WO2013191212A1 - 有機エレクトロルミネッセンス素子 - Google Patents
有機エレクトロルミネッセンス素子 Download PDFInfo
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- WO2013191212A1 WO2013191212A1 PCT/JP2013/066852 JP2013066852W WO2013191212A1 WO 2013191212 A1 WO2013191212 A1 WO 2013191212A1 JP 2013066852 W JP2013066852 W JP 2013066852W WO 2013191212 A1 WO2013191212 A1 WO 2013191212A1
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- WIPO (PCT)
- Prior art keywords
- layer
- amorphous
- electride
- cathode
- organic
- Prior art date
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 41
- 238000002347 injection Methods 0.000 claims abstract description 174
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- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- 238000007740 vapor deposition Methods 0.000 claims description 46
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 42
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- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
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- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Definitions
- the present invention relates to an organic electroluminescence element.
- Organic electroluminescence elements are widely used for displays, backlights, lighting applications, and the like.
- an organic electroluminescent element has an anode, a cathode, and an organic light emitting layer disposed between these electrodes.
- a voltage is applied between the electrodes, holes and electrons are injected from each electrode into the organic light emitting layer.
- the holes and electrons are recombined in the organic light emitting layer, binding energy is generated, and the organic light emitting material in the organic light emitting layer is excited by this binding energy. Since light is emitted when the excited light-emitting material returns to the ground state, a light-emitting element can be obtained by using this.
- the organic electroluminescence element further has a hole injection layer and / or a hole transport layer, and an electron injection layer and / or an electron transport layer.
- the hole injection layer and the hole transport layer are disposed between the anode and the organic light emitting layer, and have a role of selectively injecting holes into the organic light emitting layer.
- the electron injection layer and the electron transport layer are disposed between the cathode and the organic light emitting layer, and have a role of selectively injecting electrons into the organic light emitting layer. Therefore, by arranging these layers, the light emission efficiency of the organic electroluminescence element can be increased (Patent Document 1).
- a material such as lithium fluoride (LiF) is usually used for the electron injection layer.
- lithium fluoride is originally an insulating material
- the thickness of the layer needs to be extremely thin (for example, 0.1 nm to 0.4 nm).
- it is difficult to form such an extremely thin film For example, if the film thickness becomes too thin, it becomes difficult to obtain a layered thin film.
- the film thickness is thick, an electron injection layer having sufficient conductivity cannot be obtained.
- lithium fluoride has a problem that it is relatively unstable and easily deteriorates when exposed to the atmosphere. For this reason, it is necessary to handle the electron injection layer made of lithium fluoride in a controlled environment, and as a result, the manufacturing process becomes complicated.
- the present invention has been made in view of such a background, and an object of the present invention is to provide an organic electroluminescence element having better stability and higher reliability than conventional ones.
- an organic electroluminescence element Having an anode, a light emitting layer, and a cathode in this order, An electron injection layer is disposed between the light emitting layer and the cathode, The electron injection layer is composed of an amorphous C12A7 electride, and an organic electroluminescence device is provided.
- An electron transport layer is disposed between the light emitting layer and the electron injection layer,
- the electron transport layer may be made of a metal oxide.
- the electron transport layer may be in the form of amorphous, crystalline, or a mixed phase of amorphous and crystalline.
- the electron transport layer includes ZnO—SiO 2 , In 2 O 3 —SiO 2 , SnO 2 —SiO 2 , ZnO, In—Ga—Zn—O, In—Zn—. O or SnO 2 may be used.
- An organic electroluminescence device Having an anode, a light emitting layer, and a cathode in this order, An organic electroluminescence device is provided in which the cathode is composed of amorphous C12A7 electride.
- a laminate for forming an organic electroluminescence element which includes a substrate, an electrode, an amorphous C12A7 electride layer, and a metal oxide layer in this order.
- An organic electroluminescent element manufacturing method comprising an anode, a light emitting layer, and a cathode in this order, wherein an electron injection layer is disposed between the light emitting layer and the cathode, Using a crystalline C12A7 electride target having an electron density of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3, a film is formed by vapor deposition in an atmosphere of low oxygen partial pressure.
- a manufacturing method characterized by forming an electron injection layer composed of an amorphous thin film is provided.
- An electron injection layer is disposed between the light emitting layer and the cathode,
- the electron injecting layer is composed of a thin film of an amorphous solid material containing calcium, aluminum, and oxygen.
- An organic electroluminescence device is provided.
- FIG. 6 is a graph collectively showing the evaluation test results of electron injection characteristics in samples 304, 305, and 306; It is the figure which showed schematically the structure of the organic electroluminescent element 400 produced in the Example. It is the graph which showed collectively the evaluation test result of the light emission characteristic in the organic electroluminescent elements 400 and 401. It is the graph which showed collectively the evaluation test result of the light emission characteristic in the organic electroluminescent elements 400 and 401. It is the graph which showed collectively the evaluation test result of the light emission characteristic in the organic electroluminescent elements 400 and 401.
- FIG. 1 is a schematic cross-sectional view of an organic electroluminescence element (hereinafter referred to as “organic EL element”) according to an embodiment of the present invention.
- an organic electroluminescent device 100 includes an anode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection on a substrate 110.
- the layer 170 and the cathode 180 are stacked in this order.
- the hole injection layer 130, the hole transport layer 140, and / or the electron transport layer 160 may be omitted.
- the substrate 110 has a role of supporting each layer constituting the organic EL element 100 on the upper part.
- the substrate 110 and the anode 120 are made of a transparent material.
- the substrate 110 a glass substrate, a plastic substrate, or the like is used.
- the anode 120 a transparent metal oxide thin film such as ITO (indium tin oxide) is used.
- the operating principle of the organic EL element is well known to those skilled in the art, and the operating principle of the organic EL element 100 according to the present invention is basically the same as that known. Therefore, the description of the operation of the organic EL element 100 is omitted here.
- the organic EL device 100 has a feature that the electron injection layer 170 is formed of an amorphous C12A7 electride thin film.
- the amorphous C12A7 electride used as the electron injection layer 170 of the organic EL element 100 exhibits good conductivity. Therefore, when amorphous C12A7 electride is used as the electron injection layer 170, it is not necessary to reduce the thickness of the layer to the order of less than nm, unlike the conventional lithium fluoride electron injection layer.
- amorphous C12A7 electride is a stable ceramic material and does not deteriorate or deteriorate even when exposed to the atmosphere. Therefore, when amorphous C12A7 electride is used as the electron injection layer 170, the problem that handling must be performed in a controlled environment like a conventional lithium fluoride electron injection layer is solved.
- amorphous C12A7 electride has a low work function. Therefore, in the present invention, the barrier for electron injection from the cathode 180 to the light emitting layer 150 can be lowered, and an organic EL element with high light emission efficiency can be obtained.
- amorphous C12A7 electride has a large ionization potential. Therefore, amorphous C12A7 electride has a so-called hole blocking effect. That is, holes that have not recombined with electrons in the light emitting layer 150 are prevented from passing through the electron transport layer 160 and reaching the cathode 180, and the probability of recombination of electrons and holes is increased. Therefore, in this invention, an organic EL element with high luminous efficiency can be obtained.
- the present invention is characterized in that an amorphous C12A7 electride thin film is used as the electron injection layer 170. Accordingly, in the present invention, unlike the conventional organic EL element, it is difficult for the reliability to be lowered or desired light emission characteristics cannot be obtained, and the handling is easy and the organic EL element is highly reliable. It becomes possible to provide.
- Crystal C12A7 means a crystal of 12CaO ⁇ 7Al 2 O 3 and an isomorphous compound having a crystal structure equivalent to this.
- the mineral name of this compound is “mayenite”.
- the crystalline C12A7 in the present invention is a compound in which some or all of Ca atoms and / or Al atoms in the C12A7 crystal skeleton are substituted with other atoms within a range in which the cage structure formed by the skeleton of the crystal lattice is maintained.
- the same type compound may be used in which some or all of the free oxygen ions in the cage are replaced with other anions.
- C12A7 is sometimes denoted as Ca 12 Al 14 O 33 or Ca 24 Al 28 O 66.
- Examples of the isomorphous compound include, but are not limited to, the following compounds (1) to (4).
- metal atoms such as Sr, Mg, and / or Ba.
- a compound in which some or all of Ca atoms are substituted with Sr is strontium aluminate Sr 12 Al 14 O 33 , and calcium strontium aluminum is used as a mixed crystal in which the mixing ratio of Ca and Sr is arbitrarily changed.
- Nate Ca 12-x Sr X Al 14 O 33 (x is an integer of 1 to 11; in the case of an average value, it is a number greater than 0 and less than 12).
- a part of metal atoms and / or nonmetal atoms (excluding oxygen atoms) in the 12CaO.7Al 2 O 3 crystal (including the compounds of (1) and (2) above) is Ti, One or more transition metal atoms selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu, or one or more alkali metals selected from the group consisting of typical metal atoms, Li, Na, and K
- a compound in which some or all of the free oxygen ions included in the cage are replaced with other anions include, for example, anions such as H ⁇ , H 2 ⁇ , H 2 ⁇ , O ⁇ , O 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , and S 2 ⁇ , and nitrogen (N). There are anions.
- the “crystalline C12A7 electride” means that in the above-mentioned “crystalline C12A7”, free oxygen ions included in the cage (in the case of having other anions included in the cage, the anions) ) Means a compound in which part or all of them are substituted with electrons.
- crystalline C12A7 electride shows electroconductivity.
- crystalline C12A7 in which all free oxygen ions are replaced with electrons may be expressed as [Ca 24 Al 28 O 64 ] 4+ (4e ⁇ ).
- amorphous C12A7 electride means an amorphous solid substance having a composition equivalent to that of crystalline C12A7 electride, consisting of solvation having amorphous C12A7 as a solvent and electrons as a solute. means.
- FIG. 2 conceptually shows the structure of the amorphous C12A7 electride.
- each cage shares a plane and is three-dimensionally stacked to form a crystal lattice, and electrons are included in a part of these cages.
- a characteristic partial structure called bipolaron 250 is present in a dispersed state in solvent 220 made of amorphous C12A7.
- the bipolaron 250 is configured by two cages 230 adjacent to each other, and electrons (solutes) 240 being included in each cage 230.
- the state of the amorphous C12A7 electride is not limited to the above, and two electrons (solutes) 240 may be included in one cage 230. Further, a plurality of these cages may be aggregated, and the aggregated cage can be regarded as a microcrystal. Therefore, a state in which the microcrystal is included in the amorphous is also regarded as amorphous in the present invention.
- Amorphous C12A7 electride exhibits electrical conductivity and has a low work function.
- the work function may be 2.4 to 4.5 eV, or 3 to 4 eV.
- the work function of the amorphous C12A7 electride is preferably 2.8 to 3.2 eV.
- Amorphous C12A7 electride has a high ionization potential.
- the ionization potential may be 7.0 to 9.0 eV, or 7.5 to 8.5 eV.
- Bipolaron 250 has almost no light absorption in the visible light range where the photon energy is 1.55 eV to 3.10 eV, and shows light absorption in the vicinity of 4.6 eV. Therefore, the amorphous C12A7 electride thin film is transparent in visible light. Further, by measuring the light absorption characteristics of the sample to be inspected and measuring the light absorption coefficient in the vicinity of 4.6 eV, whether or not the bipolaron 250 exists in the sample, that is, the sample is amorphous C12A7 elect You can check if you have a ride.
- the two adjacent cages 230 constituting the bipolaron 250 are Raman-active, and show a characteristic peak in the vicinity of 186 cm ⁇ 1 in the Raman spectroscopic measurement.
- C12A7 electride means a concept including both the above-mentioned “crystalline C12A7 electride” and “amorphous C12A7 electride”.
- “Crystalline C12A7 electride” includes Ca atoms, Al atoms, and O atoms, the molar ratio of Ca: Al is in the range of 13:13 to 11:15, and the molar ratio of Ca: Al is 12 It is preferably in the range of 5: 13.5 to 11.5: 14.5, and more preferably in the range of 12.2: 13.8 to 11.8: 14.2.
- the “amorphous C12A7 electride” includes Ca atoms, Al atoms, and O atoms, and the molar ratio of Ca: Al is in the range of 13:12 to 11:16.
- the molar ratio of Ca: Al is 13:13 to 11:15 is preferable, and 12.5: 13.5 to 11.5: 14.5 is more preferable.
- the thin film of “amorphous C12A7 electride” is composed of Ca, Al, and O in the above composition range at 67% or more, preferably 80% or more, more preferably 95% or more of the whole. preferable.
- substrate 110 If the board
- the transparent material for example, a glass substrate, a plastic substrate, a resin substrate, or the like can be used.
- anode 120 As the anode 120, a metal or a metal oxide is usually used.
- the material used preferably has a work function of 4 eV or more. As described above, when the light extraction surface of the organic EL element 100 is the substrate 110 side, the anode 120 needs to be transparent.
- the anode 120 may be a metal material such as aluminum, silver, tin, gold, carbon, iron, cobalt, nickel, copper, zinc, tungsten, vanadium, and alloys thereof.
- the anode 120 is made of, for example, ITO, antimony oxide (Sb 2 O 3 ), zirconium oxide (ZrO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), IZO (Indium Zinc Oxide), AZO (ZnO—Al 2 O 3 : zinc oxide doped with aluminum), GZO (ZnO—Ga 2 O 3 : zinc oxide doped with gallium), Nb-doped TiO 2 , Ta-doped TiO 2 , and IWZO It may also be a metal oxide material such as (In 2 O 3 —WO 3 —ZnO: indium oxide doped with tungsten trioxide and zinc oxide).
- the film formation method of the anode 120 is not particularly limited.
- the anode 120 may be formed by a known film forming technique such as vapor deposition, sputtering, or coating.
- the thickness of the anode 120 is in the range of 50 nm to 150 nm.
- the thickness of the anode 120 is preferably in the range of 2 nm to 50 nm.
- the hole injection layer 130 is selected from materials having hole injection properties.
- the hole injection layer 130 may be an organic material such as CuPc and starburst amine.
- the hole injection layer 130 may be a metal oxide material, for example, an oxide including at least one metal selected from molybdenum, tungsten, rhenium, vanadium, indium, tin, zinc, gallium, titanium, and aluminum. good.
- the top electrode formed on the organic layer is formed by sputtering
- the characteristics of the organic EL element deteriorate due to sputtering damage of the organic layer. Since sputtering resistance is higher than that of the material, sputtering damage to the organic layer can be reduced by forming a metal oxide film over the organic material.
- the hole injection layer 130 may be omitted.
- the method for forming the hole injection layer 130 is not particularly limited.
- the hole injection layer 130 may be formed by a dry process such as an evaporation method or a transfer method.
- the hole injection layer 130 may be formed by a wet process such as a spin coating method, a spray coating method, or a gravure printing method.
- the thickness of the hole injection layer 130 is in the range of 1 nm to 50 nm.
- the hole transport layer 140 is selected from materials having hole transport properties.
- the hole transport layer 140 may be, for example, an arylamine compound, an amine compound containing a carbazole group, and an amine compound containing a fluorene derivative.
- the hole transport layer 140 includes 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), N, N′-bis (3-methylphenyl)- (1,1′-biphenyl) -4,4′-diamine (TPD), 2-TNATA, 4,4 ′, 4 ′′ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine ( MTDATA), 4,4′-N, N′-dicarbazole biphenyl (CBP), spiro-NPD, spiro-TPD, spiro-TAD, TNB, and the like.
- hole transport layer 140 various known materials can be used for the hole transport layer 140. Note that the hole transport layer 140 may be omitted.
- the hole transport layer 140 can be formed using a conventional general film formation process.
- the thickness of the hole transport layer 140 is in the range of 1 nm to 100 nm.
- the light emitting layer 150 may be made of any material known as a light emitting material for an organic electroluminescence element.
- the light emitting layer 150 includes, for example, epidolidine, 2,5-bis [5,7-di-t-pentyl-2-benzoxazolyl] thiophene, 2,2 ′-(1,4-phenylenedivinylene) bisbenzo Thiazole, 2,2 ′-(4,4′-biphenylene) bisbenzothiazole, 5-methyl-2- ⁇ 2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl ⁇ benzoxazole, 2,5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perinone, 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin, acridine, stilbene, 2- (4-biphenyl) -6-phenylbenzoxazole, aluminum trisoxi
- various known materials can be used for the light emitting layer 150.
- the light emitting layer 150 may be formed by a dry process such as an evaporation method or a transfer method. Alternatively, the light emitting layer 150 may be formed by a wet process such as a spin coating method, a spray coating method, or a gravure printing method.
- the thickness of the light emitting layer 150 is in the range of 1 nm to 100 nm. Further, the light emitting layer may also be used as a hole transport layer or an electron transport layer.
- the electron transport layer 160 is made of an organic material such as tris (8-quinolinolato) aluminum (Alq3). In general, however, organic materials such as Alq3 can easily degrade when exposed to air.
- the electron transport layer 160 it is preferable to use a metal oxide material as the electron transport layer 160.
- These metal oxide materials may be in an amorphous form, in a crystalline form, or in a mixed phase of an amorphous and crystalline phase.
- the metal oxide material is preferably in an amorphous form. This is because an amorphous metal oxide material can easily provide a relatively flat film.
- the electron affinity of these metal oxide materials is preferably 2.8 to 5.0 eV, more preferably 3.0 to 4.0 eV, and further preferably 3.1 eV to 3.5 eV. preferable.
- the electron affinity is 2.8 eV or more, the electron injection characteristics are high, and the light emission efficiency of the organic EL element is improved. Further, when the electron affinity is 5.0 eV or less, it is easy to obtain sufficient light emission from the organic EL element.
- the electron transport layer 160 When these metal oxide materials are used as the electron transport layer 160, the effect of improving the stability of the layer and facilitating handling can be obtained as compared with the case of using an organic material such as Alq3.
- the Alq3 material has a property that the mobility of holes is relatively high.
- any of the aforementioned metal oxide materials has a relatively small hole mobility and can selectively transport only electrons. Therefore, when these metal oxide materials are used as the electron transport layer 160, the light emission efficiency of the organic EL element can be further increased.
- the thickness of the electron transport layer 160 made of these metal oxide materials may be 1 nm to 2000 nm, preferably 100 nm to 2000 nm, more preferably 200 nm to 1000 nm, and 300 nm to 500 nm. More preferably.
- the above metal oxide material has an electron mobility of 1 to 10 cm 2 V ⁇ 1 s ⁇ 1 and is several orders of magnitude larger. Is possible.
- it is possible to suppress the short circuit of an organic EL element compared with the case where an organic electron carrying layer is used.
- the thickness of the inorganic electron transport layer exceeds 2000 nm, it takes a long time to produce a thin film, and thus the produced organic EL element is expensive.
- the film forming method of the electron transport layer 160 is not particularly limited.
- a known film formation technique such as a vapor deposition method, a sputtering method, or a coating method may be used.
- the electron transport layer 160 may be omitted.
- Electrode injection layer 170 As described above, amorphous C12A7 electride is used for the electron injection layer 170 in the organic EL 100.
- the thickness of the conventional electron injection layer 170 is, for example, in the range of 0.1 nm to 0.4 nm. This is because, as described above, LiF that has been conventionally used as an electron injection layer has high resistance and cannot be used as a conductive member unless it is made extremely thin.
- the electron injection layer 170 made of amorphous C12A7 electride has conductivity, there is no restriction on the film thickness. Therefore, the electron injection layer 170 having a relatively uniform thickness can be formed relatively easily.
- the electron injection layer 170 made of amorphous C12A7 electride has a thickness in the range of about 1 nm to 50 nm, for example. It may be 30 nm or less, or 20 nm or less. It may be 2 nm or more, 4 nm or more, or 9 nm or more.
- amorphous C12A7 electride is a ceramic material and is stable without being altered even when exposed to the atmosphere. Therefore, when amorphous C12A7 electride is used as the electron injection layer 170, the problem that handling must be performed in a controlled environment as in a conventional lithium fluoride electron injection layer is solved. As a result, it is possible to obtain an organic EL element 100 that is easy to handle and highly reliable.
- Method for forming electron injection layer 170 Here, an example of a method for forming a thin film of amorphous C12A7 electride for the electron injection layer 170 will be described.
- FIG. 3 schematically shows a flow of a method for forming a thin film of amorphous C12A7 electride.
- the method for forming a thin film of amorphous C12A7 electride is as follows: Preparing a target of crystalline C12A7 electride having an electron density of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 (S110); A step of forming a film on the cathode or the electron transport layer by a vapor deposition method in an atmosphere having an oxygen partial pressure of less than 0.1 Pa using the target (S120); Have
- the target is composed of crystalline C12A7 electride.
- the manufacturing method of the target made of crystalline C12A7 electride is not particularly limited.
- the target may be manufactured using, for example, a conventional method for manufacturing a bulk crystalline C12A7 electride.
- a crystalline C12A7 sintered body is subjected to heat treatment at about 1150 to 1460 ° C., preferably about 1200 to 1400 ° C. in the presence of a reducing agent such as Ti, Al, Ca, or C.
- a target made of quality C12A7 electride may be manufactured.
- a green compact formed by compressing a crystalline C12A7 powder may be used as a target.
- a crystalline C12A7 sintered body is effectively heat-treated at 1230 to 1415 ° C.
- a target made of quality C12A7 electride can be produced.
- a target having an area of 3 inches (76.2 mm) or more in diameter and a thickness of 2 mm or more can be produced, and more preferably, a target having an area of 4 inches (101.6 mm) or more in diameter and a thickness of 3 mm or more.
- the electron density of the target that is, crystalline C12A7 electride is in the range of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 .
- the electron density of the crystalline C12A7 electride is preferably 1 ⁇ 10 19 cm ⁇ 3 or more, more preferably 1 ⁇ 10 20 cm ⁇ 3 or more, further preferably 5 ⁇ 10 20 cm ⁇ 3 or more, and 1 ⁇ 10 21 cm ⁇ 3 or more is particularly preferable.
- the higher the electron density of the crystalline C12A7 electride constituting the target the easier it is to obtain an amorphous C12A7 electride having a lower work function.
- the electron density of the crystalline C12A7 electride is more preferably 1.4 ⁇ 10 21 cm ⁇ 3 or more, and 1.7 ⁇ 10 21 cm ⁇ 3 or more is more preferable, and 2 ⁇ 10 21 cm ⁇ 3 or more is particularly preferable.
- the electron density of the crystalline C12A7 electride is 2.3 ⁇ 10 21 cm ⁇ 3 .
- the electron density of the crystalline C12A7 electride is less than 2.0 ⁇ 10 18 cm ⁇ 3 , the electron density of the amorphous C12A7 electride thin film obtained by film formation becomes small.
- the electron density of C12A7 electride can be measured by the iodine titration method.
- the electron density of the crystalline C12A7 electride can be measured by a light absorption measurement method. Since the crystalline C12A7 electride has a specific light absorption around 2.8 eV, the electron density can be determined by measuring the absorption coefficient. In particular, when the sample is a sintered body, it is convenient to use the diffuse reflection method after pulverizing the sintered body into a powder.
- the obtained target is used as a raw material source when an amorphous C12A7 electride thin film is formed in the next step.
- the surface of the target may be polished by mechanical means before use.
- a bulk body of crystalline C12A7 electride obtained by a conventional method may have a very thin film (foreign matter) on the surface.
- the composition of the obtained thin film may deviate from a desired composition ratio.
- such a problem can be significantly suppressed by carrying out the polishing treatment of the target surface.
- vapor deposition refers to vapor deposition of a target material including a physical vapor deposition (PVD) method, a PLD method, a sputtering method, and a vacuum deposition method, and then depositing this material on a substrate.
- PVD physical vapor deposition
- PLD physical vapor deposition
- sputtering method a sputtering method
- vacuum deposition method a vacuum deposition method
- the sputtering method is particularly preferable.
- a thin film can be formed relatively uniformly in a large area.
- the sputtering method includes a DC (direct current) sputtering method, a high frequency sputtering method, a helicon wave sputtering method, an ion beam sputtering method, a magnetron sputtering method, and the like.
- process S120 will be described by taking as an example the case where film formation is performed by a sputtering method.
- the temperature of the substrate on which the thin film of electride is formed is not particularly limited, and any temperature in the range from room temperature to, for example, 700 ° C. may be adopted. It should be noted that the substrate need not necessarily be “positively” heated when depositing the electride thin film. However, there may be a case where the temperature of the deposition target substrate rises “incidentally” due to the radiation heat of the vapor deposition source. For example, the temperature of the deposition target substrate may be 500 ° C. or lower, or 200 ° C. or lower.
- the film formation substrate is not “positively” heated, it is possible to use, as the substrate material, a material whose heat resistance is reduced on the high temperature side exceeding 700 ° C., such as glass or plastic.
- the deposition target substrate may be heat-treated in a vacuum atmosphere before the electride thin film is formed.
- a vacuum atmosphere For example, when the substrate exposed to the atmosphere is held at 300 ° C. for 10 minutes at a vacuum degree of 10 ⁇ 6 Pa, moisture adsorbed on the substrate is desorbed, so that the base surface can be cleaned.
- the oxygen partial pressure during film formation is preferably less than 0.1 Pa.
- the oxygen partial pressure is preferably 0.01 Pa or less, more preferably 1 ⁇ 10 ⁇ 3 Pa or less, further preferably 1 ⁇ 10 ⁇ 4 Pa or less, and 1 ⁇ 10 ⁇ 5 Pa or less. It is particularly preferred that When the oxygen partial pressure is 0.1 Pa or more, oxygen is taken into the deposited thin film, which may reduce the electron density.
- the hydrogen partial pressure during film formation is preferably less than 0.004 Pa. If it is 0.004 Pa or more, hydrogen or OH component is taken into the formed thin film, and the electron density of the amorphous C12A7 electride thin film may be lowered.
- the sputtering gas used is not particularly limited.
- the sputtering gas may be an inert gas or a rare gas.
- the inert gas eg, N 2 gas.
- examples of the rare gas include He (helium), Ne (neon), Ar (argon), Kr (krypton), and Xe (xenon). These may be used alone or in combination with other gases.
- the sputtering gas may be a reducing gas such as NO (nitrogen monoxide).
- the pressure of the sputtering gas is not particularly limited, and can be freely selected so that a desired thin film can be obtained.
- the sputtering gas pressure (pressure in the chamber) P (Pa) is set such that the distance between the substrate and the target is t (m) and the diameter of the gas molecule is d (m). 8.9 ⁇ 10 ⁇ 22 / (td 2 ) ⁇ P ⁇ 4.5 ⁇ 10 ⁇ 20 / (td 2 ) (3) Formula It may be selected to satisfy.
- the mean free path of the sputtered particles becomes substantially equal to the distance between the target and the substrate, and the sputtered particles are suppressed from reacting with the remaining oxygen.
- a sputtering method apparatus it is possible to use an inexpensive and simple vacuum apparatus having a relatively high back pressure.
- an amorphous C12A7 electride thin film can be formed on the cathode or the electron transport layer 160.
- the obtained thin film has a composition of C12A7 by the composition analysis of a thin film.
- the thin film is an amorphous C12A7 electride by measuring the light absorption characteristics of the sample and determining the presence or absence of light absorption near the photon energy of 4.6 eV. Can do.
- the thin film is amorphous C12A7 electride by determining the presence or absence of a characteristic peak in the vicinity of 186 cm ⁇ 1 in Raman spectroscopic measurement. Can do.
- the method of forming an amorphous C12A7 electride thin film has been briefly described by taking the sputtering method as an example.
- the method for forming the amorphous C12A7 electride thin film is not limited to this, and the above-described two steps (steps S110 and S120) may be appropriately changed, or various steps may be added. It is clear.
- a pre-sputtering process (a target dry etching process) may be performed on the target before starting the film formation of the amorphous C12A7 electride by the sputtering method.
- the surface of the target is cleaned, and it becomes easy to form a thin film having a desired composition in the subsequent film formation process (main film formation).
- the target when the target is used for a long time, oxygen is taken into the surface of the target, and the electron density of the crystalline C12A7 electride constituting the target may decrease.
- the composition of the target when the target is used for a long time, the composition of the target may deviate from the initial composition due to the difference in sputtering rate of each component constituting the target (ie, crystalline C12A7 electride).
- the composition may deviate from a desired value even in the formed thin film.
- the pre-sputtering process may be performed, for example, before performing a new film formation or whenever the target usage time reaches a predetermined value.
- the gas used in the pre-sputtering process may be the same as or different from the sputtering gas used in the main film formation.
- the gas used for the pre-sputtering process is preferably He (helium), Ne (neon), N 2 (nitrogen), Ar (argon), and / or NO (nitrogen monoxide).
- the amorphous C12A7 electride thin film formed by such a method has an electron density in the range of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 . It exhibits light absorption at a photon energy position of 6 eV.
- the electron density is more preferably 1 ⁇ 10 19 cm ⁇ 3 or more, and further preferably 1 ⁇ 10 20 cm ⁇ 3 or more.
- the light absorption value at a position of 4.6 eV may be 100 cm ⁇ 1 or more. It may be 200 cm ⁇ 1 or more.
- the electron density of the amorphous C12A7 electride thin film can be measured by the above-mentioned iodine titration method.
- the density of the bipolaron can be calculated by halving the measured electron density.
- the thin film of amorphous C12A7 electride has conductivity due to hopping conduction of electrons in the cage.
- the DC conductivity at room temperature of the amorphous C12A7 electride thin film may be 10 ⁇ 9 to 10 ⁇ 1 S ⁇ cm ⁇ 1 , and 10 ⁇ 7 to 10 ⁇ 3 S ⁇ cm ⁇ . 1 may be sufficient.
- the amorphous C12A7 electride thin film according to the present invention may have, as a partial structure, an F + center in which one electron is captured in an oxygen vacancy.
- the F + center is configured by a plurality of Ca 2+ ions surrounded by one electron and does not have a cage.
- the F + center has light absorption in the visible light range of 1.55 eV to 3.10 eV centered on 3.3 eV.
- the concentration of F + center is less than 5 ⁇ 10 18 cm ⁇ 3 , the transparency of the thin film is increased, which is preferable.
- the concentration of the F + center is more preferably 1 ⁇ 10 18 cm ⁇ 3 or less, and further preferably 1 ⁇ 10 17 cm ⁇ 3 or less. Note that the concentration of the F + center can be measured by a signal intensity having a g value of 1.998 in ESR.
- the ratio of the light absorption coefficient at the position of 3.3 eV to the light absorption coefficient at the photon energy position of 4.6 eV may be 0.35 or less.
- the root mean square roughness (RMS) of the surface of the amorphous C12A7 electride thin film may be 0.1 to 10 nm, and preferably 0.2 to 5 nm.
- RMS root mean square roughness
- the electron injection layer 170 is formed of an amorphous C12A7 electride thin film having an RMS of 2 nm or less, the characteristics of the organic EL element 100 are improved, which is more preferable. Further, when the RMS is 10 nm or more, the characteristics of the organic EL element 100 may be deteriorated, so that it is necessary to add a polishing process or the like.
- RMS can be measured using, for example, an atomic force microscope.
- the cathode 180 is usually made of a metal material. When the light extraction surface of the organic EL element 100 is the cathode 180 side, the cathode 180 needs to be transparent.
- the cathode 180 may be, for example, aluminum, silver, gold, magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, molybdenum, vanadium, chromium, tantalum, and alloys thereof.
- the cathode 180 may be, for example, ITO, antimony oxide (Sb 2 O 3 ), zirconium oxide (ZrO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), IZO (Indium Zinc Oxide), AZO (ZnO—Al 2 O 3 : zinc oxide doped with aluminum), GZO (ZnO—Ga 2 O 3 : zinc oxide doped with gallium), Nb-doped TiO 2 , Ta-doped TiO 2 , and IWZO It may also be a metal oxide material such as (In 2 O 3 —WO 3 —ZnO: indium oxide doped with tungsten trioxide and zinc oxide).
- the film forming method of the cathode 180 is not particularly limited.
- the cathode 180 may be formed by, for example, an evaporation method (vacuum evaporation method, electron beam evaporation method), ion plating method, laser ablation method, sputtering method, or the like.
- the thickness of the cathode 180 is in the range of 50 nm to 150 nm.
- the thickness of the cathode 180 is preferably in the range of 2 nm to 50 nm.
- the configuration of the organic EL element has been described by taking as an example the case where the anode 120 is disposed closer to the substrate 110 and the cathode 180 is disposed farther from the substrate 110.
- the configuration of the organic EL element is not limited to this.
- the cathode 180 may be disposed on the side closer to the substrate 110, and the anode 120 may be disposed on the side farther from the substrate 110.
- the organic EL element has a configuration in which the layers 120 to 180 excluding the substrate 110 are vertically inverted in FIG.
- a sputtering film is continuously formed on a substrate in the order of a (transparent) electrode, an amorphous C12A7 electride, and an electron transport layer made of a metal oxide material
- the electrode and the amorphous C12A7 electride are chemically converted. It is preferable because it can be protected by an electron transport layer made of a metal oxide material and particularly excellent in mechanical durability and mechanical strength. Since such a laminate is excellent in stability, such as being easily transportable in the air, the production of an organic EL element becomes simple.
- the organic EL element 100 includes an electron injection layer 170 composed of a thin film of amorphous C12A7 electride.
- the electron injection layer 170 is not always necessary, and this layer may be omitted.
- the cathode 180 is formed of an amorphous C12A7 electride thin film.
- both the electron injection layer 170 and the cathode 180 may be composed of a thin film of amorphous C12A7 electride.
- an organic electroluminescence device manufacturing method comprising an anode, a light emitting layer, and a cathode in this order, and an electron injection layer disposed between the light emitting layer and the cathode.
- a manufacturing method for forming an electron injection layer composed of an amorphous thin film by forming a film on the cathode or the light emitting layer is provided.
- Another embodiment of the present invention is a method for manufacturing an organic electroluminescent element having an anode, a light emitting layer, and a cathode in this order, and has an electron density of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3.
- a cathode composed of an amorphous thin film is formed by vapor deposition under a low oxygen partial pressure atmosphere.
- the amorphous thin film constituting the electron injection layer or the cathode may be composed of an amorphous solid material containing calcium, aluminum, and oxygen. That is, the amorphous thin film constituting the electron injection layer or the cathode may be an amorphous oxide electride containing calcium atoms and aluminum atoms. A state where microcrystals are contained in an amorphous state is also regarded as an amorphous state in the present invention.
- the molar ratio of Al / Ca is preferably 0.5 to 4.7, more preferably 0.6 to 3, and further preferably 0.8 to 2.5. .
- the composition analysis of the thin film can be performed by XPS method, EPMA method, EDX method or the like.
- the composition of the amorphous thin film may be different from the stoichiometric ratio of C12A7, or may be different from the composition ratio of the target used in the production.
- crystalline when the composition is different from the stoichiometric ratio of C12A7, a mixture of C12A7 crystal and C3A (3CaO.Al 2 O 3 ) crystal and / or CA (3CaO.Al 2 O 3 ) crystal It becomes. Since the C3A crystal and the CA crystal are insulators and have a large work function, the electrical characteristics are inhomogeneous depending on the crystalline part. In addition, these crystals have different thermal and mechanical characteristics, and it is easy to form discontinuous grain boundaries, and the surface flatness is low.
- an amorphous thin film is homogeneous and has a high surface flatness because it does not produce different phases such as C3A crystal and CA crystal even if its composition is different from the stoichiometric ratio of C12A7.
- the amorphous thin film preferably contains electrons in an electron density range of 2.0 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 .
- the electron density is more preferably 1 ⁇ 10 19 cm ⁇ 3 or more, and further preferably 1 ⁇ 10 20 cm ⁇ 3 or more.
- the amorphous thin film preferably absorbs light at a photon energy position of 4.6 eV.
- An amorphous thin film exhibits semiconducting electrical characteristics and has a low work function.
- the work function may be 2.4 to 4.5 eV, or 2.8 to 3.2 eV.
- An amorphous thin film has a high ionization potential.
- the ionization potential may be 7.0 to 9.0 eV, or 7.5 to 8.5 eV.
- the amorphous thin film has a high transparency because it has an F + center of less than 5 ⁇ 0 18 cm ⁇ 3 .
- the concentration of the F + center is more preferably 1 ⁇ 10 18 cm ⁇ 3 or less, and further preferably 1 ⁇ 10 17 cm ⁇ 3 or less.
- the ratio of the light absorption coefficient at a position of 3.3 eV to the light absorption coefficient at a photon energy position of 4.6 eV may be 0.35 or less.
- the organic electroluminescence device of the present invention may have any of the following configurations.
- a substrate, an anode, and a cathode are provided in this order, and the substrate side is a light extraction surface.
- An amorphous thin film of an amorphous solid material containing calcium, aluminum, and oxygen is It exists between the cathodes or constitutes the cathode.
- a substrate, an anode, and a cathode are provided in this order, and the cathode side is a light extraction surface.
- An amorphous thin film of an amorphous solid material containing calcium, aluminum, and oxygen is It exists between the cathodes or constitutes the cathode.
- a substrate, a cathode, and an anode are provided in this order, and the substrate side is a light extraction surface.
- An amorphous thin film of an amorphous solid material containing calcium, aluminum, and oxygen is It exists between the cathodes or constitutes the cathode.
- a substrate, a cathode, and an anode are provided in this order, and the anode side is a light extraction surface.
- An amorphous thin film of an amorphous solid material containing calcium, aluminum, and oxygen is It exists between the cathodes or constitutes the cathode.
- the organic EL element of the present invention preferably has the above configurations (2) and (4) from the viewpoint of the aperture ratio when a light emitting device is configured in combination with a TFT having a transparent amorphous oxide semiconductor. .
- the configuration (3) or (4) is preferable.
- the light emitting device may be a display device or a lighting device.
- Example 1 A sample simulating the structure of the cathode portion of the organic EL element was produced by the following method, and its characteristics were evaluated.
- sample preparation A sample 300 having the structure shown in FIG. 4 was produced by the following procedure.
- a glass substrate (made of non-alkali glass) 310 having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was prepared as a substrate.
- a metal aluminum layer 320 as a cathode was formed on one surface of the glass substrate 310 by sputtering.
- the thickness of the metal aluminum layer 320 is about 100 nm.
- the glass substrate 310 with the cathode is taken out from the sputtering apparatus and introduced into another sputtering apparatus, and an amorphous C12A7 electride layer is formed as an electron injection layer 330 on the metal aluminum layer 320. did.
- the amorphous C12A7 electride layer was formed by the method shown in FIG.
- the electron density of the target crystalline C12A7 electride is 8.5 ⁇ 10 20 cm ⁇ 3 .
- an amorphous C12A7 electride layer was formed by sputtering under an oxygen partial pressure atmosphere of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 2.13 Pa.
- a pre-sputtering process using He gas was performed.
- the glass substrate 310 was not actively heated.
- the thickness of the obtained amorphous C12A7 electride layer is about 10 nm.
- the glass substrate 310 with the electron injection layer 330 (and the metal aluminum layer 320) was taken out from the sputtering apparatus.
- this glass substrate 310 was introduced into a vapor deposition apparatus, and an Alq3 layer as an electron transport layer 340 was formed on the amorphous C12A7 electride layer by vapor deposition.
- the thickness of the Alq3 layer is about 60 nm.
- the Alq3 layer was formed as a region having a diameter of 12 mm in the vicinity of the center of the surface of the electron injection layer 330 using a metal mask.
- an evaluation electrode 350 measuring 2 mm in length and 2 mm in width was installed by vapor deposition.
- the evaluation electrode 350 was made of metallic aluminum, and the thickness of the evaluation electrode 350 was about 100 nm.
- a sample 300 including a glass substrate 310, a metal aluminum layer 320, an electron injection layer 330, an electron transport layer 340, and an evaluation electrode 350 was produced.
- the sample 301 was produced by the same method. However, in this sample 301, the film formation step of the amorphous C12A7 electride layer was not performed during the production. Therefore, the sample 301 does not have the electron injection layer 330 but has the electron transport layer 340 directly on the metal aluminum layer 320.
- the electron injection property was implemented by measuring the current value obtained when a predetermined voltage was applied between the metal aluminum layer 320 and the evaluation electrode 350 in each of the samples 300 and 301.
- the applied voltage was set to a range from 0 V to 10 V (based on the metal aluminum layer 320).
- the horizontal axis indicates the applied voltage (based on the metal aluminum layer 320), and the vertical axis indicates the current density generated between the metal aluminum layer 320 and the evaluation electrode 350.
- the current density at the same voltage is significantly higher in the sample 300 having the electron injection layer 330 made of amorphous C12A7 electride than in the sample 301 having no electron injection layer 330 made of amorphous C12A7 electride. (Particularly when the applied voltage is higher than 6V).
- the electron injection layer 330 made of amorphous C12A7 electride was installed as the electron injection layer, it was confirmed that the electron injection barrier was lowered and the current characteristics of the sample were improved.
- the sample 300 after the electron injection layer 330 made of amorphous C12A7 electride is installed in the manufacturing process, the sample is once opened to the atmosphere.
- the amorphous C12A7 electride layer is the electron injection layer 330, it is relatively stable without considering the influence of the environment. It was confirmed that an organic EL element can be manufactured.
- Example 2 A device was fabricated in the same manner as in Example 1 except that the thickness of the Alq3 layer was 150 nm, and a sample 302 having an electron injection layer 330 made of amorphous C12A7 electride and an electron made of amorphous C12A7 electride A sample 303 having no injection layer 330 was produced.
- Example 3 A sample simulating the structure of the cathode portion of the organic EL element was produced by the following method, and its characteristics were evaluated.
- sample preparation In the following procedure, a sample 304 having an electron injection layer 330 made of amorphous C12A7 electride, a sample 305 having an electron injection layer 330 made of lithium fluoride, and a sample 306 having no electron injection layer 330 Produced.
- a glass substrate (made of non-alkali glass) 310 having a length of 10 mm, a width of 10 mm, and a thickness of 0.7 mm was prepared as a substrate.
- a metal aluminum layer 320 as a cathode was formed on one surface of the glass substrate 310 by sputtering.
- the metal aluminum layer 320 is 4 mm long ⁇ 1 mm wide ⁇ 100 nm thick.
- the glass substrate 310 with the cathode is taken out from the sputtering apparatus and introduced into another sputtering apparatus, and an amorphous C12A7 electride layer is formed as an electron injection layer 330 on the metal aluminum layer 320. did.
- the amorphous C12A7 electride layer was formed by the method shown in FIG.
- the electron density of the target crystalline C12A7 electride is 8.5 ⁇ 10 20 cm ⁇ 3 .
- an amorphous C12A7 electride layer was formed by sputtering under an oxygen partial pressure atmosphere of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 2.13 Pa.
- a pre-sputtering process using He gas was performed.
- the glass substrate 310 with the cathode was not actively heated.
- the thickness of the obtained amorphous C12A7 electride layer is about 1 nm.
- the glass substrate 310 with the electron injection layer 330 (and the metal aluminum layer 320) was taken out from the sputtering apparatus.
- the glass substrate 310 was introduced into a vapor deposition apparatus capable of plasma processing, and after the cleaning by the plasma processing, vapor deposition was performed.
- the plasma treatment was performed for 1 minute with He gas 0.6 Pa and RF power 50 W.
- an Alq3 layer as the electron transport layer 340 was formed on the amorphous C12A7 electride layer by vapor deposition.
- the thickness of the Alq3 layer is about 150 nm.
- the Alq3 layer was formed as a 2 mm ⁇ 2 mm region using a metal mask so as to completely cover the electron injection layer 330.
- the degree of vacuum during the deposition was about 3 ⁇ 10 ⁇ 6 Pa.
- an evaluation electrode 350 having a length of 1 mm, a width of 4 mm, and a thickness of 80 nm was placed on the glass substrate 310 with the electron transport layer 340 by a vapor deposition method so as to be orthogonal to the cathode. That is, a region of 1 mm ⁇ 1 mm where the cathode and the evaluation electrode overlap is a region that is energized by voltage application.
- the evaluation electrode 350 is made of metallic aluminum.
- a sample 304 including a glass substrate 310, a metal aluminum layer 320, an electron injection layer 330 made of amorphous C12A7 electride, an electron transport layer 340, and an evaluation electrode 350 was produced.
- a sample 305 having an electron injection layer 330 made of lithium fluoride was produced by the following method.
- a glass substrate (made of non-alkali glass) 310 having a length of 10 mm, a width of 10 mm, and a thickness of 0.7 mm was prepared as a substrate.
- a metal aluminum layer 320 as a cathode was formed on one surface of the glass substrate 310 by sputtering.
- the metal aluminum layer 320 is 4 mm long ⁇ 1 mm wide ⁇ 100 nm thick.
- the glass substrate 310 with the metal aluminum layer 320 was taken out from the sputtering apparatus.
- the glass substrate 310 was introduced into a vapor deposition apparatus capable of plasma processing, and after the cleaning by the plasma processing, vapor deposition was performed.
- the plasma treatment was performed for 1 minute with He gas 0.6 Pa and RF power 50 W.
- a lithium fluoride layer was formed as an electron injection layer 330 on the metal aluminum layer 320 by vapor deposition.
- the degree of vacuum during vapor deposition is about 3 ⁇ 10 ⁇ 6 Pa.
- the thickness of the lithium fluoride layer was about 0.5 nm.
- an Alq3 layer as the electron transport layer 340 and an evaluation electrode 350 were formed on the lithium fluoride layer in the same manner as the sample 304 by vapor deposition.
- a sample 305 including a glass substrate 310, a metal aluminum layer 320, an electron injection layer 330 made of lithium fluoride, an electron transport layer 340, and an evaluation electrode 350 was produced.
- a sample 306 having no electron injection layer 330 was produced by the following method.
- a glass substrate (made of non-alkali glass) 310 having a length of 10 mm, a width of 10 mm, and a thickness of 0.7 mm was prepared as a substrate.
- Metal aluminum layer 320 is 4mm long X width 1 mm x thickness 100 nm.
- the degree of vacuum during vapor deposition is about 3 ⁇ 10 ⁇ 6 Pa.
- an Alq3 layer as an electron transport layer 340 and an evaluation electrode 350 were formed on the metal aluminum layer 320 in the same manner as the sample 304 by vapor deposition.
- a sample 306 including a glass substrate 310, a metal aluminum layer 320, an electron transport layer 340, and an evaluation electrode 350 was produced.
- the sample 306 does not have the electron injection layer 330 but has the electron transport layer 340 directly on the metal aluminum layer 320.
- the electron injection characteristics were implemented by measuring the current value obtained when a predetermined voltage was applied between the metal aluminum layer 320 and the evaluation electrode 350 in each of the samples 304, 305, and 306.
- the applied voltage was set to a range from 0 V to 10 V (based on the metal aluminum layer 320).
- Results are shown in FIG. In FIG. 7, the horizontal axis represents the applied voltage (based on the metal aluminum layer 320), and the vertical axis represents the current density generated between the metal aluminum layer 320 and the evaluation electrode 350.
- the electron injection layer 330 made of amorphous C12A7 electride was installed as the electron injection layer, it was confirmed that the electron injection barrier was lowered and the current characteristics of the sample were improved.
- Example 4 An organic EL element was produced by the following method and its characteristics were evaluated.
- the organic EL device has a cathode as a bottom electrode on a glass substrate, and an electron injection layer, an electron transport layer / light emitting layer, a hole transport layer, a hole injection layer, and an anode as a top electrode in that order. The light is extracted from the anode side.
- the organic EL element 400 having the structure shown in FIG. 8 was produced by the following procedure.
- a glass substrate (made of non-alkali glass) 410 having a length of 30 mm, a width of 30 mm, and a thickness of 0.7 mm was prepared as a substrate.
- the cathode 420 is 28 mm long ⁇ 2 mm wide ⁇ 100 nm thick.
- the glass substrate 410 with the cathode was taken out from the sputtering apparatus into the atmosphere, introduced into another sputtering apparatus capable of heat treatment, and held at 300 ° C. in a vacuum of about 3 ⁇ 10 ⁇ 5 Pa for 10 minutes. After cooling to about 70 ° C., an amorphous C12A7 electride layer was formed as an electron injection layer 430 on the cathode 420. The substrate was not actively heated during the formation of the electride layer.
- the amorphous C12A7 electride layer was formed by sputtering using a crystalline C12A7 electride having an electron density of 1.5 ⁇ 10 21 cm ⁇ 3 as a target.
- the atmosphere during sputtering film formation was an oxygen partial pressure of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 0.21 Pa. Note that a pre-sputtering process was performed using Ar gas before the main film formation.
- the thickness of the obtained amorphous C12A7 electride layer is about 1 nm.
- the glass substrate 410 with the electron injection layer 430 (and the cathode 420) was taken out from the sputtering apparatus into the atmosphere.
- the glass substrate 410 was introduced into a vapor deposition apparatus capable of performing a substrate heat treatment, and a heat treatment was performed at 300 ° C. for 10 minutes in a vacuum of about 3 ⁇ 10 ⁇ 6 Pa. After cooling to about 70 ° C., the following vapor deposition was performed.
- an Alq3 layer was formed as an electron transport layer / light-emitting layer 440 by vapor deposition.
- the thickness of the Alq3 layer is about 50 nm.
- an ⁇ -NPD layer was formed as the hole transport layer 450.
- the thickness of the ⁇ -NPD layer is about 50 nm.
- a CuPc layer was formed as the hole injection layer 460.
- the thickness of the CuPc layer is about 30 nm.
- the Alq3 layer, ⁇ -NPD layer, and CuPc layer were formed as a 20 mm ⁇ 20 mm region using a metal mask so as to completely cover the electron injection layer 430.
- the degree of vacuum during the deposition was about 3 ⁇ 10 ⁇ 6 Pa.
- an anode 470 having a length of 2 mm ⁇ width of 13 mm ⁇ thickness of 5 nm was deposited so as to be orthogonal to the cathode. That is, a region of 2 mm ⁇ 2 mm where the cathode and the anode overlap is a region to be energized by voltage application.
- the anode 470 is made of gold.
- an organic EL element 401 having an electron injection layer 430 made of lithium fluoride was produced by the following method.
- a glass substrate (made of non-alkali glass) 410 having a length of 30 mm, a width of 30 mm, and a thickness of 0.7 mm was prepared as a substrate.
- a cathode 420 made of metallic aluminum was formed on one surface by sputtering.
- the cathode 420 is 28 mm long ⁇ 2 mm wide ⁇ 100 nm thick.
- the glass substrate 410 with the cathode 420 is taken out from the sputtering apparatus to the atmosphere and introduced into a vapor deposition apparatus capable of performing the substrate heat treatment, and the heat treatment is performed at 300 ° C. for 10 minutes in a vacuum of about 3 ⁇ 10 ⁇ 6 Pa. Went. After cooling to about 70 ° C., the following vapor deposition was performed.
- a lithium fluoride layer was formed by vapor deposition.
- the degree of vacuum during vapor deposition is about 3 ⁇ 10 ⁇ 6 Pa.
- the thickness of the lithium fluoride layer was about 0.5 nm.
- a hole transport layer 450 made of ⁇ -NPD a hole injection layer 460 made of CuPc
- an anode 470 made of gold are formed on the lithium fluoride layer by vapor deposition.
- a film was formed in the same manner as the organic EL element 400, and an organic EL element 401 was produced.
- the measurement was performed by measuring a current value and luminance obtained when a predetermined voltage was applied between the cathode 420 and the anode 470 of each organic EL element 400 or 401 in a nitrogen purged glove box. .
- the applied voltage was in the range from 0 V to 21 V (cathode 420 reference).
- a luminance meter (BM-7A) manufactured by TOPCOM was used for luminance measurement.
- FIGS. 9, 10, and 11 The average values of the six elements formed on one substrate are shown in FIGS. 9, 10, and 11.
- FIG. 9 the horizontal axis indicates the applied voltage (based on the cathode 420), and the vertical axis indicates the current density generated between the cathode 420 and the anode 470.
- the horizontal axis indicates the applied voltage (based on the cathode 420), and the vertical axis indicates the luminance.
- FIG. 11 the horizontal axis indicates the current density generated between the cathode 420 and the anode 470, and the vertical axis indicates the luminance.
- the organic EL element 400 having the electron injection layer 430 made of amorphous C12A7 electride has significantly improved current density and luminance at the same voltage.
- the organic EL element 400 having the electron injection layer 430 made of amorphous C12A7 electride and the organic EL element 401 having the electron injection layer 430 made of lithium fluoride have the same luminance / current density ratio. Degree. This indicates that an increase in luminance at the same voltage is due to an increase in current density, and that the electron injection characteristics of amorphous C12A7 electride are superior to lithium fluoride.
- amorphous C12A7 electride film was formed on a quartz substrate under the same sputtering conditions as those for producing the organic EL element 400, and the light absorption coefficient of the thin film was measured. However, in order to facilitate the analysis, the film formation time was changed from the conditions for manufacturing the element, and the film thickness was increased for analysis.
- an amorphous C12A7 electride film was formed on the ITO substrate under the same sputtering conditions as those for producing the organic EL element, and the work function of the thin film was measured using ultraviolet photoelectron spectroscopy (UPS).
- the thickness of the amorphous C12A7 electride was 10 nm.
- the measurement was performed under an ultrahigh vacuum (10 ⁇ 7 Pa), and organic substances on the surface were removed by Ar sputtering before the measurement. Further, X-ray photoelectron spectroscopy was performed before and after Ar sputtering, and it was confirmed that the thin film sample was not damaged. Further, a DC voltage (bias voltage) was applied to the sample to make it negative with respect to the measuring instrument. By applying such a bias voltage, the influence of the surface potential can be eliminated.
- bias voltage bias voltage
- FIG. 13 shows the kinetic energy distribution of electrons emitted from the sample irradiated with ultraviolet rays.
- the bias voltage is changed from 5 V to 10 V, almost the same spectrum can be obtained. Therefore, it is understood that the sample is not charged up and the spectrum shape reflects the work function. Moreover, this result has shown that the sample has electroconductivity. From the lowest kinetic energy of the photoelectrons in the figure, the work function was found to be about 2.9 eV.
- Example 5 An organic EL element was produced by the following method and its characteristics were evaluated.
- the organic EL element has a cathode disposed on a glass substrate as a bottom electrode, and an electron injection layer, an electron transport layer / light emitting layer, a hole transport layer, and an anode as a top electrode are disposed on the cathode in order. A structure for extracting light was adopted.
- a Flat-ITO substrate manufactured by Geomatic Co., Ltd. having a length of 30 mm ⁇ width of 30 mm was prepared.
- ITO having a thickness of 150 nm is formed on an alkali-free glass.
- a Kapton tape cut to a width of 1 mm was pasted on the ITO and immersed in an etching solution for 2 minutes to remove the ITO where the Kapton tape was not pasted.
- an aqueous solution in which FeCl 3 .6H 2 O and ion-exchanged water were mixed at a weight of 1: 1 was prepared, and a solution obtained by adding concentrated hydrochloric acid having the same weight as the aqueous solution was used.
- the temperature of the etching solution was 45 ° C.
- the Kapton tape was removed, and ultrasonic cleaning was performed for 5 minutes with a neutral detergent, and ultrasonic cleaning was performed twice for 5 minutes with pure water. Furthermore, ultrasonic cleaning was performed in acetone for 5 minutes, and ultrasonic cleaning was performed twice in IPA for 5 minutes. Finally, it was immersed in boiling acetone and slowly removed.
- the glass substrate 410 on which ITO (cathode 420) with a width of 1 mm was wired was introduced into an apparatus in which a sputtering film forming chamber, a vacuum deposition chamber, and a glove box were connected, and evacuated to about 3 ⁇ 10 ⁇ 5 Pa. Thereafter, an amorphous thin film was formed as the electron injection layer 430 on the cathode 420.
- the amorphous thin film was formed by a sputtering method using a crystalline C12A7 electride having an electron density of 1.4 ⁇ 10 21 cm ⁇ 3 as a target having a diameter of 2 inches.
- the atmosphere during sputtering film formation was an oxygen partial pressure of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 0.5 Pa.
- the distance between the sample and the target (TS distance) was 10 cm.
- the output of the RF power source was 50W. Note that a pre-sputtering process was performed using Ar gas before the main film formation.
- the glass substrate 410 was not actively heated.
- the thickness of the obtained amorphous thin film is about 5 nm.
- the glass substrate 410 with the electron injection layer 430 (and the cathode 420) was introduced into a vacuum deposition chamber in the apparatus, and an Alq3 layer as an electron transport layer / light emitting layer 440 was formed.
- the thickness of the Alq3 layer is about 50 nm.
- an ⁇ -NPD layer was formed as the hole transport layer 450.
- the thickness of the ⁇ -NPD layer is about 50 nm.
- the Alq3 layer and the ⁇ -NPD layer were formed as a 20 mm ⁇ 20 mm region using a metal mask so as to completely cover the electron injection layer 430.
- the degree of vacuum at the time of vapor deposition was about 8 ⁇ 10 ⁇ 6 Pa.
- an anode 470 having a width of 1 mm was deposited so as to be orthogonal to the cathode. That is, a region of 1 mm ⁇ 1 mm where the cathode and the anode overlap is a region that is energized by voltage application.
- a gold film having a thickness of 15 nm was formed as the anode 470.
- the organic EL element 402 provided with the anode 470 which consists of was produced.
- an organic EL element 403 was similarly manufactured except that the electron injection layer 430 was not provided.
- the obtained current / voltage and brightness are shown in FIG.
- the organic EL element 402 having an electron injection layer made of an amorphous thin film light emission was confirmed at about 15 V or more.
- the organic EL element 403 having no electron injection layer even when 40 V was applied, almost no current flowed and no light was emitted. This shows that the amorphous thin film has excellent electron injection characteristics.
- a current flows even at an applied voltage of 15 V or less, but since it does not accompany light emission, it is considered to be due to leakage.
- amorphous thin film was formed on a quartz substrate and a nickel plate under the same sputtering conditions as those for producing the device. However, in order to facilitate the analysis, the film formation time was changed from the conditions for manufacturing the element, and the film thickness was increased for analysis. The film thickness of the obtained sample was 202 nm.
- the light absorption coefficient of the thin film was measured using the above equation (4). From FIG. 15, light absorption is recognized when the photon energy is about 4.6 eV. As mentioned above, the amorphous C12A7 electride bipolaron exhibits light absorption in the vicinity of a photon energy of 4.6 eV. Therefore, the result of FIG. 15 suggests having bipolarons in the thin film.
- the ratio of the light absorption coefficient at the position of 3.3 eV to the light absorption coefficient at the position of 4.6 eV was 0.35 or less.
- the composition of the sample formed on the nickel substrate was analyzed by EPMA. Carbon was deposited to a thickness of 50 nm in order to avoid charge-up. In order to avoid the influence of the underlying nickel, the acceleration voltage was set to 5 kV. From the EPMA analysis, the obtained thin film contained Ca, Al, and O, and the molar ratio of Al / Ca was 1.76.
- Example 6 An organic EL element was produced by the following method and its characteristics were evaluated.
- the organic EL device has a cathode as a bottom electrode on a glass substrate, and an electron injection layer, an electron transport layer / light emitting layer, a hole transport layer, a hole injection layer, and an anode as a top electrode in that order. The light was extracted from the cathode side.
- Organic EL elements 404 and 405 were produced by the following procedure.
- a Flat-ITO substrate manufactured by Geomatic Co., Ltd. having a length of 30 mm ⁇ width of 30 mm was prepared.
- ITO having a thickness of 150 nm is formed on an alkali-free glass.
- a Kapton tape cut to a width of 1 mm was pasted on the ITO and immersed in an etching solution for 2 minutes to remove the ITO where the Kapton tape was not pasted.
- an aqueous solution in which FeCl 3 .6H 2 O and ion-exchanged water were mixed at a weight of 1: 1 was prepared, and a solution obtained by adding concentrated hydrochloric acid having the same weight as the aqueous solution was used.
- the temperature of the etching solution was 45 ° C.
- the Kapton tape was removed, and ultrasonic cleaning was performed for 5 minutes with a neutral detergent, and ultrasonic cleaning was performed twice for 5 minutes with pure water. Furthermore, ultrasonic cleaning was performed in acetone for 5 minutes, and ultrasonic cleaning was performed twice in IPA for 5 minutes. Finally, it was immersed in boiling IPA and slowly removed.
- the glass substrate 410 on which ITO (cathode 420) with a width of 1 mm was wired was introduced into an apparatus in which a sputtering film forming chamber, a vacuum deposition chamber, and a glove box were connected, and evacuated to about 3 ⁇ 10 ⁇ 5 Pa. Thereafter, an amorphous thin film was formed as the electron injection layer 430 on the cathode 420.
- the amorphous thin film was formed by a sputtering method using a crystalline C12A7 electride having an electron density of 1.4 ⁇ 10 21 cm ⁇ 3 as a target having a diameter of 2 inches.
- the atmosphere during sputtering film formation was an oxygen partial pressure of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 0.5 Pa.
- the distance between the sample and the target (TS distance) was 10 cm.
- the output of the RF power source was 50W. Note that a pre-sputtering process was performed using Ar gas before the main film formation.
- the glass substrate 410 was not actively heated.
- the thickness of the obtained amorphous thin film is about 5 nm.
- the glass substrate 410 with the electron injection layer 430 (and the cathode 420) was introduced into a vacuum vapor deposition chamber in the apparatus, and an Alq3 layer as an electron transport layer / light emitting layer 440 was formed.
- the thickness of the Alq3 layer is about 50 nm.
- an ⁇ -NPD layer was formed as the hole transport layer 450.
- the thickness of the ⁇ -NPD layer is about 50 nm.
- MoO 3 was formed as the hole injection layer 460.
- the thickness of the MoO 3 layer is about 0.8 nm.
- the Alq3 layer, the ⁇ -NPD layer, and the MoO 3 layer were formed as a 20 mm ⁇ 20 mm region using a metal mask so as to completely cover the electron injection layer 430.
- the degree of vacuum at the time of vapor deposition was about 8 ⁇ 10 ⁇ 6 Pa.
- an anode 470 having a width of 1 mm was deposited so as to be orthogonal to the cathode. That is, a region of 1 mm ⁇ 1 mm where the cathode and the anode overlap is a region that is energized by voltage application.
- a silver film having a thickness of 80 nm was formed as the anode 470.
- an organic EL element 405 was similarly manufactured except that the electron injection layer 430 was not provided.
- the obtained voltage and luminance are shown in FIG.
- the organic EL element 404 having an electron injection layer made of an amorphous thin film light emission was confirmed at about 6.8 V or more, and light emission of 2000 cd / m 2 was confirmed at about 12 V.
- the organic EL element 405 having no electron injection layer light emission was confirmed at about 7.5 V or more, and it was 60 cd / m 2 at about 9.4 V. Since the difference between the two was the presence or absence of an electron injection layer, it was confirmed that the amorphous thin film increased electron injection into Alq3 and improved the light emission characteristics.
- Example 7 An organic EL element was produced by the following method and its characteristics were evaluated.
- the organic EL device has a cathode as a bottom electrode on a glass substrate, and an electron injection layer, an electron transport layer / light emitting layer, a hole transport layer, a hole injection layer, and an anode as a top electrode in that order. The light is extracted from the anode side.
- Organic EL elements 406 and 407 were produced by the following procedure.
- a non-alkali glass substrate having a length of 30 mm, a width of 30 mm, and a thickness of 0.7 mm was prepared.
- This substrate was ultrasonically cleaned with a neutral detergent for 5 minutes, and then ultrasonically cleaned with pure water for 5 minutes twice. Furthermore, ultrasonic cleaning was performed in acetone for 5 minutes, and ultrasonic cleaning was performed twice in IPA for 5 minutes. Finally, it was immersed in boiling IPA and slowly removed.
- the cleaned glass substrate 410 was introduced into an apparatus in which a sputtering film forming chamber, a vacuum deposition chamber, and a glove box were connected, and evacuated to about 3 ⁇ 10 ⁇ 5 Pa. Next, the glass substrate 410 was introduced into a vacuum deposition chamber.
- an aluminum film having a thickness of 1 nm was formed as a cathode 420 on the glass substrate 410 by a vacuum deposition method.
- the glass substrate 410 with the cathode 420 was introduced into the sputtering film forming chamber, and an amorphous thin film was formed on the cathode 420 as the electron injection layer 430.
- the amorphous thin film was formed by a sputtering method using a crystalline C12A7 electride having an electron density of 1.4 ⁇ 10 21 cm ⁇ 3 as a target having a diameter of 2 inches.
- the atmosphere during sputtering film formation was an oxygen partial pressure of less than about 4.3 ⁇ 10 ⁇ 7 Pa.
- the sputtering gas was Ar, and the pressure of the introduced gas was 0.5 Pa.
- the distance between the sample and the target (TS distance) was 10 cm.
- the output of the RF power source was 50W. Note that a pre-sputtering process was performed using Ar gas before the main film formation.
- the glass substrate 410 was not actively heated.
- the thickness of the obtained amorphous thin film is about 2 nm.
- the glass substrate 410 with the electron injection layer 430 (and the cathode 420) was introduced into a vacuum vapor deposition chamber in the apparatus, and an Alq3 layer as an electron transport layer / light emitting layer 440 was formed.
- the thickness of the Alq3 layer is about 50 nm.
- an ⁇ -NPD layer was formed as the hole transport layer 450.
- the thickness of the ⁇ -NPD layer is about 50 nm.
- MoO 3 was formed as the hole injection layer 460.
- the thickness of the MoO 3 layer is about 0.8 nm.
- the Alq3 layer, the ⁇ -NPD layer, and the MoO 3 layer were formed as a 20 mm ⁇ 20 mm region using a metal mask so as to completely cover the electron injection layer 430.
- the degree of vacuum at the time of vapor deposition was about 8 ⁇ 10 ⁇ 6 Pa.
- an anode 470 having a width of 1 mm was deposited so as to be orthogonal to the cathode. That is, a region of 1 mm ⁇ 1 mm where the cathode and the anode overlap is a region that is energized by voltage application.
- a gold film having a thickness of 5 nm was formed as the anode 470.
- an organic EL element 407 was similarly manufactured except that LiF was used as the electron injection layer 430. LiF was deposited to a thickness of 0.5 nm by a vacuum deposition method.
- the obtained voltage and brightness are shown in FIG.
- the organic EL element 406 having an electron injection layer made of an amorphous thin film light emission of 1600 cd / m 2 was confirmed at about 10V.
- the organic EL element 407 using LiF for the electron injection layer it was 600 cd / m 2 at about 10V. Since the difference between the two is the electron injection layer, it has been confirmed that the amorphous thin film increases the electron injection into Alq3 and improves the light emission characteristics.
- Example 8 An organic EL element was produced by the following method and its characteristics were evaluated.
- a cathode is disposed as a bottom electrode on a glass substrate, and an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode as a top electrode are sequentially disposed thereon. The light is extracted from the anode side.
- Alq3 having a thickness of 50 nm was used as the electron transport layer and the light emitting layer
- ZnO—SiO 2 having a thickness of 100 nm was used as the electron transport layer
- Alq3 having a thickness of 30 nm was used as the light emitting layer. Were made similarly.
- an electron transporting layer was deposited to a thickness of a thin film of ZnO-SiO 2 is about 100 nm.
- the glass substrate on which these films were formed was introduced into a vacuum vapor deposition chamber in the apparatus, and an Alq3 layer was formed as a light emitting layer.
- the thickness of the Alq3 layer is about 30 nm.
- an ⁇ -NPD layer was formed as a hole transport layer.
- the thickness of the ⁇ -NPD layer is about 50 nm.
- MoO 3 was formed as a hole injection layer.
- the thickness of the MoO 3 layer is about 0.8 nm.
- the Alq3 layer, the ⁇ -NPD layer, and the MoO 3 layer were formed as a 20 mm ⁇ 20 mm region using a metal mask so as to completely cover the electron injection layer.
- the degree of vacuum at the time of vapor deposition was about 8 ⁇ 10 ⁇ 6 Pa.
- an anode having a width of 1 mm was deposited so as to be orthogonal to the cathode. That is, a region of 1 mm ⁇ 1 mm where the cathode and the anode overlap is a region that is energized by voltage application.
- a gold film having a thickness of 5 nm was formed.
- the present invention can be applied to an organic electroluminescence element or the like.
- the organic electroluminescence element may have a tandem structure in which a plurality of light emitting layers are connected by an intermediate layer and stacked.
- the organic electroluminescence element of the present invention can be used as a display element of a display device.
- the display device having the organic electroluminescence element of the present invention can be applied to various electronic devices.
- the display device can be incorporated into a display unit such as a display device such as a television receiver, an imaging device such as a digital camera, a digital information processing device such as a computer, or a mobile terminal device such as a mobile phone. Further, it can be incorporated as a display device in a display unit in a vehicle or a display unit of a car navigation device.
- the display device provided with the organic electroluminescence element of the present invention may be provided in a window, a door, a ceiling, a floor, a wall, a partition, or the like of a building structure or a moving body (vehicle, aircraft, ship, etc.).
- a display device for advertisement it may be provided in a public transportation vehicle, a billboard in the city, an advertising tower, and the like.
- the organic electroluminescence element of the present invention may be used as a light source for a lighting device or a light source for a display device.
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Abstract
Description
陽極、発光層、および陰極をこの順に有し、
前記発光層と前記陰極の間には、電子注入層が配置され、
該電子注入層は、非晶質C12A7エレクトライドで構成されていることを特徴とする有機エレクトロルミネッセンス素子が提供される。
前記発光層と前記電子注入層の間には、電子輸送層が配置され、
該電子輸送層は、金属酸化物で構成されても良い。
有機エレクトロルミネッセンス素子であって、
陽極、発光層、および陰極をこの順に有し、
前記陰極は、非晶質C12A7エレクトライドで構成されていることを特徴とする有機エレクトロルミネッセンス素子が提供される。
基板、電極、非晶質C12A7エレクトライドの層、および金属酸化物の層をこの順に有する、有機エレクトロルミネッセンス素子形成用積層体が提供される。
陽極、発光層、および陰極をこの順に有し、前記発光層と前記陰極の間に、電子注入層が配置される、有機エレクトロルミネッセンス素子の製造方法であって、
電子密度が2.0×1018cm-3~2.3×1021cm-3の結晶質C12A7エレクトライドのターゲットを用いて、低酸素分圧の雰囲気下で、気相蒸着法により成膜することにより、非晶質の薄膜で構成される電子注入層を形成することを特徴とする製造方法が提供される。
陽極、発光層、および陰極をこの順に有し、
前記発光層と前記陰極の間には、電子注入層が配置され、
該電子注入層は、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の薄膜で構成されていることを特徴とする有機エレクトロルミネッセンス素子が提供される。
図1には、本発明の一実施例による有機エレクトロルミネッセンス素子(以下、「有機EL素子」と称する)の概略的な断面図を示す。
ここで、本発明において、電子注入層170として使用される非晶質C12A7エレクトライド、およびこれに関連する用語について説明しておく。
本願において、「結晶質C12A7」とは、12CaO・7Al2O3の結晶、およびこれと同等の結晶構造を有する同型化合物を意味する。本化合物の鉱物名は、「マイエナイト」である。
(1)結晶中のCa原子の一部乃至全部が、Sr、Mg、および/またはBaなどの金属原子に置換された同型化合物。例えば、Ca原子の一部乃至全部がSrに置換された化合物としては、ストロンチウムアルミネートSr12Al14O33があり、CaとSrの混合比が任意に変化された混晶として、カルシウムストロンチウムアルミネートCa12-xSrXAl14O33(xは1~11の整数;平均値の場合は0超12未満の数)などがある。
(2)結晶中のAl原子の一部乃至全部が、Si、Ge、Ga、In、およびBからなる群から選択される一種以上の原子に置換された同型化合物。例えば、Ca12Al10Si4O35などが挙げられる。
(3)12CaO・7Al2O3の結晶(上記(1)、(2)の化合物を含む)中の金属原子および/または非金属原子(ただし、酸素原子を除く)の一部が、Ti、V、Cr、Mn、Fe、Co、Ni、およびCuからなる群から選択される一種以上の遷移金属原子もしくは典型金属原子、Li、Na、およびKからなる群から選択される一種以上のアルカリ金属原子、またはCe、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、およびYbからなる群から選択される一種以上の希土類原子と置換された同型化合物。
(4)ケージに包接されているフリー酸素イオンの一部乃至全部が、他の陰イオンに置換された化合物。他の陰イオンとしては、例えば、H-、H2 -、H2-、O-、O2 -、OH-、F-、Cl-、およびS2-などの陰イオンや、窒素(N)の陰イオンなどがある。
(5)ケージの骨格の酸素の一部が、窒素(N)などで置換された化合物。
本願において、「結晶質C12A7エレクトライド」とは、前述の「結晶質C12A7」において、ケージに包接されたフリー酸素イオン(ケージに包接された他の陰イオンを有する場合は、当該陰イオン)の一部乃至全部が電子に置換された化合物を意味する。
本願において、「非晶質C12A7エレクトライド」とは、結晶質C12A7エレクトライドと同等の組成を有し、非晶質C12A7を溶媒とし、電子を溶質とする溶媒和からなる非晶質固体物質を意味する。
また、これらのケージが複数凝集した状態でもよく、凝集したケージは微結晶とみなすこともできるため、非晶質中に微結晶が含まれた状態も本発明において非晶質とみなす。
本願において、「C12A7エレクトライド」とは、前述の「結晶質C12A7エレクトライド」および「非晶質C12A7エレクトライド」の両方を含む概念を意味する。
次に、図1に示した有機EL素子100を構成する各層の構成について詳しく説明する。
基板110は、上部に有機EL素子100を構成する各層を支持することができれば、その材質は特に限られない。ただし、前述のように、有機EL素子100の光取り出し面を基板110側とする場合、基板110は、透明材料で構成される。
陽極120としては、通常、金属または金属酸化物が使用される。使用材料は、仕事関数が4eV以上であるものが好ましい。なお、前述のように、有機EL素子100の光取り出し面を基板110側とする場合、陽極120は、透明である必要がある。
ホール注入層130は、ホール注入性を有する材料から選定される。
ホール輸送層140は、ホール輸送性を有する材料から選定される。
発光層150は、有機エレクトロルミネッセンス素子用の発光材料として知られるいかなる材料で構成されても良い。
通常の場合、電子輸送層160は、トリス(8-キノリノラト)アルミニウム(Alq3)のような有機材料で構成される。しかしながら、一般に、Alq3のような有機材料は、空気に触れると容易に劣化してしまうことがある。
前述のように、有機EL100において、電子注入層170には、非晶質C12A7エレクトライドが使用される。
ここで、電子注入層170用の非晶質C12A7エレクトライドの薄膜の成膜方法の一例について説明する。
電子密度が2.0×1018cm-3~2.3×1021cm-3の結晶質C12A7エレクトライドのターゲットを準備する工程(S110)と、
前記ターゲットを用いて、酸素分圧が0.1Pa未満の雰囲気下で、気相蒸着法により、陰極または電子輸送層上に成膜を行う工程(S120)と、
を有する。
まず、以降の工程S120で使用される成膜用のターゲットが準備される。
I2+e-→2I- (1)式
また、チオ硫酸ナトリウムでヨウ素水溶液を滴定した場合、
2Na2S2O3+I2→2NaI+Na2S4O6 (2)式
の反応により、未反応のヨウ素がヨウ化ナトリウムに変化する。最初の溶液中に存在するヨウ素量から、(2)式で滴定検出されたヨウ素量を差し引くことにより、(1)式の反応で消費されたヨウ素量が算定される。これにより、C12A7エレクトライドのサンプル中の電子濃度を測定することができる。ヨウ素滴定法は、C12A7エレクトライドが結晶質または非晶質のいずれにおいても適用可能である。
次に、前述の工程S110において作製されたターゲットを用いて、気相蒸着法により、電子輸送層上に成膜が行われる。
8.9×10-22/(td2)<P<4.5×10-20/(td2) (3)式
を満たすように選定されても良い。この場合、スパッタ粒子の平均自由行程が、ターゲット~基板間の距離とほぼ等しくなり、スパッタ粒子が残存酸素と反応することが抑制される。また、この場合、スパッタリング法の装置として、背圧が比較的高く、安価で簡易的な真空装置を用いることが可能となる。
陰極180は、通常、金属材料で構成される。なお、有機EL素子100の光取り出し面を陰極180側とする場合、陰極180は、透明である必要がある。
また、本発明の他の実施形態として、陽極、発光層、および陰極をこの順に有し、前記発光層と前記陰極の間に、電子注入層が配置される、有機エレクトロルミネッセンス素子の製造方法であって、電子密度が2.0×1018cm-3~2.3×1021cm-3の結晶質C12A7エレクトライドのターゲットを用いて、低酸素分圧の雰囲気下で、気相蒸着法により、陰極または発光層の上に成膜することにより、非晶質の薄膜で構成される電子注入層を形成する製造方法が提供される。
また、非晶質の薄膜は、4.6eVの光子エネルギー位置において光吸収を示すことが好ましい。
(1)基板、陽極、および陰極をこの順に有し、基板側を光取出し面とする構成であり、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の非晶質の薄膜が、陽極と陰極の間に存在するか、または陰極を構成する。
(2)基板、陽極、および陰極をこの順に有し、陰極側を光取出し面とする構成であり、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の非晶質の薄膜が、陽極と陰極の間に存在するか、または陰極を構成する。
(3)基板、陰極、および陽極をこの順に有し、基板側を光取出し面とする構成であり、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の非晶質の薄膜が、陽極と陰極の間に存在するか、または陰極を構成する。
(4)基板、陰極、および陽極をこの順に有し、陽極側を光取出し面とする構成であり、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の非晶質の薄膜が、陽極と陰極の間に存在するか、または陰極を構成する。
以下の方法により、有機EL素子の陰極部分の構成を模擬したサンプルを作製し、その特性を評価した。
以下の手順で、図4に示す構造のサンプル300を作製した。
次に、前述のサンプル300、301を用いて、電子注入特性の評価を実施した。
Alq3層の厚みを150nmとした以外は、例1と同様な方法で素子を作製し、非晶質C12A7エレクトライドからなる電子注入層330を有するサンプル302と、非晶質C12A7エレクトライドからなる電子注入層330を有しないサンプル303を作製した。
以下の方法により、有機EL素子の陰極部分の構成を模擬したサンプルを作製し、その特性を評価した。
以下の手順で、非晶質C12A7エレクトライドからなる電子注入層330を有するサンプル304と、フッ化リチウムからなる電子注入層330を有するサンプル305と、電子注入層330を有しないサンプル306と、を作製した。
×横1mm×厚さ100nmである。蒸着時の真空度は約3×10-6Paである。
次に、前述のサンプル304、305、306を用いて、電子注入特性の評価を実施した。
以下の方法により、有機EL素子を作製し、その特性を評価した。有機EL素子は、ガラス基板上に、ボトム電極として陰極を配置し、その上に順に、電子注入層、電子輸送層兼発光層、ホール輸送層、ホール注入層およびトップ電極としての陽極を配置し、陽極側から光を取り出す構造とした。
以下の手順で、図8に示す構造の有機EL素子400を作製した。
次に、前述の有機EL素子400および401を用いて、電流・電圧および輝度を測定した。
上記有機EL素子400を作製した条件と同じスパッタ条件で石英基板上に非晶質C12A7エレクトライドを成膜し、薄膜の光吸収係数を測定した。ただし、分析を容易にするため上記素子を作製した条件とは成膜時間を変え、膜厚を厚くして分析した。
A=Ln(T/(1-R))/t (4)式
図12から、光子エネルギーが約4.6eVの付近で、光吸収が認められる。前述のように、非晶質C12A7エレクトライドのバイポーラロンは、4.6eVの光子エネルギー付近で光吸収を示す。従って、図12の結果は、薄膜中にバイポーラロンを有することを示唆するものである。また、4.6eVの位置の光吸収係数に対する、3.3eVの位置の光吸収係数の比は、0.35以下であった。
以下の方法により、有機EL素子を作製し、その特性を評価した。有機EL素子は、ガラス基板上に、ボトム電極として陰極を配置し、その上に順に、電子注入層、電子輸送層兼発光層、ホール輸送層およびトップ電極としての陽極を配置し、陰極側から光を取り出す構造とした。
以下の手順で、有機EL素子402および403を作製した。
次に、前述の有機EL素子402および403を用いて、電流・電圧および輝度を測定した。測定は、窒素パージしたグローブボックス内において、各有機EL素子402または403の陰極420と陽極470の間に所定の値の電圧を印加した際に得られる電流値および輝度を測定することにより実施した。輝度測定には、TOPCOM社製の輝度計(BM-7A)を使用した。
上記素子を作製した条件と同じスパッタ条件で石英基板とニッケル板上に非晶質の薄膜を成膜した。ただし、分析を容易にするため上記素子を作製した条件とは成膜時間を変え、膜厚を厚くして分析した。得られたサンプルの膜厚は202nmであった。
以下の方法により、有機EL素子を作製し、その特性を評価した。有機EL素子は、ガラス基板上に、ボトム電極として陰極を配置し、その上に順に、電子注入層、電子輸送層兼発光層、ホール輸送層、ホール注入層およびトップ電極としての陽極を配置し、陰極側から光を取り出す構造とした。
以下の手順で、有機EL素子404および405を作製した。
次に、前述の有機EL素子404および405を用いて、電圧および輝度を測定した。測定は、窒素パージしたグローブボックス内において、各有機EL素子404または405の陰極420と陽極470の間に所定の値の電圧を印加した際に得られる輝度を測定することにより実施した。輝度測定には、TOPCOM社製の輝度計(BM-7A)を使用した。
以下の方法により、有機EL素子を作製し、その特性を評価した。有機EL素子は、ガラス基板上に、ボトム電極として陰極を配置し、その上に順に、電子注入層、電子輸送層兼発光層、ホール輸送層、ホール注入層および
トップ電極としての陽極を配置し、陽極側から光を取り出す構造とした。
以下の手順で、有機EL素子406および407を作製した。
次に、前述の有機EL素子406および407を用いて、電圧および輝度を測定した。測定は、窒素パージしたグローブボックス内において、各有機EL素子406または407の陰極420と陽極470の間に所定の値の電圧を印加した際に得られる輝度を測定することにより実施した。輝度測定には、TOPCOM社製の輝度計(BM-7A)を使用した。
以下の方法により、有機EL素子を作製し、その特性を評価した。有機EL素子は、ガラス基板上に、ボトム電極として陰極を配置し、その上に順に、電子注入層、電子輸送層、発光層、ホール輸送層、ホール注入層および
トップ電極としての陽極を配置し、陽極側から光を取り出す構造とした。例7が電子輸送層兼発光層として厚み50nmのAlq3としたのに対し、この例8では電子輸送層として厚み100nmのZnO-SiO2、発光層として厚み30nmのAlq3とした点が異なり、そのほかは同様に作製した。
その後、これらの成膜を施したガラス基板を同装置内の真空蒸着室に導入し、発光層としてAlq3層を成膜した。Alq3層の厚さは、約30nmである。
次に、ホール輸送層として、α-NPD層を成膜した。α-NPD層の厚さは、約50nmである。
さらに、ホール注入層としてMoO3を製膜した。MoO3層の厚さは、約0.8nmである。
次に、有機EL素子408について、直流電圧を印加し、電流および輝度を測定した。測定は、窒素パージしたグローブボックス内において、各有機EL素子の陰極と陽極の間に所定の値の電圧を印加した際に得られる輝度および電流を測定することにより実施した。輝度測定には、TOPCOM社製の輝度計(BM-7A)を使用した。電子輸送層にZnO-SiO2を用いた有機EL素子408は電子輸送層にAlq3を用いた場合に比べ、単位電流あたりの輝度が高く、すなわち電流効率(cd/A)が改善することが確認された。
110 基板
120 陽極
130 ホール注入層
140 ホール輸送層
150 発光層
160 電子輸送層
170 電子注入層
180 陰極
220 溶媒(非晶質C12A7)
230 ケージ
240 電子(溶質)
250 バイポーラロン
300 サンプル
310 ガラス基板
320 金属アルミニウム層
330 電子注入層
340 電子輸送層
350 評価用電極
400 有機エレクトロルミネッセンス素子
410 ガラス基板
420 陰極
430 電子注入層
440 電子輸送層兼発光層
450 ホール輸送層
460 ホール注入層
470 陽極
Claims (8)
- 有機エレクトロルミネッセンス素子であって、
陽極、発光層、および陰極をこの順に有し、
前記発光層と前記陰極の間には、電子注入層が配置され、
該電子注入層は、非晶質C12A7エレクトライドで構成されていることを特徴とする有機エレクトロルミネッセンス素子。 - 前記発光層と前記電子注入層の間には、電子輸送層が配置され、
該電子輸送層は、金属酸化物で構成されることを特徴とする請求項1に記載の有機エレクトロルミネッセンス素子。 - 前記電子輸送層は、アモルファス、結晶質、またはアモルファスと結晶質の混合相の形態であることを特徴とする請求項2に記載の有機エレクトロルミネッセンス素子。
- 前記電子輸送層は、ZnO-SiO2、In2O3-SiO2、SnO2-SiO2、ZnO、In-Ga-Zn-O、In-Zn-O、またはSnO2で構成されることを特徴とする請求項2または3に記載の有機エレクトロルミネッセンス素子。
- 有機エレクトロルミネッセンス素子であって、
陽極、発光層、および陰極をこの順に有し、
前記陰極は、非晶質C12A7エレクトライドで構成されていることを特徴とする有機エレクトロルミネッセンス素子。 - 基板、電極、非晶質C12A7エレクトライドの層、および金属酸化物の層をこの順に有する、有機エレクトロルミネッセンス素子形成用積層体。
- 陽極、発光層、および陰極をこの順に有し、前記発光層と前記陰極の間に、電子注入層が配置される、有機エレクトロルミネッセンス素子の製造方法であって、
電子密度が2.0×1018cm-3~2.3×1021cm-3の結晶質C12A7エレクトライドのターゲットを用いて、低酸素分圧の雰囲気下で、気相蒸着法により成膜することにより、非晶質の薄膜で構成される電子注入層を形成することを特徴とする製造方法。 - 有機エレクトロルミネッセンス素子であって、
陽極、発光層、および陰極をこの順に有し、
前記発光層と前記陰極の間には、電子注入層が配置され、
該電子注入層は、カルシウム、アルミニウム、および酸素を含む非晶質固体物質の薄膜で構成されていることを特徴とする有機エレクトロルミネッセンス素子。
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US9368739B2 (en) | 2016-06-14 |
TW201407849A (zh) | 2014-02-16 |
KR20150020577A (ko) | 2015-02-26 |
TWI589043B (zh) | 2017-06-21 |
JP6284157B2 (ja) | 2018-02-28 |
US20150137103A1 (en) | 2015-05-21 |
KR102013125B1 (ko) | 2019-08-22 |
JPWO2013191212A1 (ja) | 2016-05-26 |
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