1) provide glass substrate, and clean up, then adopt the mode of silk screen printing to prepare gold-tinted color converting layer on the surface at one of glass substrate, particularly, by yellow fluorescent powder [Sr, Ba, Ca]
2si
5n
8: Eu
2+with light curing agent polyacrylic resin in mass ratio 20:100 mix, be then coated in one of glass substrate on the surface, screen printing process adopt meshcount be 600 orders, the thickness of gold-tinted color converting layer is 10 μm;
(2) be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt thermal resistance evaporation technique to prepare red light color conversion layer, anode, hole transmission layer, blue light-emitting, electron transfer layer and negative electrode successively on the another side of glass substrate, obtain white light organic electroluminescence device;
Particularly, first red light color conversion layer is prepared at glass baseplate surface, material comprises TPBi and is entrained in the DCM in TPBi, wherein, the mass ratio of DCM and TPBi is 10:100, the evaporation rate of the thickness of red light color conversion layer to be the evaporation rate of 100nm, DCM be 0.01nm/s, TPBi is 0.1nm/s; Then prepare anode on red light color conversion layer surface, material is argent, and thickness is 18nm, and evaporation rate is 0.01nm/s; Then prepare hole transmission layer at anode surface, material is TPD, and thickness is 60nm, and evaporation rate is 1nm/s;
Prepare blue light-emitting on hole transmission layer surface again, material comprises NPD and is entrained in the BDAVBi in NPD, and the mass ratio of BDAVBi and NPD is 10:100, and the thickness of blue light-emitting is 5nm; Wherein the evaporation rate of BDAVBi is the evaporation rate of 0.01nm/s, NPD is 0.1nm/s;
Prepare electron transfer layer on blue light-emitting surface again, material is Bphen, and thickness is 60nm, and evaporation rate is 1nm/s;
Last electron transfer layer prepares negative electrode, and negative electrode comprises the first cathode layer, and material is CsF, and the second cathode layer, and material is metal A l, the laminated construction of composition CsF/Al; Wherein the thickness of CsF is the thickness of 2nm, metal A l is 70nm, and first prepare CsF, evaporation rate is 0.1nm/s, and the evaporation rate then preparing metal A l, metal A l is 0.2nm/s.
Embodiment 3
A preparation method for white light organic electroluminescence device, comprises the following steps:
(1) provide glass substrate, and clean up, then adopt the mode of silk screen printing to prepare gold-tinted color converting layer on the surface at one of glass substrate, particularly, by yellow fluorescent powder [Sr, Ba, Ca]
2si
5n
8: Eu
2+with light curing agent polyacrylic resin in mass ratio 10:100 mix, be then coated in one of glass substrate on the surface, screen printing process adopt meshcount be 1000 orders, the thickness of gold-tinted color converting layer is 20 μm;
(2) be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt thermal resistance evaporation technique to prepare red light color conversion layer, anode, hole transmission layer, blue light-emitting, electron transfer layer and negative electrode successively on the another side of glass substrate, obtain white light organic electroluminescence device;
Particularly, first on the another side of glass substrate, red light color conversion layer is prepared, material comprises Alq3 and is entrained in the DCM in Alq3, wherein the mass ratio of DCM and Alq3 is 5:100, the thickness of red light color conversion layer is 200nm, wherein the evaporation rate of DCM is the evaporation rate of 0.1nm/s, Alq3 is 2nm/s; Then prepare anode on red light color conversion layer surface, material is metallic gold, and thickness is 25nm, and evaporation rate is 0.2nm/s; Then prepare hole transmission layer at anode surface, material is m-MTDATA, and thickness is 40nm, and evaporation rate is 0.5nm/s;
Prepare blue light-emitting on hole transmission layer surface again, material comprises NPD and is entrained in the N-BDAVBi in NPD, and the mass ratio of N-BDAVBi and NPD is 5:100, and the thickness of blue light-emitting is 10nm.Wherein the evaporation rate of N-BDAVBi is the evaporation rate of 0.01nm/s, NPD is 0.2nm/s;
Prepare electron transfer layer on blue light-emitting surface again, material is BCP, and thickness is 40nm, and evaporation rate is 0.5nm/s;
Finally prepare negative electrode on the electron transport layer, negative electrode comprises the first cathode layer, and material is CsF, and the second cathode layer, and material is Mg-Al alloy, the laminated construction of composition CsF/Mg-Al; Wherein the thickness of CsF is the thickness of 1nm, Mg-Al alloy is 100nm, and first prepare CsF, evaporation rate is 0.1nm/s, and then prepare Mg-Al alloy, the evaporation rate of Mg-Al alloy is 1nm/s.
Comparative example
A preparation method for white light organic electroluminescence device, comprises the following steps:
(1) provide glass substrate, and clean up;
(2) be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt thermal resistance evaporation technique to prepare anode, hole transmission layer, blue light-emitting, red light luminescent layer, electron transfer layer and negative electrode successively at glass baseplate surface, obtain white light organic electroluminescence device;
First prepare anode at glass baseplate surface, material is metallic gold, and thickness is 30nm, and evaporation rate is 1nm/s; Then prepare hole transmission layer at anode surface, material is NPB, and thickness is 20nm, and evaporation rate is 0.1nm/s;
Prepare blue light-emitting on hole transmission layer surface again, material comprises MADN and is entrained in the TBPe in MADN, and the mass ratio of TBPe and MADN is 1:100, and the thickness of blue light-emitting is 20nm.Wherein the evaporation rate of TBPe is the evaporation rate of 0.01nm/s, MADN is 1nm/s;
Prepare red light luminescent layer on blue light-emitting surface again, material comprises Alq3 and is entrained in the DCM in Alq3, and wherein, the mass ratio of DCM and Alq3 is 1:100, and the evaporation rate of thickness to be the evaporation rate of 10nm, DCM be 0.01nm/s, Alq3 is 1nm/s;
Prepare electron transfer layer on red light luminescent layer surface again, material is TPBi, and thickness is 20nm, and evaporation rate is 0.1nm/s;
Finally prepare negative electrode on the electron transport layer, negative electrode comprises the first cathode layer, and material is LiF, and the second cathode layer, and material is metal A g, the laminated construction of composition LiF/Ag; The thickness of LiF is the thickness of 0.5nm, metal A g is 200nm; First on the electron transport layer prepare LiF, evaporation rate is 0.01nm/s, and the evaporation rate then preparing metal A g, metal A g is 0.01nm/s.
Effect example
Test of the present invention and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
White light organic electroluminescence device obtained by the embodiment of the present invention 1 ~ 3 and comparative example is carried out the test of luminous efficiency and luminosity, test and carry out under the driving voltage of 6V.Test result is as shown in table 1:
Table 1
As can be seen from Table 1, white light organic electroluminescence device luminous efficiency compared with the white light organic electroluminescence device of comparative example of the embodiment of the present invention is substantially suitable, but color rendering index is slightly high, from chromaticity coordinates, the white light organic electroluminescence device of the embodiment of the present invention, its illuminant colour coordinate points relatively white point region, comparative example then deviate from white light field, and color is partially blue.This is because white light organic electroluminescence device of the present invention have employed red, yellow, blue three-colour light-emitting, ruddiness, what gold-tinted adopted is look switch technology, do not need the problem considering charge carrier allotment, therefore the transmitting of blue light can obtain higher efficiency, only needs blue emission to excite ruddiness in addition, and the luminescence generated by light of gold-tinted, define multicolor luminous, therefore color rendering index is higher.
The white light organic electroluminescence device of embodiment 1 and comparative example is measured in the drive voltage range of 3V ~ 8V the variation relation of color rendering index (CRI) and driving voltage, result is as shown in table 2 and Fig. 2.
Table 2
As can be seen from table 2 and Fig. 2, embodiment 1 white light organic electroluminescence device from the driving voltage of 3V to 8.0V, the change of its color rendering index is smaller, minimum is 80, be up to 90, and in the interval of normally used driving voltage 4.0V ~ 8.0V, color rendering index amplitude of variation is very little.
And comparative example white light organic electroluminescence device from the driving voltage of 3V to 8.0V, color rendering index is minimum is 60, be up to 75, between 4.0V ~ 8.0V, it has change by a relatively large margin, therefore luminous photochromic extremely unstable, this is also because of the change along with driving voltage, the result that in multiple luminescent layer, the balance of charge carrier constantly changes.And the impact that embodiment of the present invention white light organic electroluminescence device only has blue light-emitting regulated and controled by charge carrier, under single luminescent layer, injection and the transmission of charge carrier are less on the impact of glow color, therefore light-emitting device provided by the invention is photochromic stable, and owing to being multicolor luminous, its color rendering index can keep higher level.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a white light organic electroluminescence device, the anode, hole transmission layer, blue light-emitting, electron transfer layer and the negative electrode that comprise glass substrate and be cascading on described glass substrate one surface, it is characterized in that, between described glass substrate and described anode, be provided with red light color conversion layer, at described glass substrate, the one side of air be provided with gold-tinted color converting layer;
The material of described red light color conversion layer comprises red light flourescent material and ruddiness material of main part that mass ratio is 1 ~ 10:100, and the peak value of the light absorption wavelength of described red light flourescent material is between 460nm ~ 470nm; Described ruddiness material of main part is (oxine)-aluminium or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene;
The material of described blue light-emitting comprises blue emitting phosphor material and the phosphorescent light body material that blue-light fluorescent material and Blue-light emitting host material that mass ratio is 1 ~ 10:100 or mass ratio are 5 ~ 20:100, the emission wavelength peak of described blue-light fluorescent material and described blue emitting phosphor material is all between 460nm ~ 470nm, described Blue-light emitting host material is the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene or N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines; Described phosphorescent light body material is 4,4'-bis-(9-carbazole) biphenyl;
The material of described gold-tinted color converting layer comprises yellow fluorescent powder and Photocurable adhesive that mass ratio is 1 ~ 20:100, and the peak value of the light absorption wavelength of described yellow fluorescent powder is between 460nm ~ 470nm;
The material of described anode is metallic gold or silver.
2. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, described red light flourescent material is 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl)-4H-pyrans.
3. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, described blue-light fluorescent material is 2,5,8, the tertiary Ding Ji perylene of 11-tetra-, 4,4'-two [4-(diphenylamino) styryl] biphenyl or N-(4-((E)-2-(6-((E)-4-(diphenylamino) styryl) naphthalene-2-base) vinyl) phenyl)-N-phenylaniline; Described blue emitting phosphor material is that two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium.
4. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, described yellow fluorescent powder is [Sr, Ba, Ca]
2si
5n
8: Eu
2+fluorescent material, described Photocurable adhesive is light-solidifying poly acrylic resin, and the thickness of described gold-tinted color converting layer is 10 μm ~ 50 μm.
5. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described red light color conversion layer is 100nm ~ 400nm.
6. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described blue light-emitting is 5nm ~ 20nm.
7. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyls)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl)-benzidine, the thickness of described hole transmission layer is 20 ~ 60nm.
8. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is oxine aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, the thickness of described electron transfer layer is 20 ~ 60nm.
9. white light organic electroluminescence device as claimed in claim 1, it is characterized in that, described negative electrode is laminate electrode, comprise the first cathode layer being layered in described electron transfer layer surface and the second cathode layer being layered in described first cathode layer surface, the material of described first cathode layer is CsF or LiF, and the material of described second cathode layer is metal A g, Al, Mg-Al alloy or Mg-Ag alloy; The thickness of described first cathode layer is 0.5nm ~ 2nm, and the thickness of described second cathode layer is 70nm ~ 200nm.
10. a preparation method for white light organic electroluminescence device, is characterized in that, comprises the following steps:
Clean glass substrate is provided, adopts the mode of silk screen printing to prepare gold-tinted color converting layer on the surface at one of described glass substrate: after 1 ~ 20:100 mixes in mass ratio with Photocurable adhesive by yellow fluorescent powder, to be coated in one of described glass substrate on the surface; The peak value of the light absorption wavelength of described yellow fluorescent powder is between 460nm ~ 470nm; The meshcount that described screen printing process adopts is 200 ~ 1000 orders;
Be 1 × 10 in vacuum degree
-5~ 1 × 10
-3in the vacuum coating system of Pa, adopt the mode of vacuum evaporation to prepare red light color conversion layer, anode, hole transmission layer, blue light-emitting, electron transfer layer and negative electrode successively on the surface at another of described glass substrate, obtain white light organic electroluminescence device;
The material of described red light color conversion layer comprises red light flourescent material and ruddiness material of main part that mass ratio is 1 ~ 10:100, and the peak value of the light absorption wavelength of described red light flourescent material is between 460nm ~ 470nm; Described ruddiness material of main part is (oxine)-aluminium or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; The evaporation rate of described red light color conversion layer is 0.01 ~ 2nm/s;
The material of described anode is metallic gold or silver, and evaporation rate is 0.01 ~ 1nm/s;
The material of described blue light-emitting comprises blue emitting phosphor material and the phosphorescent light body material that blue-light fluorescent material and Blue-light emitting host material that mass ratio is 1 ~ 10:100 or mass ratio are 5 ~ 20:100, the emission wavelength peak of described blue-light fluorescent material and described blue emitting phosphor material is all between 460nm ~ 470nm, described Blue-light emitting host material is the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene or N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines; Described phosphorescent light body material is 4,4'-bis-(9-carbazole) biphenyl; The evaporation rate of described blue light-emitting is 0.01 ~ 1nm/s.
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