CN103928629A - Organic electroluminescence apparatus and preparation method thereof - Google Patents
Organic electroluminescence apparatus and preparation method thereof Download PDFInfo
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- CN103928629A CN103928629A CN201310010864.7A CN201310010864A CN103928629A CN 103928629 A CN103928629 A CN 103928629A CN 201310010864 A CN201310010864 A CN 201310010864A CN 103928629 A CN103928629 A CN 103928629A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention provides an organic electroluminescence apparatus and a preparation method thereof. In the organic electroluminescence apparatus prepared by using the method, a transparent conductive oxide film is employed as a cathode, a pn junction layer is arranged between an organic luminescence function layer and the cathode, and the pn junction layer comprises a first metal layer, an intermediate layer and a second metal layer which are successively stacked, such that the electron injection capability is improved, and a stable and uniform luminous effect is obtained. The preparation method is simple in process, free from pollution and easy to control, and facilitates industrial production.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, be specifically related to a kind of Organnic electroluminescent device and preparation method thereof.
Background technology
Organnic electroluminescent device is a kind of taking organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
Organnic electroluminescent device can be prepared into large area, high efficiency active matrix organic light-emitting diode (AMOLED) panel (AMOLED) with thin-film transistor (TFT) configuration, adopts the Organnic electroluminescent device of inversion type can expand the preparation scheme of AMOLED and reduce costs.In prior art, the Organnic electroluminescent device of the inversion type of lower bright dipping uses thin layer low workfunction metal to prepare negative electrode conventionally, and negative electrode light transmission rate only has 60% ~ 70%, and illumination effect is not good.And the material of low work function is too active, affects packaged stability.
If using transparent conductive oxide film as negative electrode, because its work function is higher, can reduce the injectability of electronics to organic luminous layer, electronic injection ability is one of principal element determining Organnic electroluminescent device luminosity and luminous efficiency, therefore, lower electronic injection ability can cause Organnic electroluminescent device poor performance, luminous efficiency low.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of Organnic electroluminescent device and preparation method thereof.Organnic electroluminescent device prepared by the present invention has adopted transparent conductive oxide film as negative electrode, and ties layer raising electronic injection ability by pn is set, thereby obtains stable, uniform illumination effect.Preparation method's technique of the present invention is simple, pollution-free, be easy to control, be beneficial to suitability for industrialized production.
Solving the technical scheme that technical problem of the present invention takes is: a kind of Organnic electroluminescent device is provided, comprise the underlay substrate, negative electrode, pn knot layer, organic luminescence function layer, the anode that stack gradually, described pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, the metal surface work function of described the first metal layer is more than or equal to 5.1eV, the material in described intermediate layer is the mixture that metal and metal oxide form, described metal is the same with the material of described the first metal layer, and described metal oxide is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, the material of described the second metal level is Li, Na, Rb or Cs.
The material of negative electrode is transparent conductive oxide film.Transparent conductive oxide film has the advantages such as transmitance is high, good conductivity, makes Organnic electroluminescent device have higher light permeable rate, uniformly luminosity.Preferably, the material of transparent conductive oxide film is indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO).
Preferably, the thickness of negative electrode is 70 ~ 200nm.
Preferably, the material of the first metal layer is Au, Cu, Ni, Pt or Ag.
Preferably, the thickness of the first metal layer is 10 ~ 25nm.
The transparent conductive oxide film of the first metal layer and negative electrode with contact the contact that belongs to two kinds of conductors, there is not the problem of injection barrier, therefore can greatly improve electron injection efficiency.The metal surface work function of the first metal layer is more than or equal to 5.1eV, and the work function of the metal of selecting approaches the work function of transparent conductive oxide film, can obtain good injection effect.
Preferably, the mass ratio of metal and metal oxide is 1:2 ~ 1:10.
Metal in the material in intermediate layer is the same with the material of the first metal layer, is selected from Au, Cu, Ni, Pt or Ag.
Metal oxide in the material in intermediate layer is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, there is semiconductor property, be clipped between the metal of two different work functions, make metal that two work functions are different under external electrical field, form an internal electric field, thereby the hole of metal oxide inside is separated with electronics, be injected into respectively in two kinds of adjacent metal materials.
Use the metal the same with the material of the first metal layer to mix with metal oxide, as intermediate layer, the potential barrier that need overcome can make hole move to the first metal layer time reduces, thereby reduce on the whole the driving voltage of light-emitting device, and improved the conductivity in intermediate layer and the effect of separation of charge.
Preferably, the thickness in intermediate layer is 3 ~ 8nm.
The material of the second metal level is Li, Na, Rb or Cs, belongs to the metal of low work function.
Preferably, the thickness of the second metal level is 5 ~ 20nm.
Under the effect of external electrical field, be positioned at the inner separation of charge that forms of metal oxide in pn knot layer intermediate layer, hole and electronics move to the first metal layer and the second metal level respectively, thereby electronics is directly injected into organic luminescence function layer from the second metal level, and the transparent conductive oxide film of negative electrode and contacting of the first metal layer belong to the contact of two kinds of conductors, there is not the problem of injection barrier, therefore greatly improved electron injection efficiency.The balance that electronic injection and hole are injected, can improve hole and electronics recombination probability and the luminous quantum efficiency in luminescent layer, the final Organnic electroluminescent device with higher luminescent properties that obtains.And this inversion type structure can make the second metal level be subject to the protection of underlay substrate.
Preferably, organic luminescence function layer comprises luminescent layer, electron transfer layer, hole transmission layer and hole injection layer.In organic luminescence function layer, the material of each layer is material conventional in this area.
Preferably, the material of main part of luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 10-(2-[4-morpholinodithio)-2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7,-tetramethyl L-1H, 5H, 11H-[1] benzopyran ketone group [6, 7, 8-IJ] quinolizine-11-ketone (C545T), two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl (DPVBi), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close one or more in iridium (Ir (ppy) 3).
Preferably, the material of luminescent layer is for being doped to according to doping mass fraction 5 ~ 15% composite material forming in material of main part by one or both guest materialss, and wherein guest materials is hole mobile material or electron transport material.
Preferably, the thickness of luminescent layer is 5 ~ 20nm.
Preferably, hole mobile material comprises Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) and 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, electron transport material comprises 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), oxine aluminium (Alq3), 4, 7-diphenyl-o-phenanthroline (Bphen), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole (TAZ) and two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq).
Preferably, the material of electron transfer layer is electron transport material, be selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), oxine aluminium (Alq3), 4, 7-diphenyl-o-phenanthroline (Bphen), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole (TAZ) or two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq).
Preferably, the thickness of electron transfer layer is 30 ~ 60nm.
Preferably, the material of hole transmission layer is hole mobile material, is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, the thickness of hole transmission layer is 10 ~ 60nm.
Preferably, the material of hole injection layer is Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, the thickness of hole injection layer is 10 ~ 60nm.
Preferably, the material of anode is metal A u, Cu, Ni or Ag.
Preferably, the thickness of anode is 80 ~ 200nm.
And, a kind of preparation method of Organnic electroluminescent device, it comprises the steps:
Underlay substrate is provided, described underlay substrate is carried out to ultrasonic cleaning, after cleaning up, in ultrasonic wave, process, then dry up;
Prepare negative electrode at described underlay substrate surface sputtering, sputtering condition is vacuum degree 1.0 × 10
-31.0 × 10
-5pa, sputtering rate 0.1 ~ 1nm/s;
Utilize thermal evaporation techniques to prepare successively pn knot layer, organic luminescence function layer, anode at described cathode surface, described pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, the metal surface work function of described the first metal layer is more than or equal to 5.1eV, the material in described intermediate layer is the mixture that metal and metal oxide form, described metal is the same with the material of described the first metal layer, and described metal oxide is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, the material of described the second metal level is Li, Na, Rb or Cs; The condition of described thermal evaporation is vacuum degree 1.0 × 1
-31.0 × 10
-5pa, evaporation rate 0.02 ~ 0.5nm/s.
Remove the organic pollutant on underlay substrate surface by the method for ultrasonic cleaning.Preferably, use successively liquid detergent, the each ultrasonic 15min of deionized water.
Method by sputter is prepared negative electrode on underlay substrate surface.The material of negative electrode is transparent conductive oxide film.Preferably, the material of transparent conductive oxide film is indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO).Preferably, the thickness of negative electrode is 70 ~ 200nm.
Prepare pn knot layer by thermal evaporation techniques at cathode surface, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually.Preferably, thermal evaporation condition is vacuum degree 1.0 × 10
-4pa, evaporation rate 0.2nm/s.
Preferably, the material of the first metal layer is Au, Cu, Ni, Pt or Ag.
Preferably, the thickness of the first metal layer is 10 ~ 25nm.
The transparent conductive oxide film of the first metal layer and negative electrode with contact the contact that belongs to two kinds of conductors, there is not the problem of injection barrier, therefore can greatly improve electron injection efficiency.The metal surface work function of the first metal layer is more than or equal to 5.1eV, and the work function of the metal of selecting approaches the work function of transparent conductive oxide film, can obtain good injection effect.
The material in intermediate layer is the mixture that metal and metal oxide form.Preferably, the mass ratio of metal and metal oxide is 1:2 ~ 1:10.
Metal in the material in intermediate layer is the same with the material of the first metal layer, is selected from Au, Cu, Ni, Pt or Ag.
Metal oxide in the material in intermediate layer is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, there is semiconductor property, be clipped between the metal of two different work functions, make metal that two work functions are different under external electrical field, form an internal electric field, thereby the hole of metal oxide inside is separated with electronics, be injected into respectively in two kinds of adjacent metal materials.
Use the metal the same with the material of the first metal layer to mix with metal oxide, as intermediate layer, the potential barrier that need overcome can make hole move to the first metal layer time reduces, thereby reduce on the whole the driving voltage of light-emitting device, and improved the conductivity in intermediate layer and the effect of separation of charge.
Preferably, the thickness in intermediate layer is 3 ~ 8nm.
The material of the second metal level is Li, Na, Rb or Cs, belongs to the metal of low work function.Preferably, the material of the second metal level obtains by adding its carbonate of thermal decomposition or Azide salt.
Preferably, the thickness of the second metal level is 5 ~ 20nm.
Under the effect of external electrical field, be positioned at the inner separation of charge that forms of metal oxide in pn knot layer intermediate layer, hole and electronics move to the first metal layer and the second metal level respectively, thereby electronics is directly injected into organic luminescence function layer from the second metal level, and the transparent conductive oxide film of negative electrode and contacting of the first metal layer belong to the contact of two kinds of conductors, there is not the problem of injection barrier, therefore greatly improved electron injection efficiency.The balance that electronic injection and hole are injected, can improve hole and electronics recombination probability and the luminous quantum efficiency in luminescent layer, the final Organnic electroluminescent device with higher luminescent properties that obtains.And this inversion type structure can make the second metal level be subject to the protection of underlay substrate.
Prepare organic light emitting functional layer by thermal evaporation techniques on pn knot layer surface.Preferably, organic luminescence function layer comprises luminescent layer, electron transfer layer, hole transmission layer and hole injection layer.
Preferably, thermal evaporation condition is vacuum degree 1.0 × 10
-4pa, evaporation rate 0.2nm/s.
In organic luminescence function layer, the material of each layer is material conventional in this area.
Preferably, the material of main part of luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 10-(2-[4-morpholinodithio)-2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7,-tetramethyl L-1H, 5H, 11H-[1] benzopyran ketone group [6, 7, 8-IJ] quinolizine-11-ketone (C545T), two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl (DPVBi), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close one or more in iridium (Ir (ppy) 3).
Preferably, the material of luminescent layer is for being doped to according to doping mass fraction 5 ~ 15% composite material forming in material of main part by one or both guest materialss, and wherein guest materials is hole mobile material or electron transport material.
Preferably, the thickness of luminescent layer is 5 ~ 20nm.
Preferably, hole mobile material comprises Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) and 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, electron transport material comprises 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), oxine aluminium (Alq3), 4, 7-diphenyl-o-phenanthroline (Bphen), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole (TAZ) and two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq).
Preferably, the material of electron transfer layer is electron transport material, be selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), oxine aluminium (Alq3), 4, 7-diphenyl-o-phenanthroline (Bphen), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole (TAZ) or two (2-methyl-oxine-N1, O8)-(1, 1'-biphenyl-4-hydroxyl) aluminium (BAlq).
Preferably, the thickness of electron transfer layer is 30 ~ 60nm.
Preferably, the material of hole transmission layer is hole mobile material, is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, the thickness of hole transmission layer is 10 ~ 60nm.
Preferably, the material of hole injection layer is Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc), 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamines (2-TNATA), 4,4', 4 " tri-(1-naphthyl phenyl amino) triphenylamines (1-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-benzidine (α-NPD), 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2', 7,7'-tetra-(N, N-hexichol amido)-9,9'-spiral shell two fluorenes (S-TAD).
Preferably, the thickness of hole injection layer is 10 ~ 60nm.
Prepare anode by thermal evaporation techniques on organic luminescence function layer surface.Preferably, thermal evaporation condition is vacuum degree 1.0 × 10
-4pa, evaporation rate 0.2nm/s.
Preferably, the material of anode is metal A u, Cu, Ni or Ag.
Preferably, the thickness of anode is 80 ~ 200nm.
Compared with prior art, the present invention has the following advantages:
The invention provides a kind of Organnic electroluminescent device, the material of this device negative electrode is transparent conductive oxide film, transparent conductive oxide film has the advantages such as transmitance is high, good conductivity, make the higher light permeable rate of having of Organnic electroluminescent device, luminosity, is conducive to realize uniform illumination and demonstration uniformly.
The present invention adopts inversion type structure, makes the metal material adjacent substrate substrate of low work function, has ensured the stability of metal material.Between negative electrode and organic luminescence function layer, be provided with pn knot layer, this pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, by the structure of this pn knot layer, electronics can be injected into organic luminescence function layer effectively from the cathode thin film of high work function.Solve the negative electrode of high work function to the low problem of the electron injection efficiency of organic luminescence function layer.Therefore can obtain Organnic electroluminescent device efficient, luminous stable homogeneous.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural representation of Organnic electroluminescent device provided by the invention, parts are followed successively by underlay substrate 101, negative electrode 102, pn knot layer, organic luminescence function layer 106, anode 107, wherein, pn knot layer comprises the first metal layer 103, intermediate layer 104, the second metal level 105.
Fig. 2 is the current density voltage curve comparison diagram of the embodiment of the present invention 1 and comparative example 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
A preparation method for Organnic electroluminescent device, comprises the steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, prepare indium and tin oxide film (ITO) as negative electrode at glass baseplate surface using the speed sputter of 0.1nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-4evaporation Au, Au and TiO successively under the condition of Pa and speed 0.02nm/s
2composite material, the Li being mixed to form according to mass ratio 1:4 prepares pn knot layer; Then by thermal evaporation technique, in vacuum degree 1.0 × 10
-4under the condition of Pa and speed 0.02nm/s, evaporation TPBi, C545T are doped to Alq according to doping mass fraction 15% successively
3the composite material of middle formation, NPB, CuPc, Au prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, pn knot layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, wherein, the material of underlay substrate is glass substrate; The material of negative electrode is ITO, and thickness is 100nm; The material of the first metal layer is Au, and thickness is 10nm; The material in intermediate layer is Au and TiO
2the composite material being mixed to form according to mass ratio 1:4, thickness is 5nm; The material of the second metal level is Li, and thickness is 10nm; The material of electron transfer layer is TPBi, and thickness is 40nm; The material of luminescent layer is that C545T is doped to Alq according to doping mass fraction 15%
3the composite material of middle formation, thickness is 10nm; The material of hole transmission layer is NPB, and thickness is 20nm; The material of hole injection layer is CuPc, and thickness is 20nm; The material of anode is Au, and thickness is 100nm, and structure is specifically expressed as: glass substrate/ITO (100)/Au (10nm)/Au:TiO
2(1:4,5nm)/Li (10nm)/TPBi (40nm)/C545T:Alq
3(15%, 10nm)/NPB (20nm)/CuPc (20nm)/Au (100nm).
Refer to Fig. 1, Fig. 1 is Organnic electroluminescent device prepared by the embodiment of the present invention, parts are followed successively by underlay substrate 101, negative electrode 102, pn knot layer, organic luminescence function layer 106, anode 107, and wherein, pn knot layer comprises the first metal layer 103, intermediate layer 104, the second metal level 105.
Embodiment 2
A preparation method for Organnic electroluminescent device, comprises the steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, prepare aluminium zinc oxide film (AZO) as negative electrode at glass baseplate surface using the speed sputter of 1nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-5evaporation Cu, Cu and Ta successively under the condition of Pa and speed 0.5nm/s
2o
5composite material, the Cs being mixed to form according to mass ratio 1:2 prepares pn knot layer; Then by thermal evaporation technique, in vacuum degree 1.0 × 10
-5under the condition of Pa and speed 0.5nm/s, evaporation Bphen, DCJTB are doped to Alq according to doping mass fraction 10% successively
3the composite material of middle formation, TPD, ZnPc, Ag prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, pn knot layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, wherein, the material of underlay substrate is glass substrate; The material of negative electrode is AZO, and thickness is 70nm; The material of the first metal layer is Cu, and thickness is 15nm; The material in intermediate layer is Cu and Ta
2o
5the composite material being mixed to form according to mass ratio 1:2, thickness is 8nm; The material of the second metal level is Cs, and thickness is 5nm; The material of electron transfer layer is Bphen, and thickness is 40nm; The material of luminescent layer is that DCJTB is doped to according to doping mass fraction 10% composite material forming in Alq3, and thickness is 5nm; The material of hole transmission layer is TPD, and thickness is 40nm; The material of hole injection layer is ZnPc, and thickness is 20nm; The material of anode is Ag, and thickness is 200nm, and structure is specifically expressed as: glass substrate/AZO (70nm)/Cu (15nm)/Cu:Ta
2o
5(1:2,8nm)/Cs (5nm)/Bphen (40nm)/DCJTB:Alq
3(10%, 5nm)/TPD (40nm)/ZnPc (20nm)/Ag (200nm).
Embodiment 3
A preparation method for Organnic electroluminescent device, comprises the steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, prepare gallium zinc oxide film (GZO) as negative electrode at glass baseplate surface using the speed sputter of 0.5nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-3composite material, the Rb that under the condition of Pa and speed 0.2nm/s, evaporation Ni, Ni and NiO are mixed to form according to mass ratio 1:5 successively prepares pn knot layer; Then by thermal evaporation technique, in vacuum degree 1.0 × 10
-3under the condition of Pa and speed 0.2nm/s, evaporation TAZ, Rubrene, 2-TNATA, VOPc, Ni prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode successively.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, pn knot layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, wherein, the material of underlay substrate is glass substrate; The material of negative electrode is GZO, and thickness is 200nm; The material of the first metal layer is Ni, and thickness is 25nm; The material in intermediate layer is the composite material that Ni and NiO are mixed to form according to mass ratio 1:5, and thickness is 3nm; The material of the second metal level is Rb, and thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 60nm; The material of luminescent layer is Rubrene, and thickness is 20nm; The material of hole transmission layer is 2-TNATA, and thickness is 60nm; The material of hole injection layer is VOPc, and thickness is 10nm; The material of anode is Ni, thickness is 70nm, structure is specifically expressed as: glass substrate/GZO (200nm)/Ni (25nm)/Ni:NiO (1:5,3nm)/Rb (20nm)/TAZ (60nm)/Rubrene (20nm)/2-TNATA (60nm)/VOPc (10nm)/Ni (70nm).
Embodiment 4
A preparation method for Organnic electroluminescent device, comprises the steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, prepare indium-zinc oxide film (IZO) as negative electrode at glass baseplate surface using the speed sputter of 0.5nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-3evaporation Pt, Pt and CeO successively under the condition of Pa and speed 0.2nm/s
2composite material, the Na being mixed to form according to mass ratio 1:3 prepares pn knot layer; Then by thermal evaporation technique, in vacuum degree 1.0 × 10
-3evaporation BCP, Ir (piq) successively under the condition of Pa and speed 0.2nm/s
3be doped to according to doping mass fraction 8% composite material, 1-TNATA, CuPc, the Cu that in TCTA, form and prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, pn knot layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, wherein, the material of underlay substrate is glass substrate; The material of negative electrode is IZO, and thickness is 200nm; The material of the first metal layer is Pt, and thickness is 15nm; The material in intermediate layer is Pt and CeO
2the composite material being mixed to form according to mass ratio 1:3, thickness is 5nm; The material of the second metal level is Na, and thickness is 10nm; The material of electron transfer layer is BCP, and thickness is 30nm; The material of luminescent layer is Ir (piq)
3be doped to according to doping mass fraction 8% composite material forming in TCTA, thickness is 15nm; The material of hole transmission layer is 1-TNATA, and thickness is 20nm; The material of hole injection layer is CuPc, and thickness is 10nm; The material of anode is Cu, and thickness is 100nm, and structure is specifically expressed as: glass substrate/IZO (200nm)/Pt (15nm)/Pt:CeO
2(1:3,5nm)/Na (10nm)/BCP (30nm)/Ir (piq)
3: TCTA (8%, 15nm)/1-TNATA (20nm)/CuPc (10nm)/Cu (100nm).
Embodiment 5
A preparation method for Organnic electroluminescent device, comprises the steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, prepare indium-zinc oxide film (IZO) as negative electrode at glass baseplate surface using the speed sputter of 0.5nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-3evaporation Ag, Ag and Ag successively under the condition of Pa and speed 0.2nm/s
2composite material, the Li that O is mixed to form according to mass ratio 1:2 prepares pn knot layer; Then by thermal evaporation technique, in vacuum degree 1.0 × 10
-3under the condition of Pa and speed 0.2nm/s, evaporation PBD, DPVBi, MeO-TPD, CuPc, Cu prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode successively.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, pn knot layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, wherein, the material of underlay substrate is glass substrate; The material of negative electrode is IZO, and thickness is 200nm; The material of the first metal layer is Ag, and thickness is 10nm; The material in intermediate layer is Ag and Ag
2the composite material that O is mixed to form according to mass ratio 1:2, thickness is 6nm; The material of the second metal level is Li, and thickness is 15nm; The material of electron transfer layer is PBD, and thickness is 30nm; The material of luminescent layer is DPVBi, and thickness is 15nm; The material of hole transmission layer is MeO-TPD, and thickness is 20nm; The material of hole injection layer is CuPc, and thickness is 10nm; The material of anode is Cu, and thickness is 80nm, and structure is specifically expressed as: glass substrate/IZO (200nm)/Ag (10nm)/Ag:Ag
2o (1:2,6nm)/Li (15nm)/PBD (30nm)/DPVBi (15nm)/MeO-TPD (20nm)/CuPc (10nm)/Cu (80nm).
Comparative example 1
Prepare a kind of Organnic electroluminescent device that is not provided with pn knot layer between negative electrode and organic luminescence function layer as a comparison case 1, comprise the following steps:
Glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, then dries up with nitrogen;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, prepare indium and tin oxide film (ITO) as negative electrode at glass baseplate surface using the speed sputter of 0.1nm/s;
By thermal evaporation technique, in vacuum degree 1.0 × 10
-4under the condition of Pa and speed 0.02nm/s, evaporation TPBi, C545T are doped to Alq according to doping mass fraction 15% successively
3the composite material of middle formation, NPB, CuPc, Au prepare respectively electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode.
After above-mentioned steps completes, obtain a kind of Organnic electroluminescent device, comprise the underlay substrate, negative electrode, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer, the anode that stack gradually, concrete structure is expressed as: glass substrate/ITO (100nm)/TPBi (40nm)/C545T:Alq
3(15%, 10nm)/NPB (20nm)/CuPc (20nm)/Au (100nm).
Refer to Fig. 2, current density-voltage relationship comparison diagram of Fig. 2 Organnic electroluminescent device that to be the embodiment of the present invention 1 prepare with comparative example 1.The structure that curve 1 is prepared for embodiment 1 is glass substrate/ITO (100)/Au (10nm)/Au:TiO
2(1:4,5nm)/Li (10nm)/TPBi (40nm)/C545T:Alq
3(15%, the Organnic electroluminescent device of 10nm)/NPB (20nm)/CuPc (20nm)/Au (100nm), the structure that curve 2 is prepared for comparative example 1 is glass substrate/ITO (100nm)/TPBi (40nm)/C545T:Alq
3the Organnic electroluminescent device of (15%, 10nm)/NPB (20nm)/CuPc (20nm)/Au (100nm).As seen from the figure, under identical driving voltage, embodiment 1 has higher current density, and this electronic injection that embodiment 1 has been described is more prone to, and the electronic injection difficulty of comparative example 1.
Table 1 is embodiment 1,2,3,4,5 and the luminescent properties data of the prepared device of comparative example 1, as can be seen from the table, Organnic electroluminescent device prepared by method provided by the invention is compared with common light-emitting device, because the injection barrier of electronics reduces, therefore can improve the injection efficiency of electronics, thereby obtain lower starting resistor and luminous efficiency.
The luminescent properties data of Organnic electroluminescent device prepared by table 1 embodiment of the present invention and comparative example 1
| ? | Starting resistor | Luminous efficiency (lm/W) |
| Embodiment 1 | 2.4 | 17.5 |
| Embodiment 2 | 2.3 | 19.8 |
| Embodiment 3 | 2.2 | 20.2 |
| Embodiment 4 | 2.5 | 27.3 |
| Embodiment 5 | 2.6 | 16.2 |
| Comparative example 1 | 4.0 | 8.8 |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an Organnic electroluminescent device, it is characterized in that, comprise the underlay substrate, negative electrode, pn knot layer, organic luminescence function layer, the anode that stack gradually, described pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, the metal surface work function of described the first metal layer is more than or equal to 5.1eV, the material in described intermediate layer is the mixture that metal and metal oxide form, and described metal is the same with the material of described the first metal layer, and described metal oxide is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, the material of described the second metal level is Li, Na, Rb or Cs.
2. Organnic electroluminescent device as claimed in claim 1, is characterized in that, the material of described the first metal layer is Au, Cu, Ni, Pt or Ag.
3. Organnic electroluminescent device as claimed in claim 1, is characterized in that, in the material in described intermediate layer, the mass ratio of metal and metal oxide is 1:2 ~ 1: 10.
4. Organnic electroluminescent device as claimed in claim 1, is characterized in that, the thickness of described the first metal layer is 10 ~ 25nm, and the thickness in described intermediate layer is 3 ~ 8nm, and the thickness of described the second metal level is 5 ~ 20nm.
5. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, the material of described negative electrode is transparent conductive oxide film, and the material of described transparent conductive oxide film is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide.
6. a preparation method for Organnic electroluminescent device, is characterized in that, comprises the steps:
Underlay substrate is provided, described underlay substrate is carried out to ultrasonic cleaning, after cleaning up, in ultrasonic wave, process, then dry up;
Prepare negative electrode at described underlay substrate surface sputtering, sputtering condition is vacuum degree 1.0 × 10
-31.0 × 10
-5pa, sputtering rate 0.1 ~ 1nm/s;
Utilize thermal evaporation techniques to prepare successively pn knot layer, organic luminescence function layer, anode at described cathode surface, described pn knot layer comprises the first metal layer, intermediate layer, the second metal level that stack gradually, the metal surface work function of described the first metal layer is more than or equal to 5.1eV, the material in described intermediate layer is the mixture that metal and metal oxide form, described metal is the same with the material of described the first metal layer, and described metal oxide is AgO, TiO
2, NiO, Ta
2o
5or CeO
2, the material of described the second metal level is Li, Na, Rb or Cs; The condition of described thermal evaporation is vacuum degree 1.0 × 10
-3~ 1.0 × 10
-5pa, evaporation rate 0.02 ~ 0.5nm/s.
7. the preparation method of Organnic electroluminescent device as claimed in claim 6, is characterized in that, the material of described the first metal layer is Au, Cu, Ni, Pt or Ag.
8. the preparation method of Organnic electroluminescent device as claimed in claim 6, is characterized in that, in the material in described intermediate layer, the mass ratio of metal and metal oxide is 1:2 ~ 1:10.
9. the preparation method of Organnic electroluminescent device as claimed in claim 6, is characterized in that, the material of described the second metal level obtains by adding its carbonate of thermal decomposition or Azide salt.
10. the preparation method of Organnic electroluminescent device as claimed in claim 6, it is characterized in that, the material of described negative electrode is transparent conductive oxide film, and the material of described transparent conductive oxide film is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide.
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| CN1300523A (en) * | 1999-03-17 | 2001-06-20 | Tdk株式会社 | Organic electroluminescent |
| CN101546812A (en) * | 2008-03-25 | 2009-09-30 | 富士施乐株式会社 | Organic electroluminescent element and display device including the same |
| KR20090105316A (en) * | 2008-04-02 | 2009-10-07 | 단국대학교 산학협력단 | Organic light emitting diodes |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275304A (en) * | 1998-08-13 | 2000-11-29 | Tdk株式会社 | Organic EL device |
| CN1300523A (en) * | 1999-03-17 | 2001-06-20 | Tdk株式会社 | Organic electroluminescent |
| CN101546812A (en) * | 2008-03-25 | 2009-09-30 | 富士施乐株式会社 | Organic electroluminescent element and display device including the same |
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