WO2010058776A1 - 電荷輸送性材料および電荷輸送性ワニス - Google Patents
電荷輸送性材料および電荷輸送性ワニス Download PDFInfo
- Publication number
- WO2010058776A1 WO2010058776A1 PCT/JP2009/069522 JP2009069522W WO2010058776A1 WO 2010058776 A1 WO2010058776 A1 WO 2010058776A1 JP 2009069522 W JP2009069522 W JP 2009069522W WO 2010058776 A1 WO2010058776 A1 WO 2010058776A1
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- WIPO (PCT)
- Prior art keywords
- charge transporting
- charge
- solvent
- thin film
- varnish
- Prior art date
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
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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 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/114—Poly-phenylenevinylene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Definitions
- the present invention relates to a charge transport material and a charge transport varnish, and more specifically to a charge transport material and a charge transport varnish containing a heteropoly acid compound.
- Non-patent Document 1 Applied Physics Letters, USA, 1996, 69, p. 2160-21612. Further, it has been reported that a drive voltage can be lowered by forming a thin film by vacuum-depositing a metal oxide and using it as a hole injection layer (Non-Patent Document 2: Journal of Physics D). : Applied Physics D (Applied Physics), UK, 1996, 29, pp. 2750-2753).
- PLED organic electroluminescence
- Patent Document 1 Japanese Patent Laid-Open No. 3-273877
- Non-Patent Document 3 Nature, UK, 1992, 357, 477-47
- Non-patent Document 4 Applied Physics Letters, USA, 1998, 72, pp. 2660-2661. It has been reported that the same effect as the OLED element can be obtained by using the thin film as the hole transport layer.
- Patent Document 4 International Publication No. 2004/043117 Pamphlet
- Patent Document 5 International Publication No. 2005/107335 Pamphlet
- Non-patent Document 5 Applied Physics Letters, USA, 2007, Vol. 91, p.253504, Non-Patent Document 6: Applied Physics Letters, USA, 2008, Vol. 93, p. 043308), there is no example of a coating-type material having an oxidizing property with respect to a hole transport material. Development of new materials is required.
- the present invention has been made in view of such circumstances, and includes a charge transporting material including a substance having both high solubility in an organic solvent and charge transporting property, and further oxidizing property to a hole transporting material, and It is an object to provide a charge transporting varnish containing a charge transporting material.
- heteropolyacid compounds such as phosphomolybdic acid have high solubility and charge transportability in organic solvents, and further oxidation properties to hole transport materials. And when the charge transporting thin film containing the heteropoly acid compound is used as a hole injection layer of an OLED element, the driving voltage can be lowered and the element life can be improved. Completed the invention.
- a heteropolyacid compound such as phosphomolybdic acid typically has a Keggin-type chemical structure represented by Chemical Formula 1 or a Dawson-type chemical structure represented by Chemical Formula 2, that is, a structure in which a heteroatom is located at the center of the molecule. .
- this compound Due to these special chemical structures, there are significant differences in solubility and oxidation-reduction characteristics from isopolyacids and simple metal oxides composed only of metal oxygen acids.
- this compound has been well known as a polymerization catalyst or a color reagent for organic compounds, but there are few examples in which the compound itself is used as a charge transporting substance.
- the present inventors have found that this heteropolyacid compound functions as an effective hole injection layer by forming a layer with an ultrathin film in an organic EL device.
- a charge transport material comprising a heteropolyacid compound as a charge transport material, 2. 1 charge transporting material, wherein the heteropolyacid compound is phosphomolybdic acid, 3.
- a charge transporting varnish comprising 1 or 2 of a charge transporting material and an organic solvent, wherein the heteropolyacid compound is uniformly dissolved in the organic solvent; 4).
- a charge transporting thin film comprising one or two charge transporting materials; 7).
- An organic electroluminescent device comprising 6 or 7 charge transporting thin films; 9. The charge transporting thin film provides 8 electroluminescent elements constituting a hole injection layer.
- the charge transporting material of the present invention and the heteropolyacid compound contained in the varnish have good solubility in an organic solvent used for the preparation of a general charge transporting varnish. By dissolving in, it exhibits excellent solubility in various organic solvents including low surface tension solvents. Therefore, a low-polarity organic solvent-based charge transporting varnish can be prepared using a part or almost all of the low surface tension solvent.
- Such a low-polarity organic solvent-based charge transporting varnish can be applied not only by an inkjet coating apparatus in which solvent resistance is a problem, but also has a problem of solvent resistance such as an insulating film and partition walls on the substrate. Even when a structure exists, it can be used.
- an amorphous solid thin film having high flatness can be produced without any problem.
- the heteropolyacid compound exhibits good charge transportability by itself, the thin film obtained using only the heteropolyacid compound as the charge transport material and without using the dopant substance or other charge transport substance is good. Excellent charge transport property.
- this thin film as a hole injection layer, the driving voltage of the organic EL element can be lowered and the life of the element can be extended.
- heteropoly acid compounds generally have a high refractive index, an improvement in light extraction efficiency can be expected by an effective optical design.
- this thin film can be applied not only to an organic EL element but also to a buffer layer or a hole transport layer of a solar cell, a fuel cell electrode, a capacitor electrode protective film, and an antistatic film.
- the charge transport material according to the present invention includes a heteropolyacid compound as a charge transport material.
- the charge transportability is synonymous with conductivity, and means any one of hole transportability, electron transportability, and both charge transportability of holes and electrons.
- the heteropolyacid compound is a polyacid formed by condensing an isopolyacid that is an oxygen acid such as vanadium (V), molybdenum (Mo), or tungsten (W) and an oxyacid of a different element.
- oxygen acids of different elements mainly include oxygen acids such as silicon (Si), phosphorus (P), and arsenic (As).
- heteropolyacid compound examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid.
- high solubility in organic solvents, charge transportability In addition, phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid are preferred, and phosphomolybdic acid is particularly preferred from the viewpoints of lowering driving voltage and improving life when used in an organic EL device.
- These heteropolyacid compounds are available as commercial products.
- phosphomolybdic acid Phosphobomobic acid hydrate, or 12 Polybodo (VI) phosphoric acid n-hydrate, an illustrative formula: H 3 (PMo 12 O 40 ) ⁇ NH 2 O) is available from Kanto Chemical Co., Inc., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan Co., Ltd. and the like.
- the charge transporting varnish according to the present invention includes the heteropolyacid compound (charge transporting substance) described above and an organic solvent, and the heteropolyacid compound is uniformly dissolved in the organic solvent.
- the heteropolyacid compound that is the charge transport material of the present invention improvement in film flatness during coating and subsequent baking processes, improvement in organic EL characteristics, and suppression of solid precipitation of charge transport varnish
- a solid material suitable for each purpose may be used in combination.
- the organic solvent used when preparing the charge transporting varnish a good solvent having the ability to dissolve the heteropolyacid compound can be used.
- the good solvent means a solvent that can dissolve the heteropolyacid compound well.
- the heteropolyacid compound has high solubility in a highly polar solvent
- the good solvent is desirably highly polar.
- the boiling point at normal pressure is preferably 50 to 300 ° C.
- the heteropolyacid compound can be completely dissolved to form a uniform solution and can be removed in the film formation process.
- Examples of such a good solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2- Pyrrolidinone, cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , Propylene glycol, hexylene glycol, o-cresol, m-cresol, p-cresol, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone Cyclohexan
- a high viscosity solvent and / or a low surface tension solvent can be used together with the good solvent.
- the good solvent, the high-viscosity solvent, and the low surface tension solvent may each have properties of each other.
- a high-viscosity solvent gives a viscosity suitable for spraying and coating in various coating devices to form a uniform wet film. During firing, it causes solvent volatilization while suppressing the aggregation of the wet film and the occurrence of irregularities. It means a solvent capable of forming a thin film having uniform film thickness uniformity.
- high-viscosity solvent examples include those having a viscosity of 10 to 200 mPa ⁇ s, particularly 50 to 150 mPa ⁇ s at 25 ° C., and specifically, those having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure.
- High viscosity solvents cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4 -Butanediol, propylene glycol, hexylene glycol, o-cresol, m-cresol, p-cresol and the like are preferred.
- the proportion of use is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the entire solvent in the varnish.
- a low surface tension solvent can be used together with the good solvent.
- a low surface tension solvent means improved coating properties to the substrate by reducing surface tension, imparting volatility, imparting physical properties suitable for spraying or coating in various coating devices, and reducing corrosivity to coating devices. It means the solvent that makes it possible.
- Examples of such a low surface tension solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, p-xylene, o-xylene, and styrene; n-pentane, n-hexane, n-heptane, and n-octane.
- ethyl acetate isopropyl acetate, n-propyl acetate, i-butyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl caproate, acetic acid -Esters such as 2-methylpentyl, n-ethyl lactate, n-butyl lactate; ethylene glycol dimethyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Glycol esters or glycol ethers such as ethyl ether and diethylene glycol monoethyl ether acetate; diethyl ether, di-n-propyl ether, di-i-propyl ether
- the use ratio thereof is not particularly limited.
- the viscosity is improved and the surface tension is increased. It is possible to impart new preferable physical properties such as reduction, imparting volatility, improving paintability to the substrate surface, coating, and improving sprayability.
- the polarity of the obtained varnish being lowered, it becomes possible to use a coating apparatus, a substrate or the like in which solvent resistance is a problem, and the application range is expanded.
- the ratio of the good solvent and the low surface tension solvent is preferably about 9: 1 to 1: 9, more preferably about 1: 1 to 1: 4 in terms of mass ratio. preferable.
- the boiling point of the good solvent is desirably equal to or higher than that of other solvents.
- the method for preparing the charge transporting varnish is not particularly limited and can be prepared by mixing the heteropolyacid compound and various solvents in an arbitrary order.
- the heteropolyacid compound described above is once a good solvent. Since it has the property that precipitation does not easily occur even if a low surface tension solvent having a lower polarity is added, a solution in which a heteropolyacid compound is dissolved in a good solvent and a low surface tension solvent are used. It is preferable to prepare by mixing. When such a method is used, the ratio of the low surface tension solvent in the charge transporting varnish can be increased.
- the content of the heteropolyacid in the charge transport varnish is not particularly limited, but is usually about 0.01 to 50% by mass, and considering that a thin film of 0.1 to 200 nm is formed, 0.1 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable.
- the viscosity of the charge transporting varnish is not particularly limited. However, considering that a thin film having a thickness of 0.1 to 200 nm is prepared with high film thickness uniformity by a spin coating method, an ink jet method or a spray coating method, 25 1 to 100 mPa ⁇ s is preferred at 0 ° C., more preferably 3 to 30 mPa ⁇ s, even more preferably 5 to 20 mPa ⁇ s.
- a charge transporting thin film can be formed on a substrate by applying the charge transporting varnish described above on the substrate and evaporating the solvent.
- the method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, a spray method, and a slit coating method.
- the method for evaporating the solvent is not particularly limited.
- the solvent may be evaporated in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using a hot plate or an oven. Thereby, a thin film having a uniform film formation surface can be obtained.
- the firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C. In this case, two or more stages of temperature changes may be applied for the purpose of developing higher uniform film forming properties or allowing the reaction to proceed on the substrate.
- the thickness of the charge transporting thin film is not particularly limited, but when used as a charge injection layer in an organic EL device, it is preferably 0.1 to 200 nm, more preferably 0.5 to 50 nm, and further preferably 1.0 to 15 nm. preferable.
- As a method of changing the film thickness there are a method of changing the solid content concentration in the varnish, or changing the amount of the solution on the substrate at the time of application.
- Examples of materials used and methods for producing an OLED element using the charge transporting varnish of the present invention include the following, but are not limited thereto.
- the electrode substrate to be used is preferably cleaned in advance by liquid cleaning with detergent, alcohol, pure water or the like.
- the anode substrate is subjected to surface treatment such as ozone treatment or oxygen-plasma treatment immediately before use. Is preferred.
- the surface treatment may not be performed.
- a hole transporting varnish for an OLED element
- the hole transporting varnish is applied onto the anode substrate, evaporated and baked by the above method, and a hole transporting thin film is formed on the electrode to form a hole injection layer or a hole transport layer.
- This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited to form an OLED element.
- an element may be manufactured by removing any one layer or a plurality of layers as necessary.
- a carrier block layer may be provided between arbitrary layers.
- anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and those subjected to planarization treatment are preferable.
- ITO indium tin oxide
- IZO indium zinc oxide
- Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
- TPD triphenylamine dimer derivative
- ⁇ -NPD ⁇ -naphthyldiphenylamine dimer
- Spiro-TAD spiro-dimer
- Triarylamines such as 4,4 ′, 4 ′′ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ′′ -tris [1-naphthyl (phenyl) ) Amino] triphenylamine (1-TNATA) and other starburst amines, 5,5 ′′ -bis- ⁇ 4- [bis (4-methylphenyl) amino] phenyl ⁇ -2,2 ′: 5 ′,
- the hole transport material having reducibility with respect to the heteropolyacid compound used in the present invention is preferable from the viewpoint of lowering the driving voltage in the organic EL device characteristics.
- a layer containing these compounds is used as a hole injection layer containing the heteropolyacid compound. It is preferable to use it as a hole transport layer adjacent to.
- Materials for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq 3 ), bis (8-quinolinolato) zinc (II) (Znq 2 ), bis (2-methyl-8-quinolinolato) ( p-phenylphenolate) aluminum (III) (BAlq) and 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), and the like.
- the light emitting layer may be formed by co-evaporation.
- Examples of the electron transport material include Alq 3 , BAlq, DPVBi, (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole) (PBD), triazole derivatives ( TAZ), bathocuproine (BCP), silole derivatives and the like.
- luminescent dopant examples include quinacridone, rubrene, coumarin 540, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), tris (2-phenylpyridine) iridium ( III) (Ir (ppy) 3 ), (1,10-phenanthroline) -tris (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3-dionate) europium (III) ( Eu (TTA) 3 phen) and the like.
- Examples of the material for forming the carrier block layer include PBD, TAZ, and BCP.
- Materials for forming the electron injection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), magnesium fluoride (MgF 2 ), and strontium fluoride. (SrF 2 ), Liq, Li (acac), lithium acetate, lithium benzoate and the like.
- Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
- an electron transport varnish for an OLED element when using an electron transport varnish for an OLED element, the following method can be mentioned.
- An electron transporting varnish is applied onto a cathode substrate to produce an electron transporting thin film, which is introduced into a vacuum deposition apparatus, and using the same materials as described above, an electron transporting layer, a light emitting layer, and a hole transporting layer After forming the hole injection layer, the anode material is deposited by a method such as sputtering to obtain an OLED element.
- the manufacturing method of the PLED element using the charge transportable varnish of this invention is not specifically limited, The following methods are mentioned.
- the charge transporting varnish of the present invention is formed by forming a light emitting charge transporting polymer layer instead of performing vacuum deposition operation of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer.
- a PLED element including a charge transporting thin film formed by the above can be produced.
- the charge transporting varnish (hole transporting varnish) of the present invention is applied to prepare a hole transporting thin film by the above-described method, and a luminescent charge transporting property is high on the upper part.
- a molecular layer is formed, and a cathode electrode is further deposited to form a PLED element.
- An interlayer may be provided between the hole transporting thin film and the light emitting polymer layer in order to improve light emission efficiency and device lifetime.
- the charge transporting varnish (electron transporting varnish) of the present invention is applied on the cathode substrate to prepare an electron transporting thin film by the above-described method, and the light emitting charge transporting polymer layer and the hole are formed thereon.
- a transport layer is sequentially formed, and an anode electrode is formed by a method such as sputtering, vapor deposition, or spin coating to obtain a PLED element.
- An interlayer may be provided between the hole transporting thin film and the light emitting polymer layer in order to improve light emission efficiency and device lifetime.
- the cathode and anode material to be used the same substances as those used in the production of the OLED element can be used, and the same cleaning treatment and surface treatment can be performed.
- a method for forming the light emitting charge transporting polymer layer a solvent is added to the light emitting charge transporting polymer material or a material obtained by adding a light emitting dopant to the material, and the solution is dissolved or evenly dispersed to inject holes.
- An example is a method in which a film is formed by evaporation of a solvent after application to an electrode substrate on which a layer is formed.
- Examples of the light-emitting charge transporting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylene vinylene, and the like. And polyphenylene vinylene derivatives such as (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
- polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylene vinylene, and the like.
- polyphenylene vinylene derivatives such as (MEH-PPV)
- polythiophene derivatives such as poly (3-alkylthiophene) (PAT)
- PVCz polyvinylcarbazol
- Examples of the solvent include toluene, xylene, chloroform, and the like.
- Examples of the dissolution or uniform dispersion method include methods such as stirring, heating and stirring, and ultrasonic dispersion.
- the application method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dip method, a spin coating method, a slit coating method, a transfer printing method, a roll coating method, and a brush coating method. Application is preferably performed under an inert gas such as nitrogen or argon.
- Examples of the solvent evaporation method include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.
- the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.
- the solid content concentration described below was computed without subtracting the moisture content with the weighed value. In the weighing, pretreatment such as water removal was not performed, and the purchased compound was used as it was.
- the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
- the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
- the thin film obtained was a uniform amorphous solid.
- Example 2 To 0.30 g of phosphotungstic acid (manufactured by Nippon Shin Metals Co., Ltd., H 3 PW 12 O 40 ⁇ n hydrate), 2.93 g of DMI, which is a good solvent, was added and dissolved in a nitrogen atmosphere. To this solution, 1.47 g of propylene glycol and 4.40 g of cyclohexanol melted by heating to 40 ° C. were added and allowed to cool to room temperature to obtain a light brown transparent solution.
- the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
- the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
- the thin film obtained was a uniform amorphous solid.
- Example 3 To 0.30 g of lintongue molybdate (manufactured by Nippon Shin Metals Co., Ltd., H 3 PW 6 Mo 6 O 40 ⁇ n hydrate), 2.93 g of DMI, which is a good solvent, was added and dissolved in a nitrogen atmosphere. To this solution, 1.47 g of propylene glycol and 4.40 g of cyclohexanol melted by heating to 40 ° C. were added and allowed to cool to room temperature to obtain a light brown transparent solution.
- the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
- the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
- the thin film obtained was a uniform amorphous solid.
- Examples 4 to 7 The following experiment was conducted to conduct the conductivity measurement. In order to avoid the influence of the solvent, DMAc was used as the same solvent. In the conductivity measurement, the resistance value of the sample thin film itself needs to sufficiently exceed the resistance of the measuring element, and it is necessary to form a thick film. Therefore, a high concentration varnish was prepared.
- Phosphomolybdic acid H 3 PMo 12 O 40 ⁇ n hydrate
- phosphotungstic acid H 3 PW 12 O 40 ⁇ n hydrate
- phosphotungsto molybdic acid H 3 PW 6 Mo 6 O 40 ⁇ nhydrate
- silicotungstic acid manufactured by Nippon Shin Metals Co., Ltd., H 4 SiW 12 O 40 ⁇ n hydrate
- Each of the obtained varnishes was applied on an ITO substrate that had been cleaned with ozone for 30 minutes by a spin coating method (1500 rpm-20 seconds) and baked on an hot plate at 220 ° C. for 30 minutes in the atmosphere to form a charge transporting thin film. Formed.
- the thin film obtained was a uniform amorphous solid.
- PEDOT / PSS manufactured by HC Starck, grade name CH8000 was applied on the ITO substrate by a spin coating method, and baked on the hot plate at 100 ° C. for 60 minutes in the air to form a charge transporting thin film.
- the thin film obtained was a uniform amorphous solid.
- each of the obtained substrates was introduced into a vacuum deposition apparatus, and a sandwich type element (ITO / sample / Al (150 nm)) in which Al was deposited to a thickness of 150 nm by a deposition mask. ) was used to measure the electrical conductivity (electrode area 0.2 mm 2 , current density 100 mA / cm 2 ).
- the viscosity is about 10 mPa ⁇ s, which is suitable for film formation by a spin coating method and an ink-jet method, and the film thickness should be sufficient for the hole injection layer. It can be seen that it can be satisfied.
- all the compounds of the present invention have a small electric field dependency of conductivity, good charge transport property at a slight voltage, and high conductivity sufficient as a hole injection layer material (generally 10 ⁇ 7 S). / Cm or more is required).
- the Ip value is preferably a value close to or deeper than that of the hole transport material, that is, about 5.4 eV or a deeper value. Met.
- Example 4 the refractive index at wavelengths of 450 nm and 650 nm was measured for the thin film obtained in Example 4 (measuring device: M-2000, manufactured by JA Woollam Japan), which was 1.95 and 1.89, respectively.
- the phosphomolybdic acid thin film showed a high refractive index value.
- Example 8 Production of OLED element
- the spin rotation number was changed to form a hole transporting thin film having two kinds of film thickness on the ITO substrate, and then this substrate was introduced into a vacuum deposition apparatus.
- NPD, Alq 3 , LiF, and Al were sequentially deposited to produce an OLED element.
- the film thicknesses were 40 nm, 60 nm, 0.8 nm, and 150 nm, respectively, and the vapor deposition operation was performed after the pressure became 2 ⁇ 10 ⁇ 4 Pa or less.
- the deposition rate was 0.1 to 0.2 nm / s for ⁇ -NPD and Alq 3 , 0.01 to 0.02 nm / s for LiF, and 0.2 to 0.4 nm / s for Al.
- the transfer operation between the vapor deposition operations was performed in a vacuum.
- Example 6 An OLED element was produced using the same method as in Example 8 except that PEDOT / PSS (manufactured by HC Starck, grade name AI4083) was used as the hole injection layer. Table 2 shows the element characteristics obtained in Example 8 and Comparative Examples 5 and 6. In addition, the characteristic of the OLED element was measured using the organic electroluminescent luminous efficiency measuring apparatus (EL1003, Precise Gauge Co., Ltd. product).
- PEDOT / PSS manufactured by HC Starck, grade name AI4083
- the device of Example 8 has stable characteristics even at 10 mm square. It can be seen that the initial characteristics (voltage and current efficiency) and lifetime are equal or equal to or greater at a film thickness of 10 nm.
- triphenylamine-containing materials such as triphenylamine-containing materials are mostly used for the hole transport layer laminated adjacent to the hole injection layer.
- the following experiment was conducted. Since triphenylamine-containing compounds are similar in physical properties to other triarylamine-containing compounds used as hole transport layer materials, this makes it possible to evaluate the oxidation properties of triarylamine-based hole transport layer materials in general. . Having an oxidizing property with respect to the hole transport layer material means that carriers can be generated electrostatically in a part of the hole transport layer, thereby reducing the driving voltage in the organic EL element. It can be reduced.
- the hole injection layer containing phosphomolybdic acid forms a doping layer by oxidizing the contact interface with a hole transport layer made of a hole transport material containing triphenylamine or an analogous skeleton thereof. This suggests the possibility of contributing to a decrease in the driving voltage of the organic EL element.
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Abstract
Description
また、金属酸化物を真空蒸着させて薄膜を形成し、正孔注入層として用いることで駆動電圧の低下が可能となることが報告されている(非特許文献2:ジャーナル・オブ・フィジックス・ディー:アプライド・フィジックス(Journal of Physics D:Applied Physics)、英国、1996年、29巻、p.2750-2753)。
当該低分子オリゴマー化合物は、それ自体の粘度が低く、通常の有機溶媒を使用した場合、成膜操作におけるプロセスマージンが狭いため、スピンコート、インクジェット塗布、スプレー塗布等の種々の塗布方式や、種々の焼成条件を用いる場合、高い均一性を有する成膜を行うことは困難であった。
この点、各種添加溶媒を用いることで、粘度や、沸点および蒸気圧の調整が可能となり、種々の塗布方式に対応して高い均一性を有する成膜面を得ることが可能になってきている(特許文献4:国際公開第2004/043117号パンフレット、特許文献5:国際公開第2005/107335号パンフレット)。
一方で近年、金属酸化物を用いた正孔注入層が見直されており、正孔注入層を形成している金属酸化物が正孔輸送層との接触に際してその界面を酸化することで正孔輸送層にドーピング層を生成させ、駆動電圧を低下させうることが報告されている(非特許文献5:アプライド・フィジックス・レターズ(Applied Physics Letters)、米国、2007年、91巻、p.253504、非特許文献6:アプライド・フィジックス・レターズ(Applied Physics Letters)、米国、2008年、93巻、p.043308)が、正孔輸送材料に対して酸化性を有する塗布型材料は例がなく、新たな材料の開発が求められている。
なお、リンモリブデン酸等のヘテロポリ酸化合物は、代表的に化1で示されるKeggin型あるいは化2で示されるDawson型の化学構造、すなわちヘテロ原子が分子の中心に位置する構造を有している。
本発明者らは、このヘテロポリ酸化合物を、有機EL素子中、極薄膜で層を形成させることで有効な正孔注入層として機能することを見出した。
1. 電荷輸送性物質としてヘテロポリ酸化合物を含むことを特徴とする電荷輸送性材料、
2. 前記ヘテロポリ酸化合物が、リンモリブデン酸である1の電荷輸送性材料、
3. 1または2の電荷輸送性材料と、有機溶媒とを含み、前記ヘテロポリ酸化合物が、前記有機溶媒に均一に溶解していることを特徴とする電荷輸送性ワニス、
4. 前記有機溶媒が、少なくとも1種の良溶媒を含む混合溶媒である3の電荷輸送性ワニス、
5. 25℃での粘度が、10~200mPa・sの溶媒を含む3または4の電荷輸送性ワニス、
6. 1または2の電荷輸送性材料を含む電荷輸送性薄膜、
7. 3~5のいずれかの電荷輸送性ワニスから作製される電荷輸送性薄膜、
8. 6または7の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子、
9. 前記電荷輸送性薄膜が、正孔注入層を構成する8のエレクトロルミネッセンス素子
を提供する。
このような低極性有機溶媒系の電荷輸送性ワニスは、溶剤耐性が問題となるインクジェット塗布装置にて塗布することができるだけでなく、基板上に絶縁膜や隔壁などの耐溶剤性が問題となる構造物が存在する場合でも用いることができ、その結果、高平坦性を有する非晶質固体薄膜を問題なく作製することができる。
さらに、ヘテロポリ酸化合物はそれ単独で良好な電荷輸送性を発揮するため、電荷輸送性材料としてヘテロポリ酸化合物のみを用い、ドーパント物質やその他の電荷輸送性物質を用いなくとも得られた薄膜は良好な電荷輸送性を示す。この薄膜を、正孔注入層として使用することで、有機EL素子の駆動電圧を低下させるとともに、素子の長寿命化を実現することができる。
そして、ヘテロポリ酸化合物は一般に高屈折率であることから、有効な光学設計によって光取り出し効率の向上も期待できる。
また、この薄膜は、有機EL素子だけでなく、太陽電池のバッファ層または正孔輸送層、燃料電池用電極、コンデンサ電極保護膜、帯電防止膜へ応用することもできる。
本発明に係る電荷輸送性材料は、電荷輸送性物質としてヘテロポリ酸化合物を含むものである。
ここで、電荷輸送性とは、導電性と同義であり、正孔輸送性、電子輸送性、正孔および電子の両電荷輸送性のいずれかを意味する。
この場合、異種元素の酸素酸としては、主にケイ素(Si)、リン(P)、ヒ素(As)等の酸素酸が挙げられる。
なお、これらのヘテロポリ酸化合物は、市販品として入手可能であり、例えば、リンモリブデン酸(Phosphomolybdic acid hydrate 、または12 Molybdo(VI) phosphoric acid n-hydrate,示性式:H3(PMo12O40)・nH2O)は、関東化学(株)、和光純薬(株)、シグマアルドリッチジャパン(株)等から入手可能である。
なお、本発明の電荷輸送性材料であるヘテロポリ酸化合物に対して、塗布時やその後の焼成プロセスにおける膜の平坦性の向上、有機EL特性の向上および電荷輸送性ワニスの固体析出抑制をはじめとした保存安定性の向上のために、それぞれの目的に応じた固形材料を併用して用いても良い。
電荷輸送性ワニスを調製する際に用いられる有機溶媒としては、ヘテロポリ酸化合物の溶解能を有する良溶媒を用いることができる。
ここで、良溶媒とはヘテロポリ酸化合物を良く溶解することのできる溶媒を意味する。
ヘテロポリ酸化合物は高極性溶媒に対する溶解性が高いため、良溶媒は高極性であることが望ましい。また塗布後の焼成プロセスにて除去できる溶媒が好ましいため、常圧での沸点は50~300℃であることが好ましい。ただしヘテロポリ酸化合物を完全に溶解して均一溶液とすることができ、成膜プロセスにおいて除去可能な溶媒であれば特に限定されない。
高粘度溶媒とは、各種塗布装置における噴霧や塗布に適した粘性を付与して均一なウェット膜を形成し、焼成時にはウェット膜の凝集や凹凸の発生を抑制しながら溶媒揮発を生じさせ、高度な膜厚均一性を有する薄膜を形成し得る溶媒を意味する。
高粘度溶媒としては、25℃で10~200mPa・s、特に50~150mPa・sの粘度を有するものが挙げられ、具体的には、常圧で沸点50~300℃、特に150~250℃の高粘度溶媒であるシクロヘキサノール、エチレングリコール、1,3-オクチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、1,3-ブタンジオール、2,3-ブタンジオール、1,4-ブタンジオール、プロピレングリコール、へキシレングリコール、o-クレゾール、m-クレゾール、p-クレゾール等が好適である。
これらの高粘度溶媒を使用する場合、その使用割合は、ワニス中の溶媒全体に対して10~90質量%が好ましく、20~80質量%がより好ましい。
低表面張力溶媒とは、表面張力の低下、揮発性の付与等によって基板に対する塗れ性の向上や、各種塗布装置における噴霧あるいは塗布に適した物性を付与したり、塗布装置に対する腐食性の低下を可能にしたりする溶媒を意味する。
このような低表面張力溶媒としては、例えば、ベンゼン、トルエン、エチルベンゼン、p-キシレン、o-キシレン、スチレン等の芳香族炭化水素類;n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等の炭化水素類;酢酸エチル、酢酸イソプロピル、酢酸n-プロピル、酢酸i-ブチル、酢酸n-ブチル、酢酸n-アミル、酢酸n-ヘキシル、カプロン酸メチル、酢酸-2-メチルペンチル、乳酸n-エチル、乳酸n-ブチル等のエステル類;エチレングリコールジメチルエーテル、エチレングリコールメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート等のグリコールエステルまたはグリコールエーテル類;ジエチルエーテル、ジ-n-プロピルエーテル、ジ-i-プロピルエーテル、i-プロピルエーテル、1,4-ジオキサン、酢酸、γ-ブチルラクトン等のエーテルまたはカルボン酸類などが挙げられる。
低表面張力溶媒を使用する場合には、具体的に良溶媒と低表面張力溶媒との比率は、質量比で9:1~1:9程度が好ましく、1:1~1:4程度がより好ましい。
また、溶媒を2種以上混合して用いる場合には、良溶媒の沸点はその他の溶媒と同等またはそれ以上であることが望ましい。
このような手法を用いると、電荷輸送性ワニス中における低表面張力溶媒の割合を増加させることができる。
電荷輸送性ワニスの粘度は、特に限定されるものではないが、スピンコート法、インクジェット法あるいはスプレーコート法で0.1~200nmの薄膜を高い膜厚均一性で作製することを考慮すると、25℃で1~100mPa・sが好ましく、3~30mPa・sがより好ましく、5~20mPa・sがより一層好ましい。
ワニスの塗布方法としては、特に限定されるものではなく、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り、インクジェット法、スプレー法、スリットコート法等が挙げられる。
溶媒の蒸発法としては、特に限定されるものではなく、例えば、ホットプレートやオーブンを用いて、適切な雰囲気下、すなわち、大気、窒素等の不活性ガス、真空中等で蒸発させればよい。これにより、均一な成膜面を有する薄膜を得ることが可能である。
焼成温度は、溶媒を蒸発させることができれば特に限定されないが、40~250℃で行うことが好ましい。この場合、より高い均一成膜性を発現させたり、基材上で反応を進行させたりする目的で、2段階以上の温度変化をつけてもよい。
使用する電極基板は、洗剤、アルコール、純水等による液体洗浄を予め行って浄化しておくことが好ましく、例えば、陽極基板では使用直前にオゾン処理、酸素-プラズマ処理等の表面処理を行うことが好ましい。ただし陽極材料が有機物を主成分とする場合、表面処理を行わなくともよい。
陽極基板上に当該正孔輸送性ワニスを塗布し、上記の方法により蒸発、焼成を行い、電極上に正孔輸送性薄膜を作製して正孔注入層または正孔輸送層とする。これを真空蒸着装置内に導入し、正孔輸送層、発光層、電子輸送層、電子注入層、陰極金属を順次蒸着してOLED素子とする。ただし、必要に応じていずれかの一層または複数層を除いて素子を作製してもよい。発光領域をコントロールするために任意の層間にキャリアブロック層を設けてもよい。
陽極材料としては、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)に代表される透明電極が挙げられ、平坦化処理を行ったものが好ましい。高電荷輸送性を有するポリチオフェン誘導体やポリアニリン誘導体を用いることもできる。
本発明で用いるヘテロポリ酸化合物に対して還元性を有している正孔輸送材料は、有機EL素子特性における駆動電圧低下の観点において好ましい。特に、トリフェニルアミン、トリアリールアミン類あるいはスターバーストアミン類は、本発明で用いるヘテロポリ酸化合物によって酸化されやすいため、これらの化合物を含む層を、当該へテロポリ酸化合物を含有する正孔注入層に隣接する正孔輸送層として使用すると好適である。
電子輸送材料としては、Alq3、BAlq、DPVBi、(2-(4-ビフェニル)-5-(4-t-ブチルフェニル)-1,3,4-オキサジアゾール)(PBD)、トリアゾール誘導体(TAZ)、バソクプロイン(BCP)、シロール誘導体等が挙げられる。
電子注入層を形成する材料としては、酸化リチウム(Li2O)、酸化マグネシウム(MgO)、アルミナ(Al2O3)、フッ化リチウム(LiF)、フッ化マグネシウム(MgF2)、フッ化ストロンチウム(SrF2)、Liq、Li(acac)、酢酸リチウム、安息香酸リチウム等が挙げられる。
陰極材料としては、アルミニウム、マグネシウム-銀合金、アルミニウム-リチウム合金、リチウム、ナトリウム、カリウム、セシウム等が挙げられる。
陰極基板上に当該電子輸送性ワニスを塗布して電子輸送性薄膜を作製し、これを真空蒸着装置内に導入し、上記と同様の材料を用いて電子輸送層、発光層、正孔輸送層、正孔注入層を形成した後、陽極材料をスパッタリング等の方法により成膜してOLED素子とする。
上記OLED素子作製において、正孔輸送層、発光層、電子輸送層、電子注入層の真空蒸着操作を行う代わりに、発光性電荷輸送性高分子層を形成することによって本発明の電荷輸送性ワニスによって形成される電荷輸送性薄膜を含むPLED素子を作製することができる。
具体的には、陽極基板上に、本発明の電荷輸送性ワニス(正孔輸送性ワニス)を塗布して上記の方法により正孔輸送性薄膜を作製し、その上部に発光性電荷輸送性高分子層を形成し、さらに陰極電極を蒸着してPLED素子とする。発光効率向上および素子寿命向上のために、正孔輸送性薄膜と発光性高分子層の間にインターレイヤーを設けてもよい。
あるいは、陰極基板上に、本発明の電荷輸送性ワニス(電子輸送性ワニス)を塗布して上記の方法により電子輸送性薄膜を作製し、その上部に発光性電荷輸送性高分子層および正孔輸送層を順次形成し、さらにスパッタリング、蒸着、スピンコート等の方法により陽極電極を作製してPLED素子とする。発光効率向上および素子寿命向上のために、正孔輸送性薄膜と発光性高分子層の間にインターレイヤーを設けてもよい。
発光性電荷輸送性高分子層の形成法としては、発光性電荷輸送性高分子材料、またはこれに発光性ドーパントを加えた材料に溶媒を加えて溶解するか、均一に分散し、正孔注入層を形成してある電極基板に塗布した後、溶媒の蒸発により成膜する方法が挙げられる。
発光性電荷輸送性高分子材料としては、ポリ(9,9-ジアルキルフルオレン)(PDAF)等のポリフルオレン誘導体、ポリ(2-メトキシ-5-(2’-エチルヘキソキシ)-1,4-フェニレンビニレン)(MEH-PPV)等のポリフェニレンビニレン誘導体、ポリ(3-アルキルチオフェン)(PAT)等のポリチオフェン誘導体、ポリビニルカルバゾール(PVCz)などが挙げられる。
塗布方法としては、特に限定されるものではなく、インクジェット法、スプレー法、ディップ法、スピンコート法、スリットコート法、転写印刷法、ロールコート法、刷毛塗り等が挙げられる。なお、塗布は、窒素、アルゴン等の不活性ガス下で行うことが望ましい。
溶媒の蒸発法としては、不活性ガス下または真空中、オーブンまたはホットプレートで加熱する方法が挙げられる。
[実施例1]
リンモリブデン酸(関東化学(株)製、H3PMo12O40・n水和物)0.30gに対し、窒素雰囲気中で良溶媒であるDMI2.93gを加えて溶解した。この溶液に、プロピレングリコール1.47gおよび40℃まで加熱して融解させたシクロヘキサノール4.40gを加え、室温まで放冷して淡褐色透明溶液を得た。
得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、淡褐色透明の電荷輸送性ワニスを得た(固形分濃度3.3質量%、粘度11mPa・s,25℃)。
30分間オゾン洗浄を行ったITO基板上に、得られたワニスをスピンコート法により塗布し、ホットプレート上、大気中220℃で30分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。
リンタングステン酸(日本新金属(株)製、H3PW12O40・n水和物)0.30gに対し、窒素雰囲気中で良溶媒であるDMI2.93gを加えて溶解した。この溶液に、プロピレングリコール1.47gおよび40℃まで加熱して融解させたシクロヘキサノール4.40gを加え、室温まで放冷して淡褐色透明溶液を得た。
得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、淡褐色透明の電荷輸送性ワニスを得た(固形分濃度3.3質量%、粘度11mPa・s,25℃)。
30分間オゾン洗浄を行ったITO基板上に、得られたワニスをスピンコート法により塗布し、ホットプレート上、大気中220℃で30分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。
リンタングストモリブデン酸(日本新金属(株)製、H3PW6Mo6O40・n水和物)0.30gに対し、窒素雰囲気中で良溶媒であるDMI2.93gを加えて溶解した。この溶液に、プロピレングリコール1.47gおよび40℃まで加熱して融解させたシクロヘキサノール4.40gを加え、室温まで放冷して淡褐色透明溶液を得た。
得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、淡褐色透明の電荷輸送性ワニスを得た(固形分濃度3.3質量%、粘度11mPa・s,25℃)。
30分間オゾン洗浄を行ったITO基板上に、得られたワニスをスピンコート法により塗布し、ホットプレート上、大気中220℃で30分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。
導電率測定を行うために以下の実験を行った。溶媒による影響を避けるためにいずれも同一溶媒としてDMAcを用いた。なお導電率測定においてはサンプル薄膜自体の抵抗値が測定素子の抵抗を十分に上回る必要があり、厚膜を形成させる必要がある。そのため高濃度ワニスを調製した。
上記のリンモリブデン酸(H3PMo12O40・n水和物)、リンタングステン酸(H3PW12O40・n水和物)、リンタングストモリブデン酸(H3PW6Mo6O40・n水和物)およびケイタングステン酸(日本新金属(株)製、H4SiW12O40・n水和物)それぞれ1.00gに対し、窒素雰囲気下DMAc5.67gを加え、室温で撹拌してそれぞれのDMAc溶液を得た(固形分濃度15質量%)。いずれも透明溶液となった。
30分間オゾン洗浄を行ったITO基板上に、得られたそれぞれのワニスをスピンコート法により塗布し(1500rpm-20秒)、ホットプレート上、大気中220℃で30分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。
PEDOT/PSS(H.C.Starck社製、グレード名CH8000)をスピンコート法によりITO基板上に塗布し、ホットプレート上、大気中100℃で60分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。
酸化モリブデン(関東化学(株)製、MoO3)、モリブデン酸(関東化学(株)製、H2MoO4)、モリブデン酸アンモニウム(関東化学(株)製、(NH4)6Mo7O24)、酸化タングステン(関東化学(株)製、WO3)、酸化バナジウム(関東化学(株)製、V2O5)、酸化マンガン(関東化学(株)製、MnO2)に対し、電荷輸送性ワニスの調製を試みたが、上記良溶媒に対する十分な溶解性を有していないことから均一溶液は得られなかった。
酸化バナジウムアセチルアセトナート(関東化学(株)製、VO(acac)2)をクロロホルムに溶解して1質量%クロロホルム溶液を得た。
この溶液を用いて、上記実施例と同様にして薄膜を形成したが、膜面結晶化した。
酢酸マンガンをクロロホルムに溶解して1質量%クロロホルム溶液を得た。
この溶液を用いて、上記実施例と同様にして薄膜を試みたが、成膜時に凝集し、均一な薄膜は得られなかった。
上記実施例1~7および比較例1で得られた薄膜の物性値を表1に示す。
なお、イオン化ポテンシャルは、理研計器(株)製 光電子分光装置 AC-2を使用して測定した。膜厚は、(株)小坂研究所製 サーフコーダET-4000Aを使用して測定した。
また、実施例4~7および比較例1では、得られたそれぞれの基板を真空蒸着装置内に導入し、蒸着マスクによってAlを膜厚150nm蒸着したサンドイッチ型素子(ITO/sample/Al(150nm))を用いて導電率を測定した(電極面積0.2mm2、電流密度100mA/cm2時)。
また、本発明の化合物はいずれも導電率の電界依存性が小さく、わずかな電圧で良好な電荷輸送性を示し、正孔注入層材料として十分な高導電率を示した(一般に10-7S/cm以上が必要)。電極からの電界注入障壁が小さい材料では、Ip値は正孔輸送材料に近い値かより深い値、すなわち5.4eV程度かより深い値であることが望ましいが、Ip値はいずれも適正な範囲であった。
[実施例8]
実施例1と同様の方法を用い、スピン回転数を変化させてITO基板上に2種類の膜厚の正孔輸送性薄膜を形成した後、この基板を真空蒸着装置内に導入し、α-NPD、Alq3、LiF、Alを順次蒸着し、OLED素子を作製した。膜厚は、それぞれ40nm、60nm、0.8nm、150nmとし、それぞれ2×10-4Pa以下の圧力となってから蒸着操作を行った。蒸着レートは、α-NPDおよびAlq3では0.1~0.2nm/s、LiFでは0.01~0.02nm/s、Alでは0.2~0.4nm/sとした。蒸着操作間の移動操作は真空中で行った。
リンモリブデン酸を含む正孔輸送性薄膜を設けずに、正孔輸送層であるα-NPDの膜厚を70nmとした以外は、実施例8と同様の方法を用いてOLED素子を作製した。
正孔注入層としてPEDOT/PSS(H.C.Starck社製、グレード名AI4083)を用いた以外は、実施例8と同様の方法を用いてOLED素子を作製した。
実施例8および比較例5,6で得られた素子特性を表2に示す。
なお、OLED素子の特性は、有機EL発光効率測定装置(EL1003、プレサイスゲージ(株)製)を使用して測定した。
現在、正孔注入層に隣接して積層される正孔輸送層には、ほとんどトリフェニルアミン含有材料をはじめとしたトリアリールアミン含有材料が使用されている。本発明のヘテロポリ酸化合物のトリフェニルアミン含有化合物に対する酸化性について評価するため、以下の実験を行った。トリフェニルアミン含有化合物は正孔輸送層材料として使用されている他のトリアリールアミン含有化合物と物性が類似しているため、これによりトリアリールアミン系正孔輸送層材料全般に対する酸化性を評価できる。正孔輸送層材料に対して酸化性を有するということは、正孔輸送層の一部に静電的にキャリアを生成させることができることを意味しており、これにより有機EL素子における駆動電圧を低下させることが可能となる。
得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、淡褐色透明の電荷輸送性ワニスを得た(固形分濃度6.0質量%)。
30分間オゾン洗浄を行った石英基板上に、得られたワニスをスピンコート法により塗布し、ホットプレート上、大気中150℃で30分間焼成して電荷輸送性薄膜を形成した。得られた薄膜は均一な非晶質固体であった。得られた薄膜のUV-VISスペクトルを測定した(測定装置:UV-3100、(株)島津製作所製)ところ、550nmおよび730nmにブロードの吸収ピークが発生した。
以上の結果より、リンモリブデン酸はトリフェニルアミン2量体に対する酸化性を有していることがわかる。
このことから、リンモリブデン酸を含む正孔注入層は、トリフェニルアミンあるいはその類縁骨格を含有する正孔輸送材料からなる正孔輸送層に対し、その接触界面を酸化してドーピング層を形成する可能性があり、それにより有機EL素子の駆動電圧低下に寄与する可能性が示唆される。
リンモリブデン酸(Aldrich製)をジノニルナフタレンジスルホン酸に変更した以外は同様にして電荷輸送性薄膜を形成した。得られた薄膜のUV-VISスペクトルを測定したところ、それぞれの単体膜で得られる吸収ピーク以外の新たな吸収ピークは発生しなかった。ジノニルナフタレンジスルホン酸はトリフェニルアミン2量体に対する酸化性を有していないことがわかる。
Claims (9)
- 電荷輸送性物質としてヘテロポリ酸化合物を含むことを特徴とする電荷輸送性材料。
- 前記ヘテロポリ酸化合物が、リンモリブデン酸である請求項1記載の電荷輸送性材料。
- 請求項1または2記載の電荷輸送性材料と、有機溶媒とを含み、
前記ヘテロポリ酸化合物が、前記有機溶媒に均一に溶解していることを特徴とする電荷輸送性ワニス。 - 前記有機溶媒が、少なくとも1種の良溶媒を含む混合溶媒である請求項3記載の電荷輸送性ワニス。
- 25℃での粘度が、10~200mPa・sの溶媒を含む請求項3または4記載の電荷輸送性ワニス。
- 請求項1または2記載の電荷輸送性材料を含む電荷輸送性薄膜。
- 請求項3~5のいずれか1項記載の電荷輸送性ワニスから作製される電荷輸送性薄膜。
- 請求項6または7記載の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子。
- 前記電荷輸送性薄膜が、正孔注入層を構成する請求項8記載のエレクトロルミネッセンス素子。
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US20110220853A1 (en) | 2011-09-15 |
JPWO2010058776A1 (ja) | 2012-04-19 |
CN102272968B (zh) | 2015-07-22 |
EP2355197B1 (en) | 2019-10-09 |
KR20110095883A (ko) | 2011-08-25 |
TW201024386A (en) | 2010-07-01 |
KR20170090515A (ko) | 2017-08-07 |
US9049771B2 (en) | 2015-06-02 |
EP2355197A4 (en) | 2015-07-29 |
KR20160088440A (ko) | 2016-07-25 |
CN102272968A (zh) | 2011-12-07 |
EP2355197A1 (en) | 2011-08-10 |
JP5617640B2 (ja) | 2014-11-05 |
TWI499649B (zh) | 2015-09-11 |
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