WO1996004687A1 - Diode electroluminescente organique a jonction p-n - Google Patents
Diode electroluminescente organique a jonction p-n Download PDFInfo
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- WO1996004687A1 WO1996004687A1 PCT/JP1995/001539 JP9501539W WO9604687A1 WO 1996004687 A1 WO1996004687 A1 WO 1996004687A1 JP 9501539 W JP9501539 W JP 9501539W WO 9604687 A1 WO9604687 A1 WO 9604687A1
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- organic
- thin film
- type fluorescent
- fluorescent semiconductor
- emitting diode
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- 239000010409 thin film Substances 0.000 claims abstract description 49
- 239000004065 semiconductor Substances 0.000 claims abstract description 43
- 230000005684 electric field Effects 0.000 claims abstract description 17
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 19
- -1 polyphenylenevinylene Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229920000412 polyarylene Polymers 0.000 claims description 5
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000000295 emission spectrum Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 239000011521 glass Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229930192419 itoside Natural products 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005036 potential barrier Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 229920001109 fluorescent polymer Polymers 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- 241000132007 Bahia Species 0.000 description 1
- 229930194845 Bahia Natural products 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/114—Poly-phenylenevinylene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
Definitions
- the present invention relates to a light-emitting element having a light-emitting layer structure utilizing electroluminescence of a light-emitting substance that emits light by current injection in an applied electric field, and particularly relates to a PN device having a light-emitting layer structure made of an organic semiconductor.
- the present invention relates to an organic light emitting diode having a junction as a light emitting region.
- Electroluminescent devices emit light from substances, mainly semiconductors, by applying an electric field.
- Light-emitting diodes are a well-known example of EL devices based on inorganic semiconductors of compounds of the Periodic Table III-V primary violet compounds such as G a As or G a P. Although these elements are efficient on the long wavelength side of the visible light region and are widely used in everyday electronics, they have a limited size, and have a large area of dislocation. It has not been used economically.
- Mn or a rare earth element for example, Eu, Ce, Tb or Thin-film EL devices made from inorganic materials by doping S m
- organic EL devices ranging from blue to red are being developed.
- a detailed description of the organic electroluminescence device is described in the following documents, for example. I have.
- organic polymers such as poly (p-fuylenevinylene) having good thermal stability against light emission have been used as organic materials in EL devices by spin coating technology.
- An EL device using such poly (p-phenylenevinylene) is described in, for example, the following document.
- organic EL devices emit light in the process of excitons generated and radiatively deactivated by current injection and recombination of injected holes and electrons.
- All currently known organic EL devices have the following three types of typical two-layer or multilayer device structures. 1) As shown in FIG. 1, a two-layer structure including an organic light emitting layer 2 and a hole transport layer 3 disposed between a gold cathode 1 and a transparent cathode 4 on a transparent substrate 5 is formed. An organic EL element having holes injected from a hole transport layer into a light-emitting layer, where holes and electrons are combined to emit light.2) An electron transport layer 2 and an organic light-emitting layer 3 An organic EL device having a two-layer structure as shown in FIG.
- An organic EL device having a three-layer structure, in which both electrons from the electron transport layer and holes from the hole transport layer are injected into the light-emitting layer, where the holes and Which emission occurs binding the child is three.
- An object of the present invention is to provide an organic light emitting diode having high luminance and high luminous efficiency.
- the organic compound thin film is a kind of semiconductor, and in an organic EL device in which organic thin films are stacked, the characteristic of the junction interface determines the characteristics of the organic EL device itself. For this reason, the relationship between the ionization potential of each organic thin film layer, the electron energy band gap, the respective levels of the Furmi level and the mobility, and the work function of the anode and cathode at each junction interface is very important. .
- the present invention has provided a highly efficient organic EL device structure by using a semiconductor model in consideration of these relationships.
- Organic PN junctions are constructed by laminating two adjacent organic fluorescent semiconductor thin films with different energy band gaps. At the time of thermal equilibrium, the Furmi level in the two materials is constant as a whole. Thermal equilibrium is achieved by free electron carriers diffusing through the junction surface, resulting in an internal electric field within the junction. This internal electric field causes a vacuum level shift and band edge bending.
- the internal electric field created between the conduction bands of the P-type and N-type semiconductor materials acts as a potential barrier that prevents electrons spilling from the N-type material region into the P-type material region.
- the internal electric field created between the valence bands acts as another potential barrier that prevents holes from migrating from the P-type material region to the N-type material.
- organic P-type fluorescent material and the organic N-type fluorescent material of the present invention those having a band gap of 1 eV to 3.5 eV are preferably used.
- Equation 1 When a PN junction is fabricated using an organic P-type fluorescent material and an organic N-type fluorescent material satisfying the relationship of Formula 3 and a bias voltage is applied in the forward direction, electrons and holes are in the P-type material region and N We found that both in the mold material region recombine at the same time, so that light emission from both the P-type fluorescent material and the N-type fluorescent material was obtained. Equation 1: X 1 ⁇ X2
- Equation 2 I P 1 ⁇ I P 2
- Equation 3 — 0.2 eV ⁇ (IP2-IP1)-(X2-X1) ⁇ 0.2 eV
- XI is the absolute value of the electron affinity of the organic P-type fluorescent semiconductor
- X2 is the organic N
- IP 1 means the ionization potential of the organic P-type fluorescent semiconductor
- IP 2 means the ionization potential of the organic N-type fluorescent semiconductor.
- FIG. 1 is a cross-sectional view showing an example of an organic EL device having a laminated structure including a light emitting layer between a metal cathode and a transparent anode on a transparent substrate.
- FIG. 2 is a cross-sectional view showing another example of an organic EL device having a laminated structure including a light emitting layer between a metal cathode and a transparent anode on a transparent substrate.
- FIG. 3 is a sectional view of an organic light emitting diode showing one embodiment of the present invention.
- FIG. 4 is a graph showing a current-pressure curve, a light emission luminance-current curve, and a light emission spectrum of the device obtained in Example 1.
- FIG. 5 is a graph showing the light emission spectrum of each device obtained in Example 1, Comparative Example 1 and Comparative Example 2.
- FIG. 6 is a graph showing a current-voltage curve, a light emission luminance-current curve, and a light emission spectrum of the device obtained in Example 2.
- anode material used in the organic light emitting diode of the present invention a material having a work function that is as large as possible is preferable.
- a material having a work function that is as large as possible is preferable.
- nickel, gold, platinum, palladium, selenium, iridium, alloys thereof, or tin oxide, ITO , Copper iodide is preferred.
- conductive polymers such as poly (3-methylthiophene), polyphenylene sulfide, and polyaniline can be used. These can be used alone or as a laminate of two or more, such as those obtained by forming polyaniline on ITO.
- the cathode material silver, lead, tin, magnesium, aluminum, calcium, indium, chromium, lithium, or an alloy thereof having a small work function is used.
- At least one of the materials used as the anode and the cathode transmits at least 50% of light in the emission wavelength region of the device.
- the organic P-type fluorescent semiconductor material used in the present invention may be a material that satisfies the relationship between the ionization potential and the electron affinity of the organic N-type fluorescent material of Formulas 1 to 3 above. It is possible to use one dispersed in a polymer material or a fluorescent polymer material. Hereinafter, examples of the organic P-type fluorescent material used in the present invention will be described.
- n is an integer of 2 or more.
- a thin film can be easily formed by a method such as spin coating represented by the following formula I, and furthermore, heat An electrically stable boria arylene vinylene polymer is more preferred.
- Ar is a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted It is an unsubstituted divalent heterocyclic group, and these aromatic hydrocarbon groups and heterocyclic groups may be condensed rings, and n is an integer of 2 or more. n is not particularly limited as long as it is an integer of 2 or more, but is preferably 5 to 30,000, and more preferably 10 to 10,000.
- a vacuum preferably for 0.5 to 10 hours, more preferably for 2 to 6 hours
- the organic N-type fluorescent semiconductor material used in the present invention may be a material that satisfies the relationship between the ionization potential and the electron affinity of the organic P-type fluorescent material of Formulas 1 to 3, and may be a fluorescent dye or a fluorescent material. It is possible to use a material in which a dye is dispersed in a polymer material, or a fluorescent polymer material. Examples of the organic N-type fluorescent material used in the present invention are shown below.
- ⁇ is an integer of 2 or more.
- the organic P-type and N-type fluorescent semiconductor thin films forming the anode, the cathode, and the organic PN junction used in the organic light-emitting diode of the present invention can be formed by a known method, for example, vacuum evaporation, spin coating, sputtering, or sol-gel. It can be created by such a method.
- the thickness of the organic fluorescent semiconductor thin film is preferably 500 nm or less, and more preferably 10 nm to 200 nm.
- the thickness of the organic PN junction as long 1000 nm or less, preferably from 1 nm to 500 II m, c and more preferably from 20 nm to 400 nm, such a organic light emitting Daiodo It can be fabricated on a support, and the material used for the support is not particularly limited, but is generally used as a support material for an organic EL device such as glass, quartz, plastic, or a metal sheet. The materials used can be used.
- One example of the present invention is an organic light emitting diode as shown in FIG.
- the ITO formed on the transparent glass substrate 1 is used as the anode 2a.
- the resistance of such an ITO electrode is preferably several hundred ⁇ or less.
- 2b is a cathode having a low work function, for example, silver, lead, tin, magnesium, aluminum, calcium, indium, chromium, lithium, or an alloy thereof.
- aluminum or an alloy of magnesium and aluminum was used.
- the organic PN junction sandwiched between the anode 2a and the cathode 2b is formed by a laminate of a thin film 3 of a P-type organic fluorescent material and a thin film 4 of an N-type organic fluorescent material.
- a polyarylene vinylene polymer well-known as a fluorescent polymer material is preferably used.
- the polyarylenevinylene polymer used in the present invention can be synthesized by a known method. For example,
- the poly (vinylene vinylene) polymer used in the present invention is classified into two types: a solvent-soluble type and a solvent-insoluble type.
- Solvent-soluble compounds are synthesized and purified, then dissolved in a soluble organic solvent, and the solution is formed into a thin film on a substrate by, for example, spin coating.
- Solvent-insoluble ones are prepared by using a solution of the corresponding solvent-soluble intermediate polymer, forming a thin film by a film-forming method such as spin coating, and then heating and desorbing under vacuum to convert the conjugated polymer into a conjugated polymer. Is used.
- a polyphenylene vinylene polymer represented by Chemical Formula 7 (hereinafter abbreviated as PPV) was used.
- PPV polyphenylene vinylene polymer represented by Chemical Formula 7
- Such a PPV is prepared, for example, by mixing a bisulfonium salt obtained by the reaction of 1,4-bischloromethylbenzene with tetrahydrothiophene by a Wessling synthesis method shown below in a mixed solvent system of water and methanol. By reacting with an intermediate in the solution, an intermediate polymer soluble in methanol can be obtained.
- a methanol solution of the intermediate polymer is formed on a transparent ITO glass substrate by spin coating, and the substrate coated with the intermediate polymer is heated under vacuum for several hours (usually 25 CTC or more).
- a thin film of unsubstituted poly (vinylenevinylene) represented by the following formula can be formed on a substrate.
- n is an integer of 2 or more.
- n is an integer of 2 or more.
- reference numeral 4 denotes a thin film of an organic N-type fluorescent material, and the relation between the ionization potential and the electron affinity with each of the polyarylene vinylene polymer thin films, which is the P-type organic fluorescent material, satisfies Equations 1 to 3.
- the P-type material is PPV
- tris (8-quinolinol) aluminum (hereinafter abbreviated as “A 1 Q 3”) represented by the following formula ( ⁇ ) is preferably used.
- a 1 Q 3 (8-quinolinol) aluminum
- Example 1 Preparation of an organic PN junction light-emitting diode using boriopenylenevinylene and A1q3
- n is an integer of 2 or more.
- A1q3 thin film of magnesium (3%) and aluminum (97%) alloy is passed through a 2mm x 2mm mask at a speed of 5 seconds by resistance heating under a vacuum of 10-6 torr.
- a vapor-deposited electrode was obtained of a magnesium-aluminum alloy electrode having a size of 2 mm ⁇ 2 mm and a thickness of 150 nm, thereby forming a light emitting diode.
- a brass is applied to the ITO side of this light-emitting diode, and a negative DC electric field is applied to the gold electrode side.
- the light-emitting diode had a light-emitting peak wavelength of 545 nm and a maximum light-emitting luminance of 2000 Cd / m 2 .
- Figure 4 shows the power of this device. The current-voltage curve, the emission luminance-current curve, and the emission spectrum are shown. In addition, the emission spectrum is also shown in 5a of FIG. 5 for comparison later.
- both the PPV and A1q3 were found to be from the diode of the present invention. It turned out that light was emitted.
- the ionization potential of the deposited film of A1q3 was measured using an AC-1 type device manufactured by Riken Keiki, and the result was 5.7 eV.
- the electron affinity was calculated to be 3.0 eV from the difference between the band gap value 2.7 eV calculated from the absorption edge and the above ionization potential.
- the ionization potential was 5. leV, the band gap was 2.5 eV, and the electron affinity was 2.6 eV.
- Example 2 Organic PN junction using polyphenylenevinylene and A1q3
- ⁇ is an integer of 2 or more.
- FIG. 4 shows a current-voltage curve, a light emission luminance-current curve, and a light emission spectrum of this device. In addition, the emission spectrum is also shown in 5a of FIG. 5 for comparison later.
- the ionization potential of the evaporated A1q3 film was measured using an AC-1 type device manufactured by Riken Keiki, and was 5.7 eV.
- the electron affinity was calculated to be 3. O eV from the difference from the bandgap value of the A 1 q 3 deposited film calculated from the above ionization potential and absorption edge of 2.7 eV.
- the ionization potential was 5.1 eV
- the band gap was 2.5 eV
- the electron affinity was 2.6 eV.
- Example 3 Organic PN junction light emitting device using spirobifluorene and A1Q3
- the organic P-type fluorescent spirobifluorene compound shown in Fig. 1 is used as a 100-nm-thick transparent electrode with resistance heating under a vacuum of 10 e torr at a deposition rate of 3-7 AZ seconds. It was attached on a glass substrate (25 mm x 75 mm x 1. lmm).
- A1q3 which is an organic N-type fluorescent material, was deposited on a spiro thin film having a thickness of 20 nm.
- an alloy of magnesium (3%) and aluminum (97%) was deposited through a 2 mm x 2 mm mask at a deposition rate of 5 seconds by resistance heating under a vacuum of 10 torr.
- Magnet and aluminum alloy electrodes with a size of 2 mm and a thickness of 135 nm were provided, and when a 16 V DC electric field was created to create a light emitting diode, it exceeded 900 C d / m 2 Green light was emitted.
- the luminous efficiency was about 0.15 mZW at 42 C dZm 2 .
- the emission peak wavelength of this emission diode was about 510 nm.
- TP D 60 nm hole transporting material TP D shown in, incidentally, of 9 to the A 1 Q 3 shown by stacking deposited 50 nm, further 6 X 10_ 6 10 rr under a vacuum of, by resistance heating, the Aruminiu arm 5
- a 2 mm x 2 mm aluminum electrode was deposited at 150 nm through a 2 mm x 2 mm mask at man-second speed.
- a positive DC electric field was applied to the ITO side of this EL device and a negative DC electric field was applied to the metal electrode side, and light emission from the ITO glass substrate surface of the device was observed. It was measured.
- Launched at 5c in Figure 5 Indicates an optical spectrum.
- a 2 mm ⁇ 2 mm aluminum electrode was vapor-deposited at 150 nm through a 2 mm ⁇ 2 mm mask at a speed of 5 seconds Z seconds by resistance heating under a vacuum of 418 ⁇ 10 torr.
- a positive DC electric field was applied to the ITO side of the EL device and a negative DC electric field was applied to the gold electrode side, and the emission spectrum from the ITO glass substrate surface of the device was measured.
- 5b of FIG. 5 shows the light emission spectrum.
- an organic PN junction is created by appropriately selecting an organic P-type fluorescent semiconductor material and an organic N-type semiconductor material, and by using this, a high-brightness and high-efficiency organic light-emitting diode can be obtained. can get.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US08/765,681 US6559473B1 (en) | 1994-08-05 | 1995-08-03 | Light-emitting diodes with hetero-PN-junction |
EP95927955A EP0776052A4 (en) | 1994-08-05 | 1995-08-03 | ORGANIC LIGHT-EMITTING DIODE WITH PN TRANSITION |
Applications Claiming Priority (2)
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JP18494394 | 1994-08-05 | ||
JP6/184943 | 1994-08-05 |
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WO1996004687A1 true WO1996004687A1 (fr) | 1996-02-15 |
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PCT/JP1995/001539 WO1996004687A1 (fr) | 1994-08-05 | 1995-08-03 | Diode electroluminescente organique a jonction p-n |
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US (1) | US6559473B1 (ja) |
EP (1) | EP0776052A4 (ja) |
WO (1) | WO1996004687A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002313579A (ja) * | 2001-02-06 | 2002-10-25 | Sony Corp | 有機電界発光素子及び表示装置 |
JP2006210884A (ja) * | 2004-12-28 | 2006-08-10 | Fuji Photo Film Co Ltd | 有機電界発光素子 |
JP2007317378A (ja) * | 2006-05-23 | 2007-12-06 | Toppan Printing Co Ltd | 有機エレクトロルミネッセンス素子および有機エレクトロルミネッセンス素子の製造方法および表示装置 |
JP2014533435A (ja) * | 2011-11-01 | 2014-12-11 | メルク パテント ゲーエムベーハー | 有機エレクトロルミネッセンス素子 |
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US6593687B1 (en) * | 1999-07-20 | 2003-07-15 | Sri International | Cavity-emission electroluminescent device and method for forming the device |
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JP2003187983A (ja) * | 2001-12-17 | 2003-07-04 | Ricoh Co Ltd | 有機elトランジスタ |
KR101246247B1 (ko) * | 2003-08-29 | 2013-03-21 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 전계발광소자 및 그것을 구비한 발광장치 |
JP2007194194A (ja) * | 2005-12-22 | 2007-08-02 | Matsushita Electric Ind Co Ltd | エレクトロルミネッセンス素子およびこれを用いた表示装置、露光装置、照明装置 |
US8697254B2 (en) | 2006-11-14 | 2014-04-15 | Sri International | Cavity electroluminescent devices and methods for producing the same |
JP5552433B2 (ja) | 2008-01-24 | 2014-07-16 | エスアールアイ インターナショナル | 高効率エレクトロルミネセント素子およびそれを生産するための方法 |
CN102067730A (zh) * | 2008-05-16 | 2011-05-18 | Lg化学株式会社 | 层叠式有机发光二极管 |
US10782606B2 (en) | 2018-06-29 | 2020-09-22 | Globalfoundries Inc. | Photolithography methods and structures that reduce stochastic defects |
Citations (1)
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JPH03230583A (ja) * | 1990-02-06 | 1991-10-14 | Toshiba Corp | 有機膜発光素子 |
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JPS62222670A (ja) * | 1986-03-25 | 1987-09-30 | Toshiba Corp | 有機薄膜素子 |
JP2991450B2 (ja) * | 1990-02-06 | 1999-12-20 | 株式会社東芝 | 有機膜発光素子 |
US5093698A (en) * | 1991-02-12 | 1992-03-03 | Kabushiki Kaisha Toshiba | Organic electroluminescent device |
AU669662B2 (en) * | 1991-06-12 | 1996-06-20 | Dupont Displays, Inc | Processible forms of electrically conductive polyaniline and conductive products formed therefrom |
JPH05166583A (ja) * | 1991-12-13 | 1993-07-02 | Matsushita Electric Ind Co Ltd | 有機発光素子およびその作製方法 |
JPH05308146A (ja) * | 1992-05-01 | 1993-11-19 | Ricoh Co Ltd | 有機光起電力素子 |
US5331183A (en) * | 1992-08-17 | 1994-07-19 | The Regents Of The University Of California | Conjugated polymer - acceptor heterojunctions; diodes, photodiodes, and photovoltaic cells |
US5790687A (en) | 1996-06-18 | 1998-08-04 | Levi Strauss & Co. | Method and apparatus for the optical determination of the orientation of a garment workpiece |
-
1995
- 1995-08-03 WO PCT/JP1995/001539 patent/WO1996004687A1/ja not_active Application Discontinuation
- 1995-08-03 EP EP95927955A patent/EP0776052A4/en not_active Withdrawn
- 1995-08-03 US US08/765,681 patent/US6559473B1/en not_active Expired - Fee Related
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JPH03230583A (ja) * | 1990-02-06 | 1991-10-14 | Toshiba Corp | 有機膜発光素子 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002313579A (ja) * | 2001-02-06 | 2002-10-25 | Sony Corp | 有機電界発光素子及び表示装置 |
US6916552B2 (en) | 2001-02-06 | 2005-07-12 | Sony Corporation | Organic electroluminescent device and display unit |
JP2006210884A (ja) * | 2004-12-28 | 2006-08-10 | Fuji Photo Film Co Ltd | 有機電界発光素子 |
JP2007317378A (ja) * | 2006-05-23 | 2007-12-06 | Toppan Printing Co Ltd | 有機エレクトロルミネッセンス素子および有機エレクトロルミネッセンス素子の製造方法および表示装置 |
JP2014533435A (ja) * | 2011-11-01 | 2014-12-11 | メルク パテント ゲーエムベーハー | 有機エレクトロルミネッセンス素子 |
Also Published As
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EP0776052A4 (en) | 2002-03-13 |
EP0776052A1 (en) | 1997-05-28 |
US6559473B1 (en) | 2003-05-06 |
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