CN102244199A - Organic electroluminescent plant lighting source and preparation method thereof - Google Patents
Organic electroluminescent plant lighting source and preparation method thereof Download PDFInfo
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- CN102244199A CN102244199A CN2011101875115A CN201110187511A CN102244199A CN 102244199 A CN102244199 A CN 102244199A CN 2011101875115 A CN2011101875115 A CN 2011101875115A CN 201110187511 A CN201110187511 A CN 201110187511A CN 102244199 A CN102244199 A CN 102244199A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 43
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Abstract
The invention relates to an organic electroluminescent plant lighting source and a preparation method thereof. The ITO glass substrate, the hole transport layer, the luminescent layer, the electron transport layer and the metal electrode are used, and the luminescent layer is a host-guest material doping system; the doping concentration of the guest material is 2 t-20% of the mass of the host material; the guest material is selected from materials capable of emitting a plurality of wave crests. By selecting different types of hosts and regulating and controlling the concentration of the object luminescent material, two wave peaks emitted by the device are in the area of a plant growth light source, and light of unnecessary wave bands absorbed by some plants is reduced, so that the chlorophyll absorption efficiency is improved, the energy is saved, the plant growth period is shortened, and the plant yield is improved.
Description
Technical field
The present invention relates to a kind of plant illumination light source and preparation method thereof, particularly a kind of organic electroluminescent plant illumination light source and preparation method thereof.
Background technology
At present, the light source that is used for plant growth lighting mainly contains sunlight, incandescent lamp, fluorescent lamp, light-emitting diode etc.The solar energy 90% that can reach ground concentrates between 290 ~ 3000 nm, and the following part light of its medium wavelength 300 nm very easily makes makes the deposits yields disease.In the winter time, some local light application time is not enough.Indoor natural light replenishes so artificial lighting need be set according to being not enough to keep the plant growth.
The absworption peak of chlorophyll a is 430 nm, 660 nm, and the absworption peak of chlorophyll b is 450 nm, 640 nm.What work in the photosynthesis is chlorophyll a, and it can be converted into chemical energy by luminous energy with royal purple light and the ruddiness that absorbs; The existence of chlorophyll b has enlarged the scope of plant absorbing light, the light that they will absorb passes to special chlorophyll a, special chlorophyll a utilizes carbon dioxide to become organic substance with hydration under ruddiness (680 nm and 700 nm) effect, emits oxygen, is grown thereby make plant obtain energy.
Commonly used have incandescent lamp and a fluorescent lamp.But have many shortcomings, for example the incandescent lamp energy efficiency is low, and light intensity Chang Buneng satisfies the requirement of flowering plant; The temperature height, the life-span is short; Distribution of light is inhomogeneous etc.; Higher for its installation cost of fluorescent lamp; Light intensity can not be got together.In recent years, LED light lamp also is useful on the plant illumination.Existing white light-emitting diodes, energy mainly are distributed in the blue region of 445 nm and there are two peak values in the yellow green district of 550 nm.And the required ruddiness of plant lacks very much.
At present, that is that all right is ripe for the technology of white light OLED, does not also have finished product on the market.It is a kind of OLED of non-white light that the present invention uses the OLED lamp, is primarily aimed at the characteristics of plant growth, utilizes the monomer of single luminescent material and the light of bimolecular emission 400～480 nm royal purple light districts and 600～680nm red light district.General luminescent material spectrum has only a crest, to satisfy so plant the growth light source condition at least needs launch two kinds of luminescent materials of royal purple light and ruddiness respectively.Recently develop bimolecular (bimolecular:excimer, extromer, exciplex and the extroplex) emission that utilizes single luminescent material to form and obtained a plurality of luminous crests, its advantage is that the technology cost is low, does not exist owing to the different inhomogeneity problems that cause of the degree of aging of different luminescent materials.Can launch a plurality of crests based on bimolecular homogenous material, be a kind of effective way that obtains white light.Bimolecular formation and emissive porwer depend on the concentration of luminescent material, by controlling the light source that its doping content can realize the plant growth subtly.
Summary of the invention
One of purpose of the present invention is to overcome problems of the prior art, and a kind of organic electroluminescent plant illumination light source is provided.
Two of purpose of the present invention is to provide the preparation method of this light source.
For achieving the above object, design of the present invention is: be fit to the light (spectrum is the royal purple light district of 400～480 nm and the red light district of 600～680 nm) that green plants chlorophyll absorbs for the plant illumination light source can be sent, reduce the not light of absorption bands of other plant chlorophyll.We have obtained the ruddiness that plant needs most (crest is at 660 nm), and the crest of blue light is at 440 nm simultaneously, and its spectrum not only comprises the required green glow of plant, has also comprised the absorption spectrum of chlorophyll a and chlorophyll b.Usually need to obtain the combination of multiple different luminescent material by a plurality of crests, strictly control the concentration of each luminescent material and come its luminous intensity of balance, and the technology more complicated.The present invention is limited in hole transmission layer (hole-transporting layer to the recombination region of exciton by the design device architecture, and luminescent layer (emitting layer (HTL)), (EML)) interface, by HTL on the interface and the luminous spectrum of realizing two waveband of EML, thereby provide a kind of easy method that satisfies plant growth light source, wherein blue light is launched by HTL, and ruddiness is launched by bimolecular.
1. material solution; The light absorption and the light radiation process of general luminescent material all only occur on the molecule, and two or more molecule fellowships absorb and the process of emission but find to have in some cases in experiment.In this case, absorbing or launching is not to be produced by any unimolecule, but the complex of molecule produces.Common complex is called bimolecular by two molecular compositions, and four kinds of forms are arranged: excimer (excimer), electricity cause excimer (extromer), exciplex (exciplex) and electricity and cause exciplex (extroplex).This bimolecular luminescent material can be formed and itself monomer spectrum and bimolecular emission spectrum can be launched usually, and the bimolecular emission spectrum is compared the spectrum broad and is produced tangible red shift with monomer, if the monomer of luminescent material is in royal purple light district, bimolecular is luminous in the ruddiness zone, then can obtain the light source of plant growth needs.Excimer and extromer are in intermolecular formation of the same race, and be this simple in structure, only needs single luminescent material.Exciplex and extroplex are two kinds of different intermolecular formation, and be relatively stricter to the selection of these two kinds of materials.
The luminous guest materials of this patent selects to launch the material of a plurality of crests, can be fluorescent material, also can be phosphor material platinum complex platinum (II) [2-(and 40,60-difluorophenyl) pyridinato-N,
)] (2,4-pentanedionato) (FPt), platinum (II) complex phosphors, platinum [methyl-3,5-di-(2-pyridyl) benzoate] chloride (Pt
L 2 Cl), platinum [1,3-difluoro-4,6-di (2-pyridinyl) benzene] chloride (Pt-4) etc.Wherein the emission spectrum of monomer (monomer) is at 400-500 nm wave band, and the luminous luminescent material at 600-700 nm wave band of bimolecular (bimolecular) is all at the row of selection.The material of main part of this moment selects its triplet energy level must be higher than Pt-4's, make Pt-4 launch monomer and two crests of bimolecules simultaneously, the material of main part that satisfies this requirement can be 1,3-bis (9-carbazolyl) benzene (mCP), 4,4 '-bis (9-carbazolyl)-biphenyl (CBP), 4,4 ', 4 "-tris (N-carbazolyl)-triphenylamine (TCTA) etc.This single luminous object is one of scheme that obtains plant growth light source.
Because the blue light crest of above-mentioned material lacks the light about 440 necessary nm of some plant about 475 nm, the present invention has adopted another implementation.By selecting suitable main body and electron transport material, the exciton recombination zone territory is limited in HTL/EML at the interface, make device launch HTL blue light and bimolecular ruddiness, wavelength is corresponding 440 nm and 660 nm respectively.At first be the selection of main body, its triplet energy level must be much smaller than Pt-4, so just can suppress the light about 475 nm of Pt-4, a red-emitting part.The selection of material of main part should be satisfied following requirement: 1. the emission peak of main body is in the royal purple optical band; 2. the triplet energy level of main body is much smaller than the triplet energy level of object; 3. has cavity transmission ability.As N, N
'-bis-(1-naphthyl)-N, N
'-diphenyl-1,10-biphenyl-4,4
'-diamine (NPB), BNs (BN
1:
,
-N, N-diphenylamine-4,
-diphenyl-1,
-binaphthyl; BN
2:
,
-(9H-9-carbazole)-4,40-diphenyl-1,
-binaphthyl; And BN
3: 4,
-bis (9-(p-fluorophenyl)-9H-3-carbazolyl))-1,
-binaphthyl). series meets the demands.
Make exciton be limited in the HTL/EML interface, just need electric transmission very fast, select the fast material of electron-transporting, for example: 4,7-Diphenyl-1,10-phenanthroline (Bphen), 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI) etc.
2, the organization plan of luminescent layer: we have prepared the very simple plant illumination light source of device architecture, as shown in Figure 2, comprise the 1-anode, 2-hole transmission layer, 3-luminescent layer, 4-electron transfer layer, 5-negative electrode.Wherein luminescent layer adopts the Subjective and Objective structure, and the concentration that changes guest materials can change the relative intensity of blue light and ruddiness, thereby satisfies the needs of different plants.
According to above-mentioned design, the present invention adopts following technical scheme:
A kind of organic electroluminescent plant illumination light source by ito glass substrate, hole transmission layer, luminescent layer, electron transfer layer and metal electrode, is characterized in that described luminescent layer is the material doped system of Subjective and Objective; Described guest materials doping content is 2 wt%～20 wt% of described material of main part quality.
Above-mentioned guest materials emission spectrum simultaneously is the monomer spectrum of 400-500 nm wave band and the bimolecular spectrum of 600-700 nm wave band; Described material of main part is: 1, and 3-bis (9-carbazolyl) benzene (mCP), 4,4 '-bis (9-carbazolyl)-biphenyl (CBP), or 4,4 ', 4 "-tris (N-carbazolyl)-triphenylamine (TCTA).
Above-mentioned guest materials is the complex of phosphor material platinum.
Above-mentioned phosphor material is the complex of platinum, can be: [2-(40,60-difluorophenyl) pyridinato-N,
)] (2,4-pentanedionato), platinum (II) complex phosphors, platinum [methyl-3,5-di-(2-pyridyl) benzoate] chloride (Pt
L 2 Cl) or platinum [1,3-difluoro-4,6-di (2-pyridinyl) benzene] chloride (Pt-4).
Above-mentioned guest materials is selected the material that can launch a plurality of crests for use; Described material of main part is selected and need be met the following conditions:
A. its triplet energy level must be less than the triplet energy level of object, and energy level difference is greater than 0.25 eV;
B. emission peak is in the royal purple optical band;
C. has cavity transmission ability;
The material of described electron transfer layer, its electron-transporting is fast, and the order of magnitude reaches 10
-4
The emission crest of above-mentioned guest materials is at 600-700 nm wave band, and the emission peak of material of main part is at 400-500 nm wave band.
Above-mentioned material of main part is: N, N
'-bis-(1-naphthyl)-N, N
'-diphenyl-1,10-biphenyl-4,4
'-diamine (NPB), BNs (BN
1:
,
-N, N-diphenylamine-4,
-diphenyl-1,
-binaphthyl; BN
2:
,
-(9H-9-carbazole)-4,40-diphenyl-1,
-binaphthyl; And BN
3: 4,
-bis (9-(p-fluorophenyl)-9H-3-carbazolyl))-1,
-binaphthyl).
Above-mentioned guest materials is the phosphor material platinum complex.
Above-mentioned phosphor material platinum complex is: [2-(40,60-difluorophenyl) pyridinato-N,
)] (2,4-pentanedionato), platinum (II) complex phosphors, platinum [methyl-3,5-di-(2-pyridyl) benzoate] chloride (Pt
L 2 Cl) or platinum [1,3-difluoro-4,6-di (2-pyridinyl) benzene] chloride (Pt-4).
The material of above-mentioned electron transfer layer is: 4, and 7-Diphenyl-1,10-phenanthroline (Bphen) or 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI).
A kind of method for preparing above-mentioned organic electroluminescent plant illumination light source adopts vacuum vapour deposition, comprising: the preliminary treatment of ito glass substrate (1); The evaporation of hole transmission layer, the evaporation of electron transfer layer and evaporation metal electrode is characterized in that on electron transfer layer, and the method that adopts double source to steam altogether prepares luminescent layer by the evaporation rate of controlling two kinds of materials.
The acquisition of multiband spectrum needs a plurality of luminescent materials usually, has increased the complexity of technology.The present invention only adopts a kind of luminescent material just to obtain a plurality of wave bands, provides a kind of method simply to realize the plant illumination light source.Organic electroluminescent is except environmental protection, advantage such as energy-conservation and efficient, and it still is a kind of area source, can uniform irradiation at each position of plant.The emission crest is very wide, can select spectrum according to the needs of different plants.It can also obtain very high brightness in addition.
Description of drawings
Fig. 1 is the structural representation of the organic electroluminescent plant illumination light source of the embodiment of the invention one;
Fig. 2 is the spectrogram of the plant illumination light source of the embodiment of the invention one;
Fig. 3 is the structural representation of the organic electroluminescent plant illumination light source of the embodiment of the invention two;
Fig. 4 is the spectrogram of the plant illumination light source of embodiments of the invention two.
Embodiment
Embodiment one: referring to Fig. 1, organic function layer and Al electrode all adopt the method for vacuum thermal evaporation, and the method that luminescent layer 3 adopts double sources to steam is altogether controlled the doping content of object by evaporation rate.Doping content can change to 20 wt% from 2 wt%., under different levels of doping, emission spectrum generation obvious variation, referring to Fig. 2, what monomer launched is blue light, what bimolecular launched is ruddiness.Along with the increase of concentration, the bimolecular phenomenon is more and more obvious, thereby can obtain the required best blue light of plant and the ratio of ruddiness.Concrete preparation technology is as follows:
A) choose the ito glass substrate 1 of meet the requirements size and sheet resistance, deionized water and alcohol are ultrasonic with using respectively after the washed with de-ionized water, ultrasonic time was respectively 30 minutes and 20 minutes, and ultrasonic back is dried and handled 15 minutes with the UV ozone cleaning machine;
B) use vacuum vapour deposition, 1 evaporation preparation hole transmission layer 2 on above-mentioned ito substrate, speed is 0.03-0.1 nm/s, thickness is 40 nm.
C) above hole transmission layer, the method that adopts double source to steam altogether, preparation luminescent layer 4.Luminescent layer 4 adopts doped structure, and wiping assorted concentration can change 2%～20%, and doping content obtains by the evaporation rate of two kinds of materials of crystal-vibration-chip control.For example selecting mCP for use is main body,, Pt-4 is an object, doping content is controlled at 5%.The rate stabilization that makes Pt-4 is earlier modulated the speed of mCP again at 0.02 nm/S, makes it reach 0.4 nm/s, and the doping content of object just is controlled at 5% like this, and thickness is 20 nm.
D) method of employing vacuum evaporation, 3 preparation electron transfer layers 4 on above-mentioned luminescent layer, evaporation rate is 0.03-0.1 nm/s, thickness is 40 nm.
E) evaporation metal electrode 5 on whole base plate, evaporation rate＞5 nm/s can more than thickness 100 nm.
This has invented a kind of method of simple plant illumination light source, and all organic layers and negative electrode use vacuum vapour deposition, and vacuum degree maintains 10
-6Mbar.
Embodiment two: referring to Fig. 3, select for use emission dark blue light and triplet energy level less than the material of Pt-4 as main body, the material that electron-transporting is good is done electron transfer layer, make exciton be controlled at the HTL/EML interface, make bimolecular make the ruddiness of emission 660 nm, THL at the interface launches dark blue light simultaneously.Therefore we have obtained ruddiness about required growth light source-660 nm of plant and the dark blue light about 440 nm, referring to Fig. 4, can be absorbed effectively by chlorophyll a and chlorophyll b, thereby can improve illumination condition effectively, improve the efficiency of light energy utilization, the photosynthesis of fortification of plants.
The preparation method of organic electroluminescent plant illumination light source is as follows:
F) choose the ito glass substrate 1 of meet the requirements size and sheet resistance, deionized water and alcohol are ultrasonic with using respectively after the washed with de-ionized water, ultrasonic time was respectively 30 minutes and 20 minutes, and ultrasonic back is dried and handled 15 minutes with the UV ozone cleaning machine;
G) use vacuum vapour deposition, 1 evaporation preparation hole transmission layer 2 on above-mentioned ito substrate, speed is 0.03-0.1 nm/s, thickness is 40 nm.
H) above hole transmission layer, the method that adopts double source to steam altogether, preparation luminescent layer 4.Luminescent layer 4 adopts doped structure, and wiping assorted concentration can change 2%～20%, and doping content obtains by the evaporation rate of two kinds of materials of crystal-vibration-chip control.For example selecting NPB for use is main body, and Pt-4 is an object, and doping content is controlled at 5%.The rate stabilization that makes Pt-4 is earlier modulated the speed of NPB again at 0.02 nm/S, makes it reach 0.4 nm/s, and the doping content of object just is controlled at 5% like this, and thickness is 20 nm.
I) method of employing vacuum evaporation, 3 preparation electron transfer layers 4 on above-mentioned luminescent layer, evaporation rate is 0.03-0.1 nm/s, thickness is 40 nm.
J) evaporation metal electrode 5 on whole base plate, evaporation rate＞5 nm/s can more than thickness 100 nm.
This has invented a kind of method of simple plant illumination light source, and all organic layers and negative electrode use vacuum vapour deposition, and vacuum degree maintains 10
-6Mbar.
Claims (11)
1. organic electroluminescent plant illumination light source, by ito glass substrate (1), hole transmission layer (2), luminescent layer (3), electron transfer layer (4) and metal electrode (5), it is characterized in that described luminescent layer (3) is the material doped system of Subjective and Objective; Described guest materials doping content is 2 wt%～20 wt% of described material of main part quality.
2. organic electroluminescent plant illumination light source according to claim 1 is characterized in that described guest materials can the while emission spectrum be the monomer spectrum of 400-500 nm wave band and the bimolecular spectrum of 600-700 nm wave band; Described material of main part is: 1, and 3-bis (9-carbazolyl) benzene (mCP), 4,4 '-bis (9-carbazolyl)-biphenyl (CBP), or 4,4 ', 4 "-tris (N-carbazolyl)-triphenylamine (TCTA).
3. organic electroluminescent plant illumination light source according to claim 2 is characterized in that described guest materials is the complex of phosphor material platinum.
4. organic electroluminescent plant illumination light source according to claim 3 is characterized in that described phosphor material is the complex of platinum, can be: [2-(40,60-difluorophenyl) pyridinato-N,
)] (2,4-pentanedionato), platinum (II) complex phosphors, platinum [methyl-3,5-di-(2-pyridyl) benzoate] chloride (Pt
L 2 Cl) or platinum [1,3-difluoro-4,6-di (2-pyridinyl) benzene] chloride (Pt-4).
5. according to claim 1 organic electroluminescent plant illumination light source, it is characterized in that described guest materials selects the material that can launch a plurality of crests for use; Described material of main part is selected and need be met the following conditions:
Its triplet energy level must be less than the triplet energy level of object, and energy level difference is greater than 0.25 eV;
Emission peak is in the royal purple optical band;
Has cavity transmission ability;
The material of described electron transfer layer, its electron-transporting is fast, and the order of magnitude reaches 10
-4
6. a kind of organic electroluminescent plant illumination light source according to claim 5, the emission crest that it is characterized in that described guest materials is at 600-700 nm wave band, and the emission peak of material of main part is at 400-500 nm wave band.
7. organic electroluminescent plant illumination light source according to claim 6 is characterized in that described material of main part is: N, N
'-bis-(1-naphthyl)-N, N
'-diphenyl-1,10-biphenyl-4,4
'-diamine (NPB), BNs (BN
1:
,
-N, N-diphenylamine-4,
-diphenyl-1,
-binaphthyl; BN
2:
,
-(9H-9-carbazole)-4,40-diphenyl-1,
-binaphthyl; And BN
3: 4,
-bis (9-(p-fluorophenyl)-9H-3-carbazolyl))-1,
-binaphthyl).
8. organic electroluminescent plant illumination light source according to claim 6 is characterized in that described guest materials is the phosphor material platinum complex.
9. organic electroluminescent plant illumination light source according to claim 8 is characterized in that described phosphor material platinum complex is: [2-(40,60-difluorophenyl) pyridinato-N,
)] (2,4-pentanedionato), platinum (II) complex phosphors, platinum [methyl-3,5-di-(2-pyridyl) benzoate] chloride (Pt
L 2 Cl) or platinum [1,3-difluoro-4,6-di (2-pyridinyl) benzene] chloride (Pt-4).
10. organic electroluminescent plant illumination light source according to claim 5, the material that it is characterized in that described electron transfer layer is: 4,7-Diphenyl-1,10-phenanthroline (Bphen) or 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI).
11. a method for preparing according to each described organic electroluminescent plant illumination light source in the claim 1-9 adopts vacuum vapour deposition, comprising: the preliminary treatment of ito glass substrate (1); The evaporation of the evaporation of hole transmission layer (2), electron transfer layer (4) and evaporation metal electrode (5), it is characterized in that on electron transfer layer (4), the method that adopts double source to steam altogether prepares luminescent layer (3) by the evaporation rate of controlling two kinds of materials.
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| CN102516979A (en) * | 2011-12-01 | 2012-06-27 | 上海大学 | Color conversion organic material for plant lighting source and application thereof |
| CN103151469A (en) * | 2013-03-20 | 2013-06-12 | 上海大学 | High-rendering-index white-light organic electroluminescence device and preparation method thereof |
| CN103219473A (en) * | 2013-04-26 | 2013-07-24 | 上海大学 | White organic light emitting device with single light emitting layer structure |
| CN103606630A (en) * | 2013-12-13 | 2014-02-26 | 天津理工大学 | Organic electroluminescent red and blue light photosynthetic conversion glass plate light source |
| CN109285953A (en) * | 2017-07-21 | 2019-01-29 | 上海和辉光电有限公司 | A kind of organic light emitting display panel and electronic equipment |
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