CN100440572C - Organic / macromolecule top emission light-emitting device and its application - Google Patents

Organic / macromolecule top emission light-emitting device and its application Download PDF

Info

Publication number
CN100440572C
CN100440572C CNB2005100348966A CN200510034896A CN100440572C CN 100440572 C CN100440572 C CN 100440572C CN B2005100348966 A CNB2005100348966 A CN B2005100348966A CN 200510034896 A CN200510034896 A CN 200510034896A CN 100440572 C CN100440572 C CN 100440572C
Authority
CN
China
Prior art keywords
poly
emitting device
fluorenes
top emission
emission light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100348966A
Other languages
Chinese (zh)
Other versions
CN1731901A (en
Inventor
曹镛
侯林涛
黄飞
彭俊彪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou New Vision Optoelectronic Co., Ltd.
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CNB2005100348966A priority Critical patent/CN100440572C/en
Publication of CN1731901A publication Critical patent/CN1731901A/en
Priority to PCT/CN2006/000977 priority patent/WO2006128352A1/en
Application granted granted Critical
Publication of CN100440572C publication Critical patent/CN100440572C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3026—Top emission

Abstract

The present invention discloses an organic/ macromolecule top light emitting device which comprises a glass substrate, a negative pole, an emitting layer and an anode and is characterized in that an electron injection layer adopting a polarity unit conjugated polymer containing polar groups or ionicity groups is arranged between the cathode and the light emitting layer. The present invention also discloses the application of the top light emitting device in a high recognition panchromatic plane top transmitting display. The top light emitting device is characterized in that a compound cathode is formed by using a high work function metal cathode arranged on the substrate and a conjugation polymer containing strong polarity components of polar groups or ionicity groups to realize effective electron injection. Electric fluorescence is emitted through a translucent anode plated on the light emitting layer in a steaming mode. The present invention has the advantages of stabilisation and high efficiency.

Description

A kind of organic molecule or macromolecule top emission light-emitting device
Technical field
The present invention relates to a kind of novel top emission light-emitting device, particularly a kind of organic/polymer top emission light-emitting device.
Background technology
Nineteen ninety, research troop of univ cambridge uk is that luminescent layer has been made first polymeric light-emitting element with conjugated structure PPV macromolecular material at first.Because the luminous high polymer device has lower cost for material, is easy to the large tracts of land moulding, driving voltage is low, and energy consumption is little, and emission wavelength can pass through the outstanding advantage of the tuning grade of material structure, is considered to and might be applied in the large-area flat-plate TV.
Along with the process of progress on the display application of plane of global organic/polymer luminescent device, developing efficiently, top emission light-emitting device more and more becomes one of problem that needs urgent research.Because with respect to general luminescent device, end emission just (the electroluminescence screen sends by substrate) device, the top emission has a sequence advantage, and the most outstanding a bit is exactly to adopt emission structure at top to realizing that the large-area flat-plate display is significant efficiently.To using active driving (TFT) with the large-area flat-plate TV, but the TFT switching device itself occupies certain area of substrate, cause the aperture opening ratio (area and Substrate Area ratio that electroluminescence can be passed through generally only are Substrate Area 50～70%) of TFT substrate to reduce.And the employing emission structure at top because only from the upper surface emission of substrate, can be realized nearly 100% aperture opening ratio in theory.
But realize that the emission structure at top device acquires a certain degree of difficulty, electrode material and structure there is new requirement, particularly when adopting negative electrode to place on the substrate, more difficult when luminous by anode surface, therefore at present (on the substrate) was anode bottom the top emission light-emitting device of the most of report of institute was limited to more in the document, and top (on the luminescent layer) is the device of semitransparent cathode.Micromolecule luminous aspect, the V. of Princeton university
Figure C20051003489600051
Utilized the metallic cathode thin layer of printing opacity to make the transparent dual emission device of micromolecule that a kind of emergent light is launched simultaneously from upper and lower surface in 1996 Deng the people, over-all quantum efficiency is 0.75%, wherein bottom-face luminous efficient than end face luminous efficiency high by about 10% ( , G.Gu, P.E.Burrows, S.R.Forrest and M.E.Thompson, Nature, 380,29 (1996)).Aspect phosphorescence, people such as C.Kwong reported the phosphor material top emission light-emitting device in 2003, at 10mA/cm 2Following upper surface current efficiency is 23.1cd/A, and lower surface current efficiency is 20.3cd/A, and working life surpasses 5000 hours (Raymond C.Kwong, Michael S.Weaver, Min-Hao Michael Lu, Yeh-Jiun Tung, Anna B.Chwang, Theodore X.Zhou, Michael Hack, Julie J.Brown, Organic Electronics, 4,155 (2003)).
At present, the top emission light-emitting device overwhelming majority of most of report is that anode is on substrate, the structure of transparent cathode evaporation on luminescent layer, having only seldom, the part report adopts structure (V.Bulovic, P.Tian, the P.E.Burrows of transparent anode on luminescent layer, M.R.Gokhale, S.R.Forrest and M.E.Thompson, Appl.Phys.Lett.70,2954 (1997); Samil KHO, Sunyoung SOHN andDonggeun JUNG, Jpn.J.Appl.Phys.42,552 (2003)).Bibliographical information cathodic modification layer generally adopts the alkali metal of low work function (as potassium, lithium, or alkaline-earth metal (as calcium, barium etc.) caesium),, but the alkalies and alkaline earth of this class low work function is easy and water, the oxygen reaction causes processing difficulties, and device needs tight sealing (L.H.Smith, J.A.E.Wasey and W.L.Barnes simultaneously, Appl.Phys.Lett.84,2986 (2004); R.B.Pode, C.J.Lee, D.G.Moon and J.I.Han, Appl.Phys.Lett.84,4614 (2004)).Perhaps, sputtering ITO layer (indium tin oxide) again after having plated thin metal layer, but the sputtering ITO energy is very big, causes the damage of luminescent layer easily, influences the luminous (G.Gu of device, V.Bulovic, P.B.Burrows, S.R.Forrest and M.E.Thompson, Appl.Phys, Left.68,2606 (1996); L.S.Hung, C.W.Tang, Appl.Phys.Lett.74,3209 (1999)).Simultaneously, also by the compound no metal level that adopts transparent ITO and micromolecule electron transfer layer to form as the top emission light-emitting device negative electrode, same because the sputtering ITO layer is to carry out under high-energy, and the micromolecule electron transfer layer can not stop the infringement of luminescent layer fully, cause device failure cancellation (G.Parthasarathy easilier than metal level, P.E.Burrows, V.Khalfin, V.G.Kozlov, and S.R.Forrest, Appl.Phys.Lett.72,2138 (1998)).Perhaps, the low work function alkali metal that mixes is again arranged also between micromolecule electron transfer layer and ITO, improve device efficiency (G.Parthasarathy, C.Adachi, P.E.Burrows, and S.R.Forrest, Appl.Phys.Lett.76,2128 (2000)).Aspect sputter, also there is technology not adopt ITO, but the indium oxide (IDIXO) of sputter doping zinc, same damage luminescent layer problem (the Asuka Yamamori easily that exists of this method, Sachiko Hayashi, Toshiki Koyama, and Yoshio Taniguchi, Appl.Phys.Lett.78,3343 (2001); Takashi Hirano, US6774561).In addition, also utilize the plasma technology to form one deck insulating nitride layer at cathode surface, significantly improved device performance, but this manufacture craft relative complex, plasma time requirement strictness (Samil KHO to device substrate, Sunyoung SOHN and Donggeun JUNG, Jpn.J.Appl.Phys.42,552 (2003)).The same with the effect of plasma metal level, also there is method directly to adopt people's methods such as Hung, directly evaporation one heat insulating lamina fluoride is on luminescent material, evaporation metal electrode again on fluoride layer, and such fluoride of forming/metal composite negative electrode also can obtain effective top emission light-emitting device (L.S.Hung, C.W.Tang, M.G.Tang, M.G.Mason, P.Raychaudhuri and J.Madathil, Appl.Phys.Lett.78,544 (2001); Chieh-Wei Chen, Chun-Liang Lin andChung-Chih Wu, Appl.Phys.Lett.85,2469 (2004); S.Han, X.Feng, Z.H.Lu, D.Johnson and R.Wood, Appl.Phys.Lett.82,2715 (2003); HAN Sijin, FENG Xiadong, LU Zhenghong, WOOD, Richard, P., JOHNSON, David, J., WO2004049465); Akio Fukase, US2004/0239239).In addition, the redox polymers (EB-PAni) that is reported in the polyaniline compound that adds one deck conduction between substrate metal layer and the luminescent layer is also arranged, perhaps mix and give body or acceptor material, realize injection (the Satoshi Seo in electronics or hole, Hiroko Yamazaki, US6838836).
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and a kind of organic/polymer top emission light-emitting device is provided.These top emission light-emitting device characteristics are to use one to place the high-work-function metal negative electrode on the substrate to form composite cathode with the conjugated polymer of the strong polar compound that contains polar group or ionic group, realize that effective electronics injects, electroluminescence is sent stability and high efficiency by the translucent anode of evaporation on luminescent layer.
The present invention is achieved through the following technical solutions: a kind of organic/polymer top emission light-emitting device, comprise substrate, negative electrode, luminescent layer, anode, it is characterized in that, establish an electron injecting layer between negative electrode and luminescent layer, described electron injecting layer adopts the conjugated polymer of the polarity unit that contains polar group or ionic group.Described substrate, negative electrode, luminescent layer, anode set gradually from the bottom up.
Described electron injecting layer is the conjugated polymer with polarity unit that contains polar group or ionic group of following structure:
Figure C20051003489600071
N wherein 1=0.5～0.99; n 2=0.1～0.5; n 3=0～0.5; n 1+ n 2+ n 3=1.0;
Wherein A is the polar compound that contains polar group or ionic group, has the combination of following wherein one or more structures:
Poly-fluorenes:
Figure C20051003489600072
R wherein 1, R 2For having wherein one or more side chain of amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, phosphate; n 1=0.5～0.99;
Poly-to benzene:
Figure C20051003489600081
R wherein 1, R 2For having amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, wherein one or more side chains of phosphate; n 1=0.5～0.99;
Wherein B has one or more following structures for not containing the component of polarity or ionic group:
Poly-fluorenes:
Figure C20051003489600082
R wherein 3, R 4Be H, C 1～C 20Alkyl; n 2=0.1～0.5;
Poly-to benzene:
Figure C20051003489600083
R wherein 3, R 4Be H, C 1～C 20Alkyl, alkoxyl; n 2=0.1～0.5;
Wherein C is any sulphur that contains, nitrogen, and the heterocycle of selenium comprises diazosulfide, selenole; Diazosulfide:
Figure C20051003489600084
n 3=0～0.5; Selenole:
Figure C20051003489600085
n 3=0～0.5.
The conjugated polymer monomer A also comprises p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole in the described electron injecting layer; The conjugated polymer monomers B also comprises p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole.
Above A, B, three kinds of compositions of C can obtain the target conjugated polymer by the Suzuki coupling reaction.
Synthetic and the chemistry of monomer and polymer, optical physics characteristic and standard back emission (substrate surface emission) preparation of devices reference literature carry out (Huang et al.J.Am.Chem.Soc.2004; 126 (31): 9845-9853; Chem.Mater.2004,16:708-716; PCT application No.PCT/CN2004/001417 (Dec.6,2004)).
Described electron injecting layer is PF-NR 2(poly-[9,9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-]), PF-N +R 3(poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group fluorenes) dibromo]), PFP-NR 2(poly-[1,4-phenylene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-]), PFP-N +R 3(poly-[1,4-phenylene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) the propyl group fluorenes) dibromo]), PFN-BTDZ (poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes-2,1, the 3-diazosulfide]), PFNBr-BTDZ (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-diazosulfide] dibromo), PFN-BseD (poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes-2,1, the 3-selenole]), PFNBr-BseD (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-selenole] dibromo), PFN-DBT (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide]), PFNBr-DBT (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide] dibromo), PFN-DBSe (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole]), PFNBr-DBSe (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole] dibromo), PFN-TPA-BTDZ (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2,1,3-diazosulfide-N-(4-phenyl)-4,4 '-diphenylamine]), PFNI-TPA-BTDZ (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-2,1,3-diazosulfide N-(4-phenyl)-4,4 '-diphenylamine] diiodo-), PFN-TH (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2, the 5-thiophene]) or PFNBr-TH (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-the N-ethyl ammonium) propyl group) fluorenes-2, the 5-thiophene] dibromo) in any one.
Described electron injecting layer thickness is 0.5～30 nanometer; Electron injecting layer by the solution in organic solvent by spin coated, ink-jet, the mode of solution film formings such as printing is coated on the luminescent layer.
Described negative electrode directly adopts work function more than or equal to 3.6 electron-volts high-work-function metal.
Described high-work-function metal is gold, aluminium, copper, silver, indium, nickel, lead, tin, carbon or its alloy.
Described luminescent layer adopts any organic molecule luminescent material or high-molecular luminous material; Described high-molecular luminous material comprises poly-fluorenes, poly-to benzene, p-phenylene vinylene, poly-spiral shell (SPIRO)-to benzene, trapezoidal poly-one or more co-mixing system in benzene (ladder-PPP) or the polyparaphenylene's acetylene.
Another object of the present invention is exactly the application of this organic/polymer top emission light-emitting device in the panchromatic planar top emission display of high-resolution.
Table 1 is that this tests used polarity electronics injection material.Three component copolymers (the monomer diazosulfide of narrow band gap) that comprise Ionized poly-[9,9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-] copolymerization narrow band gap (PFNBr-BTDZ05) and its neutral persursor material (PFN-BTDZ05).
Table 1 polarity electronics used in the present invention injection material
Figure C20051003489600091
Figure C20051003489600101
Figure C20051003489600111
Figure C20051003489600121
* the mole ratio of numeral heterocyclic monomer in copolymer after being called for short, as PFNBr-BTDZ10, the mole ratio of the BTDZ content in the expression copolymer is 10%.
The good metal of employing environmental stability of the present invention is such as aluminium during directly as the substrate negative electrode, employing by the conjugated polymer of the strong polar compound that contains ionic group or polar group as electron transfer layer, manufacture craft is very simple, and obtains the top emission light-emitting device of stability and high efficiency.In preparation top emission light-emitting device of the present invention, for overcome low workfunction metal in the device preparation process, be easy to solvent in residual water, the oxygen reaction, cause device efficiency to lower, the rapid difficulty in ageing failure and the processing that causes thus, and the low electron injection efficiency of employed high-work-function metal among the present invention, the solution of above-mentioned ionic polymers and neutral presoma thereof is passed through rotation, modes such as printing apply skim on the high-work-function metal cathode layer, swaying hair photosphere thereon plates translucent high-work-function metal again as anode then, and it is good to obtain environmental stability, efficiently, the top emission light-emitting device of the electronics of balance injection.
The present invention compared with prior art has following advantage and beneficial effect:
(1) no matter the used electric transmission co-polymer of the present invention can realize that to the red, green, blue three-colour light-emitting material of which kind of band gap width excellent electronics injects;
(2) with red, green, electronics can not be subjected to the influence of cathodic metal work function in the multilayer top emission light-emitting device that blue three-colour light-emitting polymer is formed, even use work function as gold is done negative electrode and anode simultaneously up to the high stable metal of 5.2eV, also can obtain and low work function injecting electrode high-quantum efficiency equally or more, the luminescent device that long-time stability are good is applicable to the panchromatic top of high-resolution plane of departure display;
(3) this class material of having a polar group is dissolvable in water in water or the methyl alcohol isopolarity solvent, and the luminous high polymer material generally is insoluble to this kind solvent, therefore between electron transfer layer and the luminescent layer mixing phenomena can not take place when constructing multilayer device;
(4) because high-work-function metals such as aluminium have excellent air and steam stability, the stability that the combination electrode tool that uses the metal of polymer provided by the present invention and high work function to form is processed in atmosphere, the stability of device itself also improves greatly, huge potential using value in organic and macromolecule top emission light emitting display technology;
(5) the top emission light-emitting device negative electrode in the invention is attached on the substrate, and general top emission light-emitting device is that anode is attached on the substrate, has great superiority when using on active driving display screen.
Description of drawings
Fig. 1 (a) is common end ballistic device structure chart.1a is a substrate glass, and 2a is transparent ito anode, and 3a is a hole transmission layer, and 4a is a luminescent layer, and 5a is an electron transfer layer, and 6a is a metallic cathode.
Fig. 1 (b) for transparent cathode make progress anode under the top emission light-emitting device structure chart.1b is a substrate, and 2b is an anode, and 3b is a hole transmission layer, and 4b is a luminescent layer, and 5b is an electron transfer layer, and 6b is a transparent cathode.
Fig. 1 (c) for transparent anode make progress negative electrode under the top emission light-emitting device structure chart.1c is a substrate, and 2c is a negative electrode, and 3c is an electron transfer layer, and 4c is a luminescent layer, and 5c is a hole transmission layer, and 6c is a transparent anode.The black representative is light tight among the figure.
Fig. 2 is the structural representation of top emission light-emitting device of the present invention.1 is substrate, and 2 is negative electrode, and 3 is electron injecting layer, and 4 is luminescent layer, and 5 is transparent anode.
Fig. 3 (a) makes electron injecting layer to PFNBr-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 3 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 4 (a) makes electron injecting layer to PFN-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 4 (b) is voltage-to-current-luminosity comparison diagram of making negative electrode, make the top emission light-emitting device of transparent anode with gold with golden.
Fig. 4 (c) makes negative electrode, makes the top emission light-emitting device electroluminescent spectrum of transparent anode with gold with aluminium.
Fig. 5 (a) is to PF-N +R 3Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 5 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 6 (a) is to PF-NR 2Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 6 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 7 (a) be to PFNBr-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 7 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Among Fig. 8 (a) be to PFN-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 8 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 9 (a) be with PFN-BTDZ05 as electron injecting layer, to the poly-fluorenes (PFO) of blue light-emitting, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 9 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Be to make negative electrode, make the voltage-to-current-luminosity figure of the individual layer top emission light-emitting device of transparent anode among Figure 10 (a) with gold with aluminium.
Figure 10 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but embodiments of the present invention are not limited thereto.
Being existing common end ballistic device structure chart as shown in Figure 1a, is end emission (the electroluminescence screen sends by substrate) device.As Fig. 1 b be depicted as existing transparent cathode make progress anode under top ballistic device structure chart, its structure of this top emission light-emitting device be anode on the substrate, the transparent cathode evaporation is on luminescent layer.The transparent anode that is depicted as existing report as Fig. 1 c make progress negative electrode under top ballistic device structure chart, this top emission light-emitting device adopts the structure of transparent anode on luminescent layer.The black representative is light tight among the figure.
As shown in Figure 2, be top emission light-emitting device of the present invention, stack gradually and constitute by glass substrate 1, high-work-function metal negative electrode 2, electron injecting layer 3, macromolecule/organic luminous layer 4, translucent high-work-function metal anode 5.
Below with Ionized poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized replacing (2,5-pair (3-[N, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N +R 3) or its neutral presoma copolymer (PF-NR 2) illustrate.Top emission light-emitting device is taked sandwich construction or single layer structure.When between traditional luminescent conjugated polymers and work function metal higher, that environmental stability, adaptability are good such as aluminium, gold, inserting the polyelectrolytes film of skim, the injection barrier of minority carrier electronics will be reduced greatly, thereby strengthen the injection efficiency of electronics, the balanced bipolar charge carrier, make hole-electron recombination, and then the efficient of radioluminescence (electroluminescent internal quantum efficiency) is improved.
Embodiment 1
The ITO electro-conductive glass, square resistance～20 Ω/ does not perhaps have the simple glass of ITO, precuts into 15 millimeters * 15 millimeters square sheets.Use acetone, micron order semiconductor special purpose detergent, deionized water, isopropyl alcohol ultrasonic cleaning successively, it is standby that the nitrogen purging is placed on constant temperature oven, is for further processing in the oxygen plasma washer before use.
Fluorescent conjugated polymer after the weighing, changes nitrogen protection film forming special gloves case (VAC company) in clean bottle, dissolve in toluene, with 0.45 micron membrane filtration.Polymer light-emitting layer optimum thickness is 70～90 nanometers.Thickness is measured with the TENCORALFA-STEP-500 surface profiler.With PFNBr-BTDZ05, PFN-BTDZ05, PF-N +R 3, PF-NR 2In methyl alcohol, dissolve respectively, be mixed with 0.02%, 0.1%, the solution of 0.2% 3 kind of concentration.Utilize sol evenning machine spin coated on the metallic cathode layer of evaporation in advance to generate their skim polymer, its thickness is respectively about 5,10,20 nanometers when getting rid of film when rotating with 2000rpm with 0.02%, 0.1%, 0.2% concentration.Aluminium or gold electrode evaporation vacuum degree in vacuum coating equipment reach 3 * 10 -4Finish when Pa is following.The thickness of plated film speed and each layer electrode is by quartz vibrator film thickness monitor (STM-100 type, Sycon company) monitoring in real time.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual zone that covers of ITO.All preparation process are all carried out the I-E characteristic of device in the glove box of nitrogen inert atmosphere is provided, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode.
Evaporation high work function aluminium (4.4 electron-volts) is on substrate, with Ionized poly-[9 of variable concentrations, 9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized alternately (2, two (the 3-[N of 5-, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N +R 3) or its neutral presoma copolymer (PF-NR 2) methanol solution under the thin layer of spin coating on the Al cathode layer as electron injecting layer, adopt the poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1 of 90 nanometer thickness, the 4-phenylacetylene)] (MEH-PPV) conjugated polymer thin films is a luminescent layer, vacuum evaporation covers gold (Au on the luminescent layer, 5.3 electron-volt) the 20nm laminate structure is made the polymer top emission light-emitting diode that sends tangerine color of light as transparent anode.As luminescent layer, to different electronics injection materials, measurement result is listed in table 2 (PFNBr-BTDZ05 makes electron injecting layer) respectively, table 3 (PFN-BTDZ05 makes electron injecting layer), table 4 (PF-N with MEH-PPV +R 3Make electron injecting layer), table 5 (PF-NR 2Make electron injecting layer).
Table 2 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFNBr-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on red light material MEH-PPV
Figure C20051003489600161
Top emission light-emitting device structure in the table 2 is ITO/Al/PFNBr-BTDZ05/MEH-PPV/Au.
Fig. 3 (a) makes electron injecting layer to PFNBr-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 3 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 3 based on red light material poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) is used the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron transfer layer
Figure C20051003489600172
Top emission light-emitting device structure in the table 3 is ITO/Al/PFN-BTDZ05/MEH-PPV/Au, and structure I TO/Au/PFN-BTDZ05/MEH-PPV/Au is a comparative device.
Fig. 4 (a) makes electron injecting layer to PFN-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 4 (b) be with gold do negative electrode, with golden do the top emission light-emitting device of transparent anode voltage-to-current-luminosity figure as a comparison.Fig. 4 (c) makes negative electrode, makes the top emission light-emitting device electroluminescent spectrum of transparent anode with gold with aluminium.
Table 4 is made negative electrode, is made transparent anode, uses PF-N with gold with aluminium based on red light material MEH-PPV +R 3Electroluminescent properties as the top emission light-emitting device of electron injecting layer
Figure C20051003489600173
Top emission light-emitting device structure in the table 4 is ITO/Al/PF-N +R 3/ MEH-PPV/Au.
Fig. 5 (a) is to PF-N +R 3Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 5 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 5 is made negative electrode, is made transparent anode, uses PF-NR with gold with aluminium based on red light material MEH-PPV 2Electroluminescent properties as the top emission light-emitting device of electron injecting layer
Figure C20051003489600182
Top emission light-emitting device structure in the table 5 is ITO/Al/PF-NR 2/ MEH-PPV/Au.
Fig. 6 (a) is to PF-NR 2Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 6 (b) is the electroluminescent spectrum of this top emission light-emitting device.
The result of example can prove absolutely the MEH-PPV to glowing thus, directly with placing the high work functions such as aluminium on the substrate to make negative electrode, make anode with transparent high-work-function metal Au, with Ionized poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized alternately (2, two (the 3-[N of 5-, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N +R 3) or its neutral presoma copolymer (PF-NR 2) make electron transport material respectively, realized red top emission light-emitting device.
Embodiment 2
Repeat example 1, replace p-phenylene vinylene (P-PPV) but the polymer light-emitting stratification is changed to the phenyl of green light, electron injecting layer adopts PFNBr-BTDZ05 or neutral presoma PFN-BTDZ05 respectively.Experimental result is summarized in table 6 and table 7 respectively.
Table 6 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFNBr-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on green light material P-PPV
Figure C20051003489600191
Top emission light-emitting device structure in the table 6 is ITO/Al/PFNBr-BTDZ05/P-PPV/Au.
Fig. 7 (a) be to PFNBr-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 7 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 7 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on green light material P-PPV
Top emission light-emitting device structure in the table 7 is ITO/Al/PFN-BTDZ05/P-PPV/Au.
Among Fig. 8 (a) be to PFN-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 8 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Make anode with transparent high-work-function metal Au, make the electronics injection material, realized green top emission light-emitting device with ionization PFNBr-BTDZ05 or neutral presoma PFN-BTDZ05.
Embodiment 3
Repeat the poly-fluorenes (PFO) that example 2 is changed to the polymer light-emitting stratification blue light-emitting, with poly-[9,9-dioctyl fluorene-9, two (N, N-dimethyl amine propyl group) fluorenes of 9-] three component copolymers (the monomer diazosulfide of narrow band gap) of copolymerization narrow band gap (PFN-BTDZ05) make electron injecting layer.Experimental result is summarized in table 8.Fig. 9 (a) be with PFN-BTDZ05 as electron injecting layer, to the poly-fluorenes (PFO) of blue light-emitting, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 9 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 8 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on blue light material PFO
Figure C20051003489600201
Top emission light-emitting device structure in the table 8 is ITO/Al/PFN-BTDZ05/PFO/Au.
The result of example can prove absolutely the PFO to blue light-emitting thus, directly makes negative electrode, makes anode with transparent high-work-function metal Au with high work functions such as aluminium, makes electron transport material with PFN-BTDZ05, has realized blue top emission light-emitting device.
Embodiment 4
Directly with polar polymer PFN-BTDZ05 as luminescent layer, other condition is constant.Experimental result is summarized in table 9.Be to make negative electrode, make the voltage-to-current-luminosity figure of the individual layer top emission light-emitting device of transparent anode among Figure 10 (a) with gold with aluminium.Figure 10 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 9 is based on material PFN-BTDZ05, makes negative electrode, makes the electroluminescent properties of the individual layer top emission light-emitting device of transparent anode with gold with aluminium
Top emission light-emitting device structure in the table 9 is ITO/Al/PFN-BTDZ05/Au.
The result of example can prove absolutely the polar material PFN-BTDZ05 for individual layer thus, directly makes negative electrode, makes anode with transparent high-work-function metal Au with high work functions such as aluminium, has realized the individual layer top emission light-emitting device.
Embodiment 5
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
Be luminescent layer wherein, make the high-work-function metal negative electrode, make transparent anode, use PFP-NR with gold with gold with red light material MEH-PPV 2As the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 0.5 nanometer.
Embodiment 6
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with copper, uses PFP-N +R 3As the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 1 nanometer.
Embodiment 7
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with silver, and with the top emission light-emitting device of PFN-BseD as electron injecting layer, electron injecting layer thickness is 5 nanometers.
Embodiment 8
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with indium, and with the top emission light-emitting device of PFNBr-BseD as electron injecting layer, electron injecting layer thickness is 10 nanometers.
Embodiment 9
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
Co-mixing system with MEH-PPV and P-PPV is a luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with nickel, and with the top emission light-emitting device of PFN-DBT as electron injecting layer, electron injecting layer thickness is 15 nanometers.
Embodiment 10
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With p-phenylene vinylene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with lead, and with the top emission light-emitting device of PFNBr-DBT as electron injecting layer, electron injecting layer thickness is 20 nanometers.
Embodiment 11
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
To gather benzene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with tin, and with the top emission light-emitting device of PFN-DBSe as electron injecting layer, electron injecting layer thickness is 25 nanometers.
Embodiment 12
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With poly-spiral shell (SPIRO)-to benzene is luminescent layer, makes negative electrode, makes transparent anode with gold with carbon, and with the top emission light-emitting device of PFNBr-DBSe as electron injecting layer, electron injecting layer thickness is 30 nanometers.
Embodiment 13
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With trapezoidal poly-be luminescent layer to benzene (ladder-PPP), make negative electrode, make transparent anode with graphite with gold, usefulness PFN-TPA-BTDZ is as the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 12 nanometers.
Embodiment 14
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With polyparaphenylene's acetylene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with terne metal, and with the top emission light-emitting device of PFNI-TPA-BTDZ as electron injecting layer, electron injecting layer thickness is 8 nanometers.
Embodiment 15
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With micromolecule luminescent material tris-(8-hydroxyquinoline) aluminum (AlQ3) is luminescent layer, makes negative electrode, makes transparent anode with gold with aluminium, and with the top emission light-emitting device of PFN-TH as electron injecting layer, electron injecting layer thickness is 12 nanometers.
Embodiment 16
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With the metal complex phosphor material Bis (1-phenylisoquinoline) of triplet state phosphor material such as iridium (acetylacetonate) iridium (III) be luminescent layer (PhqIr), make the high-work-function metal negative electrode, make transparent anode with aluminium with gold, with the top emission light-emitting device of PFNBr-TH as electron injecting layer, electron injecting layer thickness is 9 nanometers.

Claims (9)

1, a kind of organic molecule or macromolecule top emission light-emitting device, comprise substrate, negative electrode, luminescent layer, anode, it is characterized in that, between negative electrode and luminescent layer, establish an electron injecting layer, described electron injecting layer adopts the conjugated polymer of the polarity unit that contains polar group or ionic group, and described substrate, negative electrode, luminescent layer, anode set gradually from the bottom up;
Described electron injecting layer is the conjugated polymer with polarity unit that contains polar group or ionic group of following structure:
Figure C2005100348960002C1
N wherein 1=0.5～0.99; n 2=0.1～0.5; n 3=0～0.5; n 1+ n 2+ n 3=1.0;
Wherein A is the polar compound that contains polar group or ionic group,
Figure C2005100348960002C2
Combination with following wherein one or more structures:
Poly-fluorenes:
Figure C2005100348960002C3
R wherein 1, R 2For having wherein one or more side chain of amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, phosphate; n 1=0.5～0.99;
Poly-to benzene:
Figure C2005100348960002C4
R wherein 1, R 2For having wherein one or more side chain of amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, phosphate; n 1=0.5～0.99;
Wherein B is the component that does not contain polar group or ionic group,
Figure C2005100348960002C5
Have one or more following structures:
Poly-fluorenes:
Figure C2005100348960002C6
R wherein 3, R 4Be H or C 1～C 20Alkyl; n 2=0.1～0.5;
Poly-to benzene:
Figure C2005100348960002C7
R wherein 3, R 4Be H or C 1～C 20Alkyl or alkoxyl; n 2=0.1～0.5;
Wherein C comprises diazosulfide or selenole;
Diazosulfide:
Figure C2005100348960003C1
Selenole:
Figure C2005100348960003C2
2, a kind of organic molecule according to claim 1 or macromolecule top emission light-emitting device is characterized in that, conjugated polymer in the described electron injecting layer
Figure C2005100348960003C3
Also comprise p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole; Conjugated polymer
Figure C2005100348960003C4
Also comprise p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole.
3, a kind of organic molecule according to claim 1 and 2 or macromolecule top emission light-emitting device, it is characterized in that, described electron injecting layer is poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) the propyl group fluorenes) dibromo], poly-[1,4-phenylene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes], poly-[1,4-phenylene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) the propyl group fluorenes) dibromo], poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes-2,1,3-diazosulfide], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-diazosulfide] dibromo, poly-[9,9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes-2,1 of 9-, 3-selenole], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-selenole] dibromo, poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide] dibromo, poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole] dibromo, poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2,1,3-diazosulfide-N-(4-phenyl)-4,4 '-diphenylamine], poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-2,1,3-diazosulfide N-(4-phenyl)-4,4 '-diphenylamine] diiodo-, poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2, the 5-thiophene] or poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2, the 5-thiophene] in the dibromo any one.
4, a kind of organic molecule according to claim 1 and 2 or macromolecule top emission light-emitting device is characterized in that, described electron injecting layer thickness is 0.5～30 nanometer.
5, a kind of organic molecule according to claim 3 or macromolecule top emission light-emitting device is characterized in that, described electron injecting layer thickness is 0.5～30 nanometer.
6, a kind of organic molecule according to claim 1 or macromolecule top emission light-emitting device is characterized in that, described negative electrode directly adopts work function more than or equal to 3.6 electron-volts high-work-function metal.
7, a kind of organic molecule according to claim 6 or macromolecule top emission light-emitting device is characterized in that, described high-work-function metal is gold, aluminium, copper, silver, indium, nickel, lead, tin or its alloy.
8, a kind of organic molecule according to claim 1 or macromolecule top emission light-emitting device is characterized in that, described luminescent layer adopts organic molecule luminescent material or high-molecular luminous material; Described high-molecular luminous material comprises poly-fluorenes, poly-to benzene, p-phenylene vinylene, poly-spiral shell-to one or more the co-mixing system in benzene or the polyparaphenylene's acetylene.
9, a kind of organic molecule according to claim 8 or macromolecule top emission light-emitting device is characterized in that, described gathering comprises trapezoidal gathering benzene to benzene.
CNB2005100348966A 2005-05-31 2005-05-31 Organic / macromolecule top emission light-emitting device and its application Expired - Fee Related CN100440572C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CNB2005100348966A CN100440572C (en) 2005-05-31 2005-05-31 Organic / macromolecule top emission light-emitting device and its application
PCT/CN2006/000977 WO2006128352A1 (en) 2005-05-31 2006-05-15 An organic/high molecular light emitting device of top emission type and utilization thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100348966A CN100440572C (en) 2005-05-31 2005-05-31 Organic / macromolecule top emission light-emitting device and its application

Publications (2)

Publication Number Publication Date
CN1731901A CN1731901A (en) 2006-02-08
CN100440572C true CN100440572C (en) 2008-12-03

Family

ID=35964175

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100348966A Expired - Fee Related CN100440572C (en) 2005-05-31 2005-05-31 Organic / macromolecule top emission light-emitting device and its application

Country Status (2)

Country Link
CN (1) CN100440572C (en)
WO (1) WO2006128352A1 (en)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009536980A (en) 2006-05-11 2009-10-22 ノースウェスタン ユニバーシティ Silole-based polymers and semiconductor materials prepared from these polymers
EP2249411A4 (en) 2008-03-07 2014-03-26 Sumitomo Chemical Co Layered structure
CN102612764B (en) 2009-09-30 2015-09-30 住友化学株式会社 Laminate structure, polymer, electroluminescent cell and photo-electric conversion element
WO2012002284A1 (en) 2010-06-29 2012-01-05 住友化学株式会社 Light emitting element, photoelectric conversion element, method for producing light emitting element, and method for producing photoelectric conversion element
JP2013533918A (en) * 2010-07-12 2013-08-29 ウェイク フォレスト ユニバーシティ Conjugated polymer systems and their applications
CN103120020B (en) * 2010-07-21 2016-03-23 住友化学株式会社 The manufacture method of organic electroluminescent device
JP5982747B2 (en) * 2010-07-21 2016-08-31 住友化学株式会社 Organic EL device
JP2012216815A (en) 2011-03-28 2012-11-08 Sumitomo Chemical Co Ltd Electronic device, polymer compound
JP2012214689A (en) 2011-03-28 2012-11-08 Sumitomo Chemical Co Ltd Composition
US9306169B2 (en) 2011-03-28 2016-04-05 Sumitomo Chemical Company, Limited Electronic device, polymer compound, organic compound, and method of producing polymer compound
US9541480B2 (en) 2011-06-29 2017-01-10 Academia Sinica Capture, purification, and release of biological substances using a surface coating
CN102417587A (en) * 2011-11-04 2012-04-18 华南理工大学 Electro-phosphorescence polymer containing (alkyl-substituted-)S,S- dioxo-dibenzothiophene unit and application thereof
CN102718946A (en) * 2012-05-30 2012-10-10 华南理工大学 Organic semiconducting polymer and solar battery comprising same
CN103833983B (en) * 2012-11-27 2016-04-13 海洋王照明科技股份有限公司 And [3,2-b] two selenophens-benzo two (selenole) multipolymer and its preparation method and application
CN103833979B (en) * 2012-11-27 2016-04-13 海洋王照明科技股份有限公司 And three thiophene-benzo two (selenole) multipolymer and its preparation method and application
CN104072733B (en) * 2013-03-29 2016-04-13 海洋王照明科技股份有限公司 Containing the multipolymer and its preparation method and application of di-thiophene-benzo two (selenole)
TW201623605A (en) 2014-04-01 2016-07-01 中央研究院 Methods and systems for cancer diagnosis and prognosis
JP6329427B2 (en) * 2014-05-09 2018-05-23 住友化学株式会社 Photoelectric conversion element
CN104788649B (en) * 2015-03-06 2017-12-01 华南理工大学 A kind of electron transport layer materials and perovskite solar cell
CN104821374B (en) * 2015-03-12 2017-10-20 华南理工大学 The preparation method and application of organic electro-optic device cathode interface layer based on conjugated polyelectrolytes
WO2017003382A1 (en) * 2015-07-01 2017-01-05 National University Of Singapore A n-doped electrically conductive polymeric material
US10107726B2 (en) 2016-03-16 2018-10-23 Cellmax, Ltd. Collection of suspended cells using a transferable membrane
CN106206984A (en) 2016-08-18 2016-12-07 京东方科技集团股份有限公司 Top emission type organic electroluminescence device and preparation method thereof, display device
TWI740036B (en) * 2018-05-03 2021-09-21 國立陽明交通大學 Organic light emitting device and method of manufacturing the same
CN115611827A (en) * 2021-07-15 2023-01-17 中国科学院化学研究所 Fluorescent sensing material, preparation method thereof and application thereof in organic arsenic detection

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6580214B2 (en) * 1998-02-27 2003-06-17 Sanyo Electric Co., Ltd. Color display apparatus having electroluminescence elements
CN1456026A (en) * 2001-01-15 2003-11-12 索尼公司 Luminescence device and its manufacturing method
CN1555103A (en) * 2003-12-25 2004-12-15 �Ϻ���ͨ��ѧ Organic/high molecular light emitting diode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1104036A3 (en) * 1999-11-29 2005-05-04 Canon Kabushiki Kaisha Liquid crystal device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6580214B2 (en) * 1998-02-27 2003-06-17 Sanyo Electric Co., Ltd. Color display apparatus having electroluminescence elements
CN1456026A (en) * 2001-01-15 2003-11-12 索尼公司 Luminescence device and its manufacturing method
CN1555103A (en) * 2003-12-25 2004-12-15 �Ϻ���ͨ��ѧ Organic/high molecular light emitting diode

Also Published As

Publication number Publication date
WO2006128352A1 (en) 2006-12-07
CN1731901A (en) 2006-02-08

Similar Documents

Publication Publication Date Title
CN100440572C (en) Organic / macromolecule top emission light-emitting device and its application
US10673009B2 (en) Planar electroluminescent devices and uses thereof
Lee et al. Highly efficient, deep‐blue doped organic light‐emitting devices
US9437842B2 (en) Light-emitting transistors with improved performance
EP1010359B1 (en) Color variable bipolar/ac light-emitting devices
US8586968B2 (en) Organic light emitting diode having high efficiency and process for fabricating the same
CN100446634C (en) Organic photoelectric assembly, electrode structure for it and method for improving its operation effect
KR100560785B1 (en) Organic electroluminecent display device driven by low voltage
US7621793B2 (en) Organic electro luminescent device and method of manufacturing organic electro luminescent device
US20050276994A1 (en) Light-emitting device
US20060081840A1 (en) Organic electronic device and method for producing the same
EP3426008B1 (en) Transparent layers of high conductivity and high efficiency in oleds and process for their production
US20050236973A1 (en) Electroluminescent assembly
KR100579342B1 (en) Electroluminescent device
US8569743B2 (en) Light-emitting component
KR20070067535A (en) Organic electroluminescence device
CN101599532A (en) A kind of organic electro-optic device and preparation method thereof
Cacialli et al. Naphthalimide polymers for organic light-emitting diodes
US20080191616A1 (en) Polymer light-emitting devices based on interfaces enables by internally compensated doped conjugated ionomers
KR100567220B1 (en) Organic light emitting device and display on the basis of organic light emitting device with improved effciency
Kim et al. Red Organic Light-emitting Diodes utilizing Energy Transfer and Charge Trapping
Xie et al. The effect of the CsCl buffer layer on the performances of the organic electro-luminescent devices
Vyavahare et al. Enhanced Performance of Organic Light Emitting Diodes using LiF Buffer Layer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: GUANGZHOU SOUTH CHINA UNIVERSITY OF TECHNOLOGY STA

Free format text: FORMER OWNER: SOUTH CHINA UNIVERSITY OF TECHNOLOGY

Effective date: 20100521

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 510640 NO.381 WUSHAN ROAD, TIANHE DISTRICT, GUANGZHOU CITY, GUANGDONG PROVINCE TO: 510640 FLOOR 3, HUAGONGDA GROUP BUILDING, NO. 381, WUSHAN ROAD, TIANHE DISTRICT, GUANGZHOU CITY, DONGGUAN CITY, GUANGDONG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20100521

Address after: 510640, No. 381, No. five, mountain road, Tianhe District, Guangdong, Guangzhou, China

Patentee after: Guangzhou South China University of Technology Asset Management Co., Ltd.

Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381,

Patentee before: South China University of Technology

ASS Succession or assignment of patent right

Owner name: GUANGZHOU NEW VISION PHOTOELECTRIC TECHNOLOGY CO.,

Free format text: FORMER OWNER: GUANGZHOU SOUTH CHINA UNIVERSITY OF TECHNOLOGY CAPITAL MANAGEMENT CO., LTD.

Effective date: 20101102

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 510640 3/F, SOUTH CHINA UNIVERSITY OF TECHNOLOGY GROUP BUILDING, NO.381, WUSHAN ROAD, TIANHE DISTRICT, GUANGZHOU CITY, GUANGDONG PROVINCE TO: 510663 1/F, BUILDING A1, NO.11, KAIYUAN AVENUE, SCIENCE CITY, GUANGZHOU NEW + HIGH TECHNOLOGY INDUSTRY DEVELOPMENT ZONE, GUANGZHOU CITY, GUANGDONG PROVINCE, 2/F

TR01 Transfer of patent right

Effective date of registration: 20101102

Address after: 510663, A1 building, No. 11, Kaiyuan Avenue, Science City, Guangzhou hi tech Industrial Development Zone, Guangdong, Guangzhou, first, second

Patentee after: Guangzhou New Vision Optoelectronic Co., Ltd.

Address before: 510640, No. 381, No. five, mountain road, Tianhe District, Guangdong, Guangzhou, China

Patentee before: Guangzhou South China University of Technology Asset Management Co., Ltd.

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20081203

Termination date: 20200531

CF01 Termination of patent right due to non-payment of annual fee