WO2008013171A1 - Élément émetteur de lumière et dispositif d'affichage - Google Patents
Élément émetteur de lumière et dispositif d'affichage Download PDFInfo
- Publication number
- WO2008013171A1 WO2008013171A1 PCT/JP2007/064498 JP2007064498W WO2008013171A1 WO 2008013171 A1 WO2008013171 A1 WO 2008013171A1 JP 2007064498 W JP2007064498 W JP 2007064498W WO 2008013171 A1 WO2008013171 A1 WO 2008013171A1
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- WO
- WIPO (PCT)
- Prior art keywords
- semiconductor material
- light emitting
- semiconductor
- electrode
- display device
- Prior art date
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- 239000000463 material Substances 0.000 claims abstract description 142
- 239000004065 semiconductor Substances 0.000 claims abstract description 136
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 27
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- -1 tube Chemical compound 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000005204 segregation Methods 0.000 claims description 6
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
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- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910007709 ZnTe Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims 1
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- 238000000034 method Methods 0.000 description 14
- 229910003437 indium oxide Inorganic materials 0.000 description 11
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- 239000010409 thin film Substances 0.000 description 7
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- 239000010955 niobium Substances 0.000 description 4
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 238000005566 electron beam evaporation Methods 0.000 description 3
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- 150000004706 metal oxides Chemical class 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 241001249696 Senna alexandrina Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
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- 229910052741 iridium Inorganic materials 0.000 description 2
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- 238000005191 phase separation Methods 0.000 description 2
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- 229920000128 polypyrrole Polymers 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical class [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
- C09K11/582—Chalcogenides
- C09K11/584—Chalcogenides with zinc or cadmium
-
- 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
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/16—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
- H01L33/18—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous within the light emitting region
Definitions
- the present invention relates to an electoric luminescence (hereinafter abbreviated as EL) element and a display device using the EL element.
- EL electoric luminescence
- a display device using this EL element has features such as self-luminous property, excellent visibility, wide viewing angle, and quick response.
- currently developed EL devices include inorganic EL devices that use inorganic materials as light emitters and organic EL devices that use organic materials as light emitters.
- inorganic EL elements for example, an inorganic phosphor such as zinc sulfide is used as a light emitter, and electrons accelerated by a high electric field of 10 6 V / cm collide and excite the emission center of the phosphor to relax them. When it emits light.
- inorganic EL elements have a light-emitting layer in which phosphor powder is dispersed in a polymer organic material, etc., and two layers between the pair of electrodes.
- a thin-film EL element provided with a dielectric layer and a thin-film light emitting layer sandwiched between two dielectric layers.
- the former distributed EL element is easy to manufacture, but its use has been limited due to its low brightness and short lifetime.
- the double insulation structure element proposed by Higuchi et al. In 1974 showed high brightness and long life, and was put into practical use for in-vehicle displays (for example, And Patent Document 1).
- FIG. 13 is a cross-sectional view perpendicular to the light emitting surface of the thin-film EL element 50 having a double insulation structure.
- This EL element 50 has a structure in which a transparent electrode 52, a first dielectric layer 53, a light emitting layer 54, a second dielectric layer 55, a back electrode 56 and 1S are laminated in this order on a substrate 51. Yes.
- An AC voltage is applied from the AC voltage source 57 between the transparent electrode 52 and the back electrode 56 to extract light emission from the transparent electrode 52 side.
- the dielectric layers 53 and 55 have a function of limiting the current flowing in the light emitting layer 54, and prevent dielectric breakdown of the EL element 50.
- the transparent electrode 52 and the back electrode 56 are patterned on the stripe so as to be orthogonal to each other, and a voltage is applied to a specific pixel selected by the matrix, thereby performing a passive matrix that displays an arbitrary pattern.
- Drive-type display devices are known.
- the dielectric material used as the dielectric layers 53 and 55 has a high dielectric constant, high insulation resistance, and high withstand voltage.
- Dielectric material with perovskite structure such as iO, PbTiO, CaTiO, Sr (Zr, Ti) 0
- the inorganic fluorescent material used as the light-emitting layer 54 is generally a material in which an insulator crystal is used as a base crystal and an element serving as a light emission center is doped therein. Since this host crystal is physically and chemically stable, inorganic EL devices are highly reliable and have a lifetime of more than 30,000 hours.
- the emission luminance is improved by doping the light emitting layer mainly with ZnS and doping with transition metal elements such as Mn, Cr, Tb, Eu, Tm, and Yb or rare earth elements (for example, patents). (Ref. 2).
- a Group 12-Group 16 compound semiconductor such as ZnS used for the light-emitting layer 54 is composed of a polycrystal. Therefore, many crystal grain boundaries exist in the light emitting layer 54. This grain boundary acts as a scatterer for electrons accelerated by the application of an electric field, so that the excitation efficiency of the emission center is significantly reduced. In addition, there are many non-radiative recombination centers that are harmful to EL emission due to large lattice distortions due to misalignment of crystal orientation at the grain boundaries. For these reasons, the light emission luminance of inorganic EL elements is low and practically insufficient.
- Patent Document 2 Japanese Patent Publication No. 54-8080
- Patent Document 3 Japanese Patent Laid-Open No. 6-36876
- Patent Document 4 JP-A-6-196262
- an inorganic EL element as described above is used as a high-definition display device such as a television, a luminance of about 300 cd / m 2 is required.
- the light emission luminance is still 150 cd / m 2 , which is still insufficient.
- An object of the present invention is to provide a display device capable of emitting light at a low voltage and having high luminance and high efficiency.
- the light emitting device according to the present invention includes a pair of electrodes at least one of which is transparent or translucent,
- a light-emitting layer provided between the electrodes and having a polycrystalline structure made of a first semiconductor material
- a second semiconductor material different from the first semiconductor material is segregated at grain boundaries of the polycrystalline structure.
- the first semiconductor material and the second semiconductor material have semiconductor structures of different conductivity types. Further, it is preferable that the first semiconductor material has an n-type semiconductor structure and the second semiconductor material has a p-type semiconductor structure. Still further, the first semiconductor material and the second semiconductor material may each be a compound semiconductor. Further, the first semiconductor material may be a Group 12 and Group 16 compound semiconductor.
- the first semiconductor material may have a cubic structure.
- the first semiconductor material is Cu, Ag, Au, Al, Ga, In, Mn, Cl, Br, I, Li, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb force, or at least one element selected from the group consisting of these.
- the average crystal particle diameter of the polycrystalline structure made of the first semiconductor material may be in the range of 5 nm to 500 nm.
- the first semiconductor substance is a zinc-based material containing zinc
- at least one of the pair of electrodes is preferably made of a material containing zinc.
- the zinc-containing material constituting the one electrode is mainly composed of zinc oxide, and at least a group force consisting of aluminum, gallium, titanium, niobium, tantalum, tungsten, copper, silver, and boron is also selected. It is preferable to include one kind.
- a support substrate may be further provided that supports at least one of the electrodes.
- a color conversion layer may be further provided opposite to the pair of electrodes and in front of the direction in which light is extracted from the light emitting layer.
- a display device includes a substrate,
- a plurality of scan electrodes extending in parallel with each other in a first direction on the substrate; and a plurality of data electrodes extending in parallel with each other in a second direction perpendicular to the scan electrodes;
- At least one of the scan electrode and the data electrode is transparent or semi-transparent, and the light emitting layer has a polycrystalline structure made of a first semiconductor material, and the first electrode is formed at a grain boundary of the polycrystalline structure.
- the second semiconductor material that is different from the semiconductor material is segregated.
- the first semiconductor material and the second semiconductor material have semiconductor structures of different conductivity types. Further, it is preferable that the first semiconductor material has an n-type semiconductor structure and the second semiconductor material has a p-type semiconductor structure. Furthermore, each of the first semiconductor material and the second semiconductor material may be a compound semiconductor. . Further, the first semiconductor material may be a Group 12 and Group 16 compound semiconductor.
- the first semiconductor material may have a cubic structure. Furthermore, the first semiconductor material is Cu, Ag, Au, Al, Ga, In, Mn, Cl, Br, I, Li, Ce, Pr.
- Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb may contain at least one element selected from the group consisting of forces.
- the average crystal particle diameter of the polycrystalline structure made of the first semiconductor material is 5 to
- the second semiconductor material may be Cu S, ZnS, ZnSe, ZnSSe, ZnSeTe, ZnTe, G
- Either aN or InGaN may be used.
- the first semiconductor substance is a zinc-based material containing zinc
- the electrodes is made of a material containing zinc.
- the material containing zinc constituting the one electrode is mainly composed of zinc oxide, and is selected from the group consisting of aluminum, gallium, titanium, niobium, tantalum, tungsten, copper, silver, and boron. It is preferable to include at least one kind.
- a support substrate may be further provided that faces and supports at least one of the electrodes.
- a color conversion layer may be further provided facing the electrode and in front of the light emission extraction direction.
- FIG. 1 is a schematic configuration diagram seen from a direction perpendicular to a light emitting surface of a light emitting element according to Embodiment 1 of the present invention.
- FIG. 2 is an enlarged schematic view showing the configuration of the light emitting layer of the light emitting element according to Embodiment 1 of the present invention.
- FIG. 3 is a schematic configuration diagram perpendicular to the light emitting surface of another example of the light emitting element according to the first embodiment of the present invention.
- FIG. 4 (a) is a schematic diagram of the vicinity of the interface between the light-emitting layer made of ZnS and the transparent electrode (or back electrode) made of AZO, and (b) shows the displacement of potential energy in (a).
- FIG. 4 (a) is a schematic diagram of the vicinity of the interface between the light-emitting layer made of ZnS and the transparent electrode (or back electrode) made of AZO, and (b) shows the displacement of potential energy in (a).
- FIG. 5 (a) is a schematic diagram of an interface between a light-emitting layer made of ZnS and a transparent electrode made of ITO as a comparative example, and (b) is a schematic diagram for explaining the potential energy displacement of (a).
- a is a schematic diagram of an interface between a light-emitting layer made of ZnS and a transparent electrode made of ITO as a comparative example
- (b) is a schematic diagram for explaining the potential energy displacement of (a).
- FIG. 6 is a schematic configuration diagram perpendicular to a light emitting surface of a light emitting element of still another example according to Embodiment 1 of the present invention.
- FIG. 7 is a block diagram showing a configuration of a passive matrix display device according to a second embodiment of the present invention.
- FIG. 8 is a perspective view showing a configuration of a display unit that constitutes the display device of FIG.
- FIG. 9 is a cross-sectional view perpendicular to the light emitting surface along line AA in FIG.
- FIG. 10 is a schematic diagram showing a configuration when each pixel C in FIG. 9 is considered as one light emitting element.
- FIG. 11 is an enlarged schematic view showing a configuration of a light emitting layer of a display device according to Embodiment 2 of the present invention.
- FIG. 12 is a schematic diagram showing a configuration of another example of a color display device.
- FIG. 13 is a schematic configuration diagram viewed from a direction perpendicular to the light emitting surface of a conventional inorganic EL element.
- FIG. 1 is a schematic configuration diagram of a cross section perpendicular to the light emitting surface of the light emitting element 10 of the present embodiment, viewed from a direction parallel to the light emitting surface.
- the light emitting element 10 includes a substrate 1, a transparent electrode 2 as a first electrode provided on the substrate 1, a light emitting layer 3 provided on the transparent electrode 2, and a transparent on the light emitting layer 3.
- the back electrode 4 which is the 2nd electrode provided facing the electrode 2 is provided.
- the light emitting layer 3 is sandwiched between a transparent electrode 2 as a first electrode and a back electrode 4 as a second electrode.
- the substrate 1 is adjacent to the transparent electrode 2 to support the entire light emitting element 10. It is provided in contact.
- the transparent electrode 2 and the back electrode 4 are electrically connected via a power source 5.
- a power source 5 In the light emitting element 10, when electric power is supplied from the power source 5, a potential difference is generated between the transparent electrode 2 and the back electrode 4, and a voltage is applied to the light emitting layer 3. Then, the light emitter of the light emitting layer 3 sandwiched between the transparent electrode 2 and the back electrode 4 emits light, and the light 7 passes through the transparent electrode 2 and the substrate 1 and is extracted outside the light emitting element 10.
- a DC power source is used as the power source 5.
- the polarity of this power supply 5 is not limited to the example shown in Fig. 1, but it can be connected in reverse polarity!
- the light emitting layer 3 has a polycrystalline structure composed of the first semiconductor material 21, and the second semiconductor material 23 segregates at the grain boundary 22 of the polycrystalline structure. It is characterized by having.
- the first semiconductor material 21 is an n-type semiconductor material
- the second semiconductor material 23 is a p-type semiconductor material.
- the p-type semiconductor material segregated at the grain boundary of the n-type semiconductor material improves the hole injection property, efficiently generates recombination of electrons and holes, and emits light with high brightness at low voltage. An element can be realized.
- the light-emitting element 10 is not limited to the above-described configuration, and a plurality of light-emitting layers 3 are provided, and a plurality of thin dielectric layers are provided between the electrode and the light-emitting layer 3 for current limitation.
- back electrode 4 is black electrode, seal all or part of light emitting element 10 It is possible to appropriately change to each configuration, such as further including a structure, a structure such as a color conversion layer that converts the color of light emitted from the light emitting layer 3 in front of the light emission extraction direction.
- the substrate 1 is made of a material that can support each layer formed thereon and has high electrical insulation.
- the material when light is extracted from the substrate 1 side, the material is required to be light transmissive with respect to the wavelength of light emitted from the light emitter.
- a material for example, glass, quartz, ceramic or the like such as Couting 1737 can be used.
- non-alkali glass is a soda lime glass that is coated on the glass surface with alumina or the like as an ion-noble layer. There may be.
- a combination of polyester, polyethylene terephthalate, polychloroethylene, ethylene, and nylon 6, a fluororesin material, a resin film such as polyethylene, polypropylene, polyimide, and polyamide can be used.
- a resin film it is preferable to use a material having excellent durability, flexibility, transparency, electrical insulation, and moisture resistance. Note that the description of the above material is an example, and the material of the substrate 1 is not particularly limited thereto.
- the electrodes there are a transparent electrode 2 on the light extraction side and a back electrode 4 on the other side.
- the transparent electrode 2 is provided on the substrate 1 as shown in FIG. 1
- the present invention is not limited to this.
- a back electrode 4 may be provided on 1 and a light emitting layer 3 and a transparent electrode 2 may be laminated on the back electrode 4 in this order.
- both the transparent electrode 2 and the back electrode 4 may be transparent electrodes.
- the power source 5 may be connected in the opposite polarity to that in FIG.
- the material of the transparent electrode 2 preferably has a high transmittance particularly in the visible light region as long as it has a light transmitting property so that the light generated in the light emitting layer 3 can be extracted to the outside. Further, it is preferable that the electrode has a low resistance, and further, it is preferable that the electrode 1 has excellent adhesion to the substrate 1 and the light emitting layer 3.
- a particularly suitable material for the transparent electrode 2 is ITO (InO doped with SnO.
- These transparent electrodes 2 can be formed by a film forming method such as a sputtering method, an electron beam evaporation method, an ion plating method, etc. for the purpose of improving the transparency or reducing the resistivity. Further, after film formation, surface treatment such as plasma treatment may be performed for the purpose of resistivity control.
- the film thickness of transparent electrode 2 is required It is determined from the sheet resistance value and visible light transmittance.
- the carrier concentration of the transparent electrode 2 is preferably in the range of lE17 ⁇ lE22cm_ 3.
- the transparent electrode 2 has a volume resistivity of 1E-3 ⁇ 'cm or less and a transmittance of 75% or more at a wavelength of 380 to 780 nm.
- the refractive index of the transparent electrode 2 is preferably 1.85 to 1.95.
- the film thickness of the transparent electrode 2 is 30 nm or less, a dense and stable film can be realized.
- the back electrode 4 can be any conductive material that is generally well known. Furthermore, it is preferable that the adhesiveness with the light emitting layer 3 is excellent. Suitable examples include, for example, metal oxides such as ITO, InZnO, ZnO, SnO, Pt, Au, Pd, Ag, Ni, Cu,
- Metals such as Al, Ru, Rh, Ir, Cr, Mo, W, Ta, Nb, laminated structures of these, or polyaniline, polypyrrole, PEDOT [poly (3,4-ethylenedioxythiophene) ] / Use of conductive polymer such as PSS (polystyrene sulfonic acid) or conductive carbon.
- PSS polystyrene sulfonic acid
- the transparent electrode 2 and the back electrode 4 may be configured to cover the entire surface of each layer, or a plurality of electrodes may be configured in a stripe shape in the layer. Further, the transparent electrode 2 and the back electrode 4 are both configured as a plurality of striped electrodes, and each striped electrode of the transparent electrode 2 and all the striped electrodes and the force S of the back electrode 4 are twisted. And each of the striped electrodes of the transparent electrode 2 projected onto the light emitting surface and all the striped electrodes of the back electrode 4 projected onto the light emitting surface intersect each other. You may comprise. In this case, by applying a voltage between a pair of electrodes selected from each of the striped electrodes of the transparent electrode 2 and each of the striped electrodes of the back electrode 4, a display that emits light at a predetermined position is configured. It becomes possible.
- FIG. 2 is a schematic configuration diagram in which a part of the cross section of the light emitting layer 3 is enlarged.
- the light emitting layer 3 has a polycrystalline structure made of the first semiconductor material 21 and has a structure in which the second semiconductor material 23 is prayed at the grain boundary 22 of the polycrystalline structure.
- the first semiconductor material 21 a semiconductor material in which majority carriers are electrons and exhibits n-type conduction is used.
- the second semiconductor material 23 is a semi-conductor exhibiting p-type conduction, with majority carriers being holes. Conductive material is used. Further, the first semiconductor material 21 and the second semiconductor material 23 are electrically joined.
- the first semiconductor material 21 has a band gap size from the near ultraviolet region to the visible light region.
- Inter-group 16 compounds and mixed crystals thereof for example, CaSSe
- Group 13-15 compounds such as A1P, AlAs, GaN, GaP, and mixed crystals thereof (for example, In GaN), ZnMgS, CaSSe, CaSrS A mixed crystal of the above-described compound can be used.
- a chalcopyrite type compound such as CuAlS may be used.
- the first chalcopyrite type compound such as CuAlS may be used.
- the polycrystalline body made of the semiconductor material 21 preferably has a cubic structure in the main part. Furthermore, Cu, Ag, Au, Al, Ga, In, Mn, Cl, Br, I, Li, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, One or more kinds of atoms or ions selected from the group consisting of Yb may be contained as an additive. The color of light emitted from the light emitting layer 3 is also determined by the type of these elements.
- GaN, InGaN can be used. These materials may contain one or more elements from N, Cu, and In as additives for imparting p-type conduction.
- a feature of the light-emitting element 10 according to the present embodiment is that the light-emitting layer 3 has a polycrystalline structure made of an n-type semiconductor material 21, and a p-type semiconductor material 23 is formed at the grain boundary 22 of the polycrystalline structure. Is that it has a segregated structure.
- the crystallinity of the light-emitting layer is enhanced to prevent scattering of electrons accelerated by a high electric field! /,!, But ZnS, ZnSe, etc. generally have n-type conductivity. For this reason, it is not possible to expect high-intensity light emission due to recombination of electrons and holes with insufficient supply of holes.
- the grain boundary when the crystal grain of the light emitting layer grows, the grain boundary also extends uniquely unless it is a single crystal.
- the grain boundary in the film thickness direction becomes a conductive path, resulting in a problem that the breakdown voltage is lowered.
- the present inventor has made the light emitting layer 3 a polycrystalline structure made of an n-type semiconductor material 21.
- the p-type semiconductor material 23 segregates at the grain boundary 22 of this polycrystalline structure, the p-type semiconductor material segregated at the grain boundary improves the hole injection property. I found it.
- the transparent electrode 2 and the back electrode 4 are, for example, ZnO, AZO (for example, zinc oxide) It is preferable to use an electrode made of a metal oxide containing zinc, such as one doped with aluminum) or GaZO (zinc oxide doped with gallium, for example).
- a zinc-based material such as ZnS
- AZO for example, zinc oxide
- the work function of Z ⁇ is 5.8 eV
- ITO indium oxide
- the work function of tin is 7. OeV.
- the work function of the zinc-based material which is the first semiconductor material of the light-emitting layer 3
- the work function of ZnO is closer to the work function of the zinc-based material than that of ITO.
- FIG. 4 (a) is a schematic view of the vicinity of the interface between the light-emitting layer 3 made of ZnS and the transparent electrode 2 (or the back electrode 4) made of AZO.
- Fig. 4 (b) is a schematic diagram for explaining the potential energy displacement of Fig. 4 (a).
- FIG. 5 (a) is a schematic diagram of the interface between the light emitting layer 3 made of ZnS and the transparent electrode made of ITO as a comparative example.
- Fig. 5 (b) is a schematic diagram for explaining the displacement of the potential energy in Fig. 5 (a).
- the first semiconductor material constituting the light emitting layer 3 is used. Since 21 is a zinc-based material (ZnS) and the transparent electrode 2 (or back electrode 4) is a zinc oxide-based material (AZO), the transparent electrode 2 (or back electrode 4) and the light emitting layer 3
- the oxide that forms at the interface is zinc oxide (ZnO).
- the doping material (A1) diffuses during film formation, and a low-resistance oxide film is formed.
- the zinc oxide-based (AZO) transparent electrode 2 (or back electrode 4) has a hexagonal crystal structure, but the zinc-based material (ZnS), which is the first semiconductor substance 21 constituting the light-emitting layer 3, is used.
- ZnS zinc-based material
- the displacement of potential energy is small.
- the transparent electrode is ITO which is not a zinc-based material, so that the oxide film (ZnO) formed at the interface has a crystal structure different from that of ITO. Therefore, the energy barrier at the interface increases. Therefore, as shown in FIG. 5 (b), the displacement of potential energy increases at the interface, and the light emission efficiency of the light emitting element decreases.
- the transparent electrode 2 (or the back electrode 4) made of a zinc oxide-based material.
- a light-emitting element with high light emission efficiency can be provided.
- the transparent electrode 2 (or the back electrode 4) containing zinc
- the force described by taking AZO doped with aluminum and GZO doped with gallium as examples.
- the light emitting element 10b of this another example uses a substrate 1 (4) that also serves as a back electrode 4, and a light emitting layer 3 and a transparent electrode 2 are sequentially laminated on a substrate 1 (4). Configured. Further, a material system mainly composed of ZnS is used as the first semiconductor substance 21 of the light emitting layer 3. Note that the first and second semiconductor substances 21 and 23 of the light emitting layer 3 can be formed by the same manufacturing method when other materials than the above are used.
- a conductive silicon substrate 1 (4) that also serves as the back electrode 4 is prepared as a substrate.
- the light emitting layer 3 is formed on the substrate 1 (4) which also serves as the back electrode 4.
- a thin light-emitting layer sputtering, electron beam evaporation, resistance heating evaporation, ion
- the above-described light-emitting layer can be formed using a plating method, a CVD method, or the like.
- the n-type semiconductor material is fired in vacuum.
- a p-type semiconductor can be deposited at the grain boundary of a polycrystalline structure.
- the light emitting layer 3 is formed by the following two processes using an electron beam evaporation apparatus.
- each material is irradiated with an electron beam to form a light emitting layer 3 on the substrate 1.
- the substrate temperature is set to 200 ° C, and ZnS and CuS are co-evaporated.
- a light emitting layer 3 having a polycrystalline structure of ZnS and having a polycrystalline structure in which CuxS is segregated at the crystal grain boundary is formed.
- An ITO film is formed on the light emitting layer 3 as a transparent electrode 2 by a sputtering method (lm m square pattern shape).
- the substrate 1 (4) is not limited to the force that also serves as the back electrode 4, but the substrate 1 and the back surface as in the light-emitting element 10a shown in FIG.
- the electrode 4 may be provided separately.
- a conductive silicon substrate that is opaque to light emission is used as the substrate 1 (4) that also serves as the back electrode 4, and the light emitting layer 3 and the transparent layer are formed from the substrate 1 (4) side.
- the electrode 2 is formed, the order is not limited to this stacking order. For example, like the light-emitting element 10 shown in FIG.
- a substrate 1 that is transparent to light emission is used, and each layer is laminated on the substrate 1 in the order of transparent electrode 2, light-emitting layer 3, and back electrode 4. May be. Further, in order to stabilize the characteristics of the light emitting element, an aging treatment after the element creation may be performed.
- the light emitting device of this embodiment it was possible to emit light at a lower voltage and to obtain higher luminance than the conventional inorganic EL device.
- FIG. 7 is a block diagram showing a schematic configuration of a passive matrix display device 100 according to Embodiment 2 of the present invention.
- the passive matrix display device 100 includes a display unit 101, a driving unit 102 that selectively drives each pixel C of the display unit 101, and a control unit 103 that controls the driving unit 102 and supplies power. Is done.
- a DC power source is used as shown in FIG.
- the drive unit 102 includes a data electrode drive circuit 121 that drives the data electrode X and a scan electrode drive circuit 122 that drives the scan electrode Y.
- FIG. 8 is a perspective view showing the configuration of the display unit 101.
- the display unit 101 includes a substrate 1 and a plurality of data electrodes X, X, X,... Arranged in parallel with each other along the first direction (column direction in FIGS. 7 and 8). ⁇ ⁇ ⁇ ⁇ , the light emitting layer 3, and the second direction perpendicular to the first direction
- a plurality of scanning electrodes Y, Y, Y ⁇ are arranged so as to extend in parallel to each other along the direction (row direction in FIGS. 7 and 8).
- a portion where the pair of data electrodes X and scan electrodes Y intersect is called a pixel C.
- the display unit 101 has N ⁇ M pixels C-power three-dimensional array.
- Each pixel C represents the pixel position by its subscripts i and j.
- pixel C in Figure 7 is data
- pixel C includes data electrode X and scan electrode Y.
- the pixel C is connected to the scan electrode Y.
- pixel C and pixel C are
- FIG. 9 is a cross-sectional view perpendicular to the light emitting surface along the line AA in FIG.
- each pixel C has a data electrode X (back electrode 4), It consists of the light emitting layer 3 and the scanning electrode Y (transparent electrode 2).
- Each pixel C corresponds to one EL element. Therefore, the display unit 101 can think that a plurality of EL elements are two-dimensionally arranged.
- the force in which the light-emitting layer 3 is provided as a continuous layer over each pixel C is not limited to such a configuration, and the light-emitting layer 3 is provided separately for each pixel C. It may be a configuration.
- the light emitting layer 3 may be separated for each pixel C.
- the EL element is a data electrode Xi and a scan electrode.
- An EL element array in which EL elements are separated except for Y and each EL element is two-dimensionally arranged may be used.
- all of the intersecting pixels C of the N data electrodes X and the M scan electrodes Y are configured as EL elements.
- FIG. 10 is a schematic schematic diagram when one pixel C in FIG. 9 is considered as one EL element 10.
- This EL element 10 is configured by laminating a back electrode 4, a light emitting layer 3, and a transparent electrode 2 in this order on a substrate 1, and a voltage is applied to the light emitting layer 3 by a DC power source 5 to emit light from the light emitting layer 3.
- the back electrode 4 corresponds to the data electrode X
- the transparent electrode 2 corresponds to the scanning electrode Y.
- FIG. 11 is a schematic configuration diagram in which a part of the cross section of the light emitting layer 3 is enlarged.
- the light emitting layer 3 of the EL element of each pixel C has a polycrystalline structure made of the first semiconductor material 21, and the second semiconductor material 23 is placed on the grain boundary 22 of the polycrystalline structure.
- the first semiconductor material 21 is an n-type semiconductor material
- the second semiconductor material 23 is a p-type semiconductor material.
- the p-type semiconductor material segregated at the grain boundary of the n-type semiconductor material improves the hole injection property, efficiently generates recombination light emission of electrons and holes, and can emit light at a low voltage.
- a color display device can be obtained by forming the light-emitting layer 3 by color-coding the phosphors of RGB colors.
- a light emitting unit for each color of RGB such as transparent electrode / light emitting layer / back electrode may be laminated.
- a color filter and / or a color filter and / or a display device with a single color or two-color light emitting layer is prepared. Can also display RGB colors using a color conversion filter.
- FIG. 12 is a cross-sectional view showing a configuration of a display unit of another color display device.
- a color conversion layer 115 and a color filter 116 are further provided between the substrate 1 and the plurality of data electrodes 4.
- the color conversion layer 115 is provided between the light emitting layer 3 and the color filter 116, and converts light from the light emitting layer 3 into white light.
- the color filter 116 is provided with one of a red filter R, a green filter G, and a blue filter B for each data electrode.
- White light from the color conversion layer 115 is transmitted through the red filter R, the green filter G, and the blue filter B, respectively, and the red light, the green light, and the blue light are transmitted and displayed.
- the present invention is not limited to the above-described configuration, and a plurality of light emitting layers 3 are provided, a plurality of thin dielectric layers are provided between the electrodes and the light emitting layers for the purpose of current limitation, driven by an AC power source, and scanning power Both the electrode and the data electrode are transparent electrodes, and one of the electrodes is a black electrode.
- the display device 100 further includes a structure for sealing all or part of the display device 100. It is possible to make appropriate changes, such as further providing a structure for color conversion of the emission color of
- control unit 103 drives the data electrode drive circuit 121 and the scan electrode drive circuit 122 based on information such as whether or not each pixel emits light.
- the scan electrode driving circuit 122 applies a voltage to the scan electrode 2 corresponding to the pixel C to emit light.
- the data electrode drive circuit 121 applies a voltage to the data electrode 4 corresponding to the pixel C that emits light.
- the data electrode X is the back electrode 4 and the scanning electrode Y is the transparent electrode 2 as in FIG.
- a similar manufacturing method can be used for the light emitting layer 3 made of the other materials described above.
- the data electrode Xi (back electrode 4) is formed.
- A1 is used, and patterns are formed substantially in parallel at a predetermined interval by a photolithographic method.
- the film thickness is 20 Onm.
- the light emitting layer 3 is formed on the substrate 1.
- ZnS and Cu S powders for multiple evaporation sources are formed on the substrate 1.
- the substrate temperature is 200 ° C and ZnS and Cu S are co-evaporated.
- the light emitting layer 3 After the light emitting layer 3 is formed, it is baked at 700 ° C for about 1 hour in a sulfur atmosphere. By examining this film by X-ray diffraction and SEM, a polycrystalline structure of minute ZnS crystal grains and a segregation part of Cu S at the grain boundary are observed. Although details are not clear, it is considered that phase separation of ZnS and Cu S occurs and the segregation structure is formed.
- the scan electrode Y (transparent electrode 2) is patterned using, for example, ITO.
- the scanning electrode Y is substantially parallel to the data electrode with a predetermined interval.
- the film thickness of the scan electrode Y is 200 ⁇ m.
- a transparent insulator layer such as silicon nitride is formed on the light emitting layer 3 and the data electrode Y as a protective layer (not shown).
- display device 100 according to the present embodiment is obtained.
- This display device does not need a high voltage with an alternating current like a conventional EL element. Necessary and sufficient light emission luminance can be obtained with a direct current voltage of a certain degree.
- the light emitting layer may be formed by color-coding with RGB phosphors.
- light emitting units for each RGB color such as transparent electrode / light emitting layer / back electrode may be laminated.
- a RGB color can be displayed using a color filter and / or a color conversion filter after creating a display device with a single color or two color light emitting layers.
- the display device can obtain necessary and sufficient light emission luminance with a low DC voltage that does not require an AC high voltage, unlike a conventional display device.
- the light emitting device can emit light at a low voltage and can emit light with high luminance. It is particularly useful as a variety of light sources used for display devices such as televisions, communications, and lighting.
- the display device provides a display device capable of obtaining a high luminance display by low voltage driving. It is particularly useful as a display device for digital cameras, car navigation systems, televisions, etc.
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Description
Claims
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JP2008526775A JPWO2008013171A1 (ja) | 2006-07-25 | 2007-07-24 | 発光素子、及び、表示装置 |
US12/374,976 US7982388B2 (en) | 2006-07-25 | 2007-07-24 | Light emitting element and display device |
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Cited By (4)
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WO2008072520A1 (ja) * | 2006-12-15 | 2008-06-19 | Panasonic Corporation | 線状発光装置 |
WO2008102559A1 (ja) * | 2007-02-23 | 2008-08-28 | Panasonic Corporation | 表示装置 |
JP2009246179A (ja) * | 2008-03-31 | 2009-10-22 | Tdk Corp | 発光素子 |
JP2020513639A (ja) * | 2016-11-14 | 2020-05-14 | 京東方科技集團股▲ふん▼有限公司Boe Technology Group Co.,Ltd. | 量子ドット発光ダイオードおよびその製造方法、並びに表示パネルおよび表示装置 |
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US7982388B2 (en) | 2011-07-19 |
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