WO2020111277A1 - Procédé de fabrication de film, procédé de fabrication d'élément semi-conducteur organique et élément semi-conducteur organique - Google Patents

Procédé de fabrication de film, procédé de fabrication d'élément semi-conducteur organique et élément semi-conducteur organique Download PDF

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WO2020111277A1
WO2020111277A1 PCT/JP2019/046923 JP2019046923W WO2020111277A1 WO 2020111277 A1 WO2020111277 A1 WO 2020111277A1 JP 2019046923 W JP2019046923 W JP 2019046923W WO 2020111277 A1 WO2020111277 A1 WO 2020111277A1
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compound
group
film
producing
vapor deposition
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PCT/JP2019/046923
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Japanese (ja)
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直人 能塚
順一 西出
礼隆 遠藤
勇人 垣添
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株式会社Ｋｙｕｌｕｘ
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Priority to CN201980076806.XA priority Critical patent/CN113170549B/zh
Priority to JP2020557887A priority patent/JP7393799B2/ja
Priority to KR1020217020178A priority patent/KR20210095933A/ko
Publication of WO2020111277A1 publication Critical patent/WO2020111277A1/fr

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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
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • 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
    • C23C14/12—Organic material
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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

Definitions

  • the present invention relates to a method for manufacturing a film used for forming a layer of an organic semiconductor element, for example.
  • Patent Document 1 proposes an organic electroluminescent element in which a fluorescent material and a delayed fluorescent material are allowed to coexist in a light emitting layer to enhance the light emission efficiency (see, for example, Patent Document 1).
  • the “delayed fluorescent material” is an organic material that causes an inverse intersystem crossing from the excited triplet state to the excited singlet state when the molecule transits to the excited triplet state. Each molecule that transits to the excited singlet state then emits fluorescence when it undergoes radiation deactivation from the excited singlet state to the ground singlet state. Fluorescence emitted through such intersystem crossing is called “delayed fluorescence” because it is usually observed later than fluorescence from excited singlet state caused by direct transition from ground state. ..
  • the delayed single fluorescent material coexists with the fluorescent material in the light emitting layer, so that the energy of the excited singlet state generated by the intersystem crossing of the delayed fluorescent material is changed to the fluorescent material.
  • the fluorescent material To be used for light emission of the fluorescent material.
  • a normal fluorescence emitting layer that does not use a delayed fluorescent material, since the transition from the excited triplet state to the ground singlet state is a forbidden transition, even if excited to the excited triplet state, the excited triplet state To the ground singlet state (radiation deactivation) does not occur and deactivates without radiation, and the excited triplet energy cannot be used for light emission.
  • Patent Document 1 describes that a light emitting layer in which a fluorescent material and a delayed fluorescent material coexist is formed by a co-evaporation method in which the fluorescent material and the delayed fluorescent material are deposited from different evaporation sources.
  • the method for producing the light emitting layer since the method for producing the light emitting layer has not been examined in detail, the method for producing the light emitting layer adopted therein is not always satisfactory. Therefore, the present inventors have made earnest studies for the purpose of developing a new manufacturing method for obtaining a film in which a fluorescent material and a delayed fluorescent material coexist.
  • the present inventors have found that co-evaporation from a vapor deposition source containing both a delayed fluorescent material and a fluorescent material enables stable deposition of the delayed fluorescent material and the fluorescent material to form a high-quality film. I found it.
  • the present invention has been proposed on the basis of these findings, and specifically has the following configurations.
  • a film containing the first compound and the second compound is formed by co-evaporating from a vapor deposition source containing both a first compound satisfying the following formula (1) and a second compound satisfying the following formula (2).
  • a method for producing a film comprising the steps of: ⁇ E ST (1) ⁇ 0.3 eV Formula (1) E S1 (1)> E S1 (2) Formula (2) (In the above equation, ⁇ E ST (1) is the difference between the lowest excited singlet energy level E S1 (1) of the first compound and the lowest excited triplet energy level E T1 (1) of the first compound. E S1 (2) is the lowest excited singlet energy level of the second compound.) [2] The method for producing a film according to [1], wherein the second compound satisfies the following formula (3).
  • ⁇ E ST (2) is the difference between the lowest excited singlet energy level E S1 (2) of the second compound and the lowest excited triplet energy level E T1 (2) of the second compound. is there.
  • [3] The method for producing a film according to [1] or [2], wherein the first compound emits delayed fluorescence.
  • [4] The method for producing a film according to [1], wherein the second compound emits fluorescence.
  • [5] The method for producing a film according to any one of [1] to [3], wherein the second compound emits delayed fluorescence.
  • [6] The method for producing a film according to any one of [1] to [5], wherein the film contains the first compound in a larger amount than the second compound.
  • [9] The method for producing a film according to any one of [1] to [8], wherein the vapor deposition source further contains a host material, and the film further contains the host material.
  • thermogravimetric analysis is performed at a constant heating rate to clarify the relationship between the temperature T and the weight reduction rate W, and The temperature T GR at which the dW/dT of the second compound becomes the same is specified
  • a film containing the first compound and the second compound is formed by co-evaporating at a temperature T GR from an evaporation source containing both the mixture of the first compound and the second compound, [1] to [15].
  • a method for producing an organic semiconductor device which comprises a step of forming a layer by the production method according to any one of [1] to [17].
  • the organic semiconductor device according to [20] which emits delayed fluorescence.
  • the first compound and the second compound can be stably deposited to form a good quality film.
  • an organic semiconductor element having a layer containing the first compound and the second compound can be easily produced.
  • thermogravimetric analysis result of compound T9 It is a schematic sectional drawing which shows the example of a layer structure of an organic electroluminescent element. It is a schematic diagram showing an example of a vacuum evaporation system used by a manufacturing method of a film of the present invention. It is a graph which shows the thermogravimetric analysis result of compound T9. It is a graph which shows the thermogravimetric analysis result of compound T10.
  • the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • the isotopic species of hydrogen atoms present in the molecule of the compound used in the present invention are not particularly limited, and for example, all the hydrogen atoms in the molecule may be 1 H, or some or all of them may be 2 H. (Deuterium D) may be used.
  • excitation light refers to light that excites an irradiation target, and unless otherwise specified, it is light having a wavelength that matches the absorption wavelength of the irradiation target.
  • ⁇ Membrane manufacturing method> In the method for producing a film of the present invention, the first compound and the second compound are co-evaporated from a vapor deposition source containing both a first compound that satisfies the following formula (1) and a second compound that satisfies the following formula (2). It has a step of forming a film containing a compound.
  • ⁇ E ST (1) ⁇ 0.3 eV Formula (1)
  • E S1 (2) Formula (2)
  • ⁇ E ST (1) is the difference between the lowest excited singlet energy level E S1 (1) of the first compound and the lowest excited triplet energy level E T1 (1) of the first compound.
  • E S1 (2) is the lowest excited singlet energy level of the second compound.
  • the difference between the lowest excited singlet energy level E S1 (2) of the second compound and the lowest excited triplet energy level E T1 (2) of the second compound is expressed as ⁇ E ST (2). Further, generally, the difference between the lowest excited singlet energy level E S1 and the lowest excited triplet energy level E T1 of a particular compound is expressed as ⁇ E ST .
  • a sample of a solution in which the compound to be measured is dissolved in toluene or a sample of a film co-deposited with the host material so that the concentration of the compound to be measured is 6% by weight is prepared.
  • the host material is selected from those having a higher excited singlet energy level than E S1 of the compound to be measured and a higher excited triplet energy level than E T1 of the compound to be measured.
  • Delta] E ST as described in the claims is a value measured using a sample of film with a thickness of 100nm was co-evaporated with mCP as the concentration of the measurement target compounds on the Si substrate of 6 wt%.
  • E S1 Lowest excited singlet energy level
  • the fluorescence spectrum of the sample is measured at room temperature (300K). Emission intensity immediately after the excitation light is incident to 100 nanoseconds after the excitation light is integrated to obtain a fluorescence spectrum with the emission intensity on the vertical axis and the wavelength on the horizontal axis. In the fluorescence spectrum, the vertical axis indicates emission and the horizontal axis indicates wavelength. A tangent line is drawn to the rising edge of the emission spectrum on the short wave side, and the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis is obtained. The value obtained by converting this wavelength value into an energy value by the conversion formula shown below is E S1 .
  • E S1 [eV] 1239.85/ ⁇ edge
  • a nitrogen laser MNL200 manufactured by Lasertechnik Berlin
  • a streak camera C4334 manufactured by Hamamatsu Photonics
  • E T1 Lowest excited triplet energy level
  • the phosphorescence spectrum of the emission intensity on the vertical axis and the wavelength on the horizontal axis is obtained by integrating the emission from 1 millisecond after the excitation light is incident to 10 milliseconds after the incidence.
  • a tangent line is drawn to the rising edge of the phosphorescence spectrum on the short wavelength side, and the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis is obtained.
  • the value obtained by converting this wavelength value into an energy value using the conversion formula shown below is E T1 .
  • Conversion formula: E T1 [eV] 1239.85/ ⁇ edge
  • the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side is drawn as follows.
  • the present invention is characterized in that, when co-evaporating the first compound and the second compound, an evaporation source containing both of these materials is used.
  • an evaporation source containing both of these materials is used.
  • the first compound and the second compound can be stably deposited to form a good quality film.
  • the vapor deposition source used in the present invention will be described.
  • the vapor deposition source contains both the first compound and the second compound.
  • the vapor deposition source used in the present invention may include only the first compound and the second compound, may include other vapor deposition materials, and may include a container or a holding material that holds these materials. Good.
  • the materials that will be the material of the film, that is, the first compound, the second compound, and other vapor deposition materials may be collectively referred to as “vapor deposition material”.
  • the first compound, the second compound, other vapor deposition materials included in the vapor deposition source, the content of each material, and the mode of the vapor deposition source will be described in order.
  • the first compound contained in the vapor deposition source that is, the material having ⁇ E ST of 0.3 eV or less, has the lowest excited singlet energy level E S1 and the lowest excited triplet energy level E T1 close to each other. To an excited singlet state tends to occur. It is confirmed that the first compound causes an intersystem crossing by observing delayed fluorescence emitted when the excited singlet state generated by the intersystem crossing is deactivated by radiation to the ground singlet state. be able to.
  • the “delayed fluorescence” in the present specification means that the fluorescence emission lifetime ( ⁇ ) is 200 ns (nanosecond) or more.
  • fluorescence emission lifetime ( ⁇ ) means the emission decay measurement after completion of photoexcitation in a solution or vapor-deposited film sample in the absence of oxygen such as under a nitrogen atmosphere or under vacuum. It means the time required by doing.
  • the emission lifetime of the fluorescent component having the longest emission lifetime is “fluorescence emission lifetime ( ⁇ )”.
  • the first compound used for the vapor deposition source is preferably a material that causes inverse intersystem crossing from an excited triplet state to an excited singlet state, and more preferably a material that emits delayed fluorescence.
  • the ⁇ E ST of the first compound is preferably lower, specifically 0.2 eV or less, more preferably 0.1 eV or less, and further preferably 0.05 eV or less. More preferably, it is even more preferably 0.01 eV or less, and ideally 0 eV.
  • the smaller the ⁇ E ST the more likely the first compound is to undergo inverse intersystem crossing, and the effect of converting the excited triplet state to the excited singlet state can be effectively exhibited.
  • the first compound used for the vapor deposition source may be a material composed of a single compound satisfying the formula (1) or may be a material composed of two or more kinds of compounds forming an exciplex.
  • the difference ⁇ E ST between the lowest excited singlet energy level E S1 and the lowest excited triplet energy level E T1 of the exciplex is 0.3 eV or less. Is preferred.
  • the first compound is liable to cause radiation deactivation from the excited triplet state to the ground singlet state at room temperature (300 K). It is preferable that the phosphor is not a usual phosphorescent material.
  • the first compound contained in the vapor deposition source may be of one type or of two or more types.
  • the first compounds may have different structures of the compounds constituting the material, or may be composed of a single compound or form an exciplex. It may be different in whether or not it is composed of two or more compounds. Further, the two or more kinds of first compounds may differ in the lowest excited singlet energy level E S1 , the lowest excited triplet energy level E T1 , their energy difference ⁇ E ST, and the like.
  • Examples of the first compound include compounds represented by the following general formula (1a).
  • D represents a substituent having a substituted amino group
  • L represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group
  • A is a cyano group, or at least one It represents a substituted or unsubstituted heteroaryl group containing a nitrogen atom as a ring skeleton-constituting atom.
  • the arylene group or heteroarylene group represented by L may be a single ring or a condensed ring in which two or more rings are condensed.
  • the number of condensed rings is preferably 2 to 6, and can be selected from, for example, 2 to 4.
  • Specific examples of the ring forming L include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, and a naphthalene ring.
  • arylene group or heteroarylene group represented by L include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group, 2 ,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, 1, 4-anthracenylene group, 1,3-anthracenylene group, a group in which one of the ring skeleton constituent atoms of these groups is substituted with a nitrogen atom, a group in which two of the ring skeleton constituent atoms of these groups are substituted with nitrogen atoms, and these A group in which three of the ring skeleton-constituting atoms of the above group are substitute
  • the arylene group or heteroarylene group represented by L may have a substituent or may be unsubstituted. When it has two or more substituents, the plural substituents may be the same or different from each other. Examples of the substituent include a hydroxy group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a carbon number.
  • Examples thereof include a trialkylsilylalkyl group having 20 carbon atoms, a trialkylsilylalkenyl group having 5 to 20 carbon atoms, a trialkylsilylalkynyl group having 5 to 20 carbon atoms, a substituent having a substituted amino group, and a cyano group.
  • substitutable with a substituent may be substituted. More preferred substituents are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted groups having 3 to 40 carbon atoms. Alternatively, it is an unsubstituted heteroaryl group.
  • More preferred substituents are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and a carbon number. 3 to 12 substituted or unsubstituted heteroaryl groups.
  • the number of nitrogen atoms as a ring skeleton constituting atom is preferably 1 to 3.
  • the preferred range and specific examples of the heteroarylene group represented by L can be read as a monovalent group.
  • the heteroaryl group for A is preferably a group consisting of a 6-membered ring containing 1 to 3 nitrogen elements as ring skeleton-constituting atoms, more preferably a pyridinyl group, a pyrimidinyl group or a triazinyl group, and triazinyl More preferably, it is a group.
  • the heteroaryl group may be substituted with a substituent.
  • A may be a substituted or unsubstituted heteroaryl group, but is preferably a cyano group. Particularly, those in which A is a cyano group are more preferable than those in which A is a triazinyl group.
  • Examples of the compound represented by the general formula (1a) include a compound containing a cyanobenzene skeleton represented by the following general formula (1b) and a compound containing a triazine skeleton represented by the general formula (1c).
  • one 0-4 of R 1 ⁇ R 5 represents a cyano group, at least one of R 1 ⁇ R 5 is a substituent having a substituted amino group, the remaining R 1 ⁇ R 5 Represents a hydrogen atom, or a substituent having a substituted amino group and a substituent other than a cyano group.
  • the number of cyano groups in R 1 to R 5 may be any number from 0 to 4, but is preferably 2. That is, among the compounds containing the cyanobenzene skeleton, the compounds containing the dicyanobenzene skeleton are more preferable.
  • R 6 ⁇ R 8 is a substituent having a substituted amino group, the remaining R 6 ⁇ R 8 is other than substituent with a cyano group having a hydrogen atom or a substituted amino group, Represents a substituent.
  • the substituent having a substituted amino group in the general formulas (1a) to (1c) is preferably a substituent having a diarylamino group, and the two aryl groups constituting the diarylamino group are linked to each other, for example, carbazolyl. It may be the base. Further, the substituent having a substituted amino group in the general formula (1b) may be any of R 1 to R 5 , and examples thereof include R 2 , R 3 , R 4 , R 1 and R 3 , R 1 and R 5.
  • R 1 and R 5 , R 2 and R 3 , R 2 and R 3 , R 1 and R 3 and R 5 , R 1 and R 2 and R 3 , R 1 and R 3 and R 4 , R 2 and Preferable examples include R 3 and R 4 , R 1 and R 2 , R 3 and R 4 , R 1 , R 2 , R 3 , R 4 and R 5 .
  • the substituent having a substituted amino group in the general formula (1c) may be any of R 6 to R 8 , and examples thereof include R 6 , R 6 and R 7 , R 6 and R 7 and R 8 . can do.
  • the substituent having a substituted amino group in the general formulas (1a) to (1c) is preferably a substituent represented by the following general formula (2a).
  • the number of the substituents represented by the general formula (2a) is preferably 2 or more in the molecule, and more preferably 3 or more.
  • the substitution position of the substituent represented by formula (2a) is not particularly limited.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
  • L represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • * Represents a bonding position to the carbon atom (C) in the general formulas (1a) to (1c).
  • Ar 1 and Ar 2 in the general formula (2a) may bond to each other to form a cyclic structure together with the nitrogen atom in the general formula (2a).
  • the arylene group or heteroarylene group represented by Ar 1 and Ar 2 may be a single ring or a condensed ring in which two or more rings are condensed.
  • the number of condensed rings is preferably 2 to 6, and can be selected from, for example, 2 to 4.
  • Specific examples of the ring forming Ar 1 and Ar 2 include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring and a naphthalene ring.
  • arylene group or heteroarylene group represented by Ar 1 and Ar 2 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a 2-pyridyl group. Examples thereof include a 3-pyridyl group and a 4-pyridyl group.
  • the arylene group or heteroarylene group represented by Ar 1 and Ar 2 may have a substituent or may be unsubstituted. When it has two or more substituents, the plural substituents may be the same or different from each other.
  • Examples include an alkylamide group having 20 to 20 carbon atoms, an arylamide group having 7 to 21 carbon atoms, and a trialkylsilyl group having 3 to 20 carbon atoms.
  • substitutable with a substituent may be substituted. More preferable substituents are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl-substituted amino group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. An aryl-substituted amino group, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms.
  • the substituent represented by the general formula (2a) is preferably a substituent represented by the following general formula (2b).
  • R 11 to R 20 each independently represent a hydrogen atom or a substituent.
  • L represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 And R 20 may combine with each other to form a linking group necessary for forming a cyclic structure.
  • R 15 and R 16 may be bonded to each other to form a single bond or a linking group.
  • * Represents a bonding position to the carbon atom (C) in the general formulas (1a) to (1c).
  • R 11 to R 20 can have, refer to the corresponding description of the substituents of the arylene group or heteroarylene group represented by Ar 1 and Ar 2 in the general formula (1a). it can.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 R 20 is a cyclic structure formed by bonding may be aliphatic ring even aromatic rings, also may be one containing a hetero atom, further cyclic structure 2 or more rings fused with May be
  • the hetero atom referred to herein is preferably selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom.
  • Examples of the formed cyclic structure benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole ring, iso Examples thereof include a thiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring and a cycloheptaene ring.
  • L represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • L is preferably a single bond or a substituted or unsubstituted arylene group.
  • the aromatic ring forming the arylene group represented by L may be a single ring, a condensed ring in which two or more aromatic rings are condensed, or a linking ring in which two or more aromatic rings are linked. When two or more aromatic rings are linked, they may be linearly linked or branched.
  • the aromatic ring constituting the arylene group represented by L preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 14 carbon atoms, and 6 to 10 carbon atoms. Are even more preferred.
  • Specific examples of the arylene group include a phenylene group, a naphthalenediyl group, and a biphenylene group.
  • the heterocycle constituting the heteroarylene group represented by L is a monocycle, a condensed ring formed by condensing one or more heterocycles with an aromatic ring or a heterocycle, and one or more heterocycles with an aromatic ring. It may be a linking ring in which a ring or a heterocycle is linked.
  • the carbon number of the heterocycle is preferably 5 to 22, more preferably 5 to 18, even more preferably 5 to 14, and even more preferably 5 to 10.
  • the heteroatoms forming the heterocycle are preferably nitrogen atoms.
  • Specific examples of the heterocycle include a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazole ring and a benzotriazole ring.
  • a more preferred group represented by L is a phenylene group. When L is a phenylene group, the phenylene group may be any of a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group, but is preferably a 1,4-phenylene group. preferable.
  • L may be substituted with a substituent.
  • the number and the substitution position of the substituent of L are not particularly limited.
  • the description and the preferable range of the substituent that can be introduced into L the description and the preferable range of the substituent that R 11 to R 20 can take can be referred to.
  • the substituent represented by the general formula (2b) is preferably a substituent represented by any one of the following general formulas (3) to (7).
  • R 21 to R 24 , R 27 to R 38 , R 41 to R 48 , R 51 to R 58 , R 61 to R 65 , and R 81 to R 90 are independent of each other.
  • R 21 to R 24 , R 27 to R 38 , R 41 to R 48 , R 51 to R 58 , R 61 to R 65 , R 71 to R 79 , and R 81 to R 90 are each independently the above general formula ( It is also preferably a group represented by any of 3) to (7).
  • R 21 , R 23 , R 28 , and R 30 in the general formula (3) are preferably substituted or unsubstituted alkyl groups, and R 21 , R 23 , R 28 , and R 30 It is more preferred that all of R are substituted or unsubstituted alkyl groups, R 21 and R 30 are substituted or unsubstituted alkyl groups, or R 23 and R 28 are substituted or unsubstituted alkyl groups. More preferably, the substituted or unsubstituted alkyl group is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
  • R 89 and R 90 in the general formula (7) are preferably substituted or unsubstituted alkyl groups, and more preferably substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • the number of substituents in the general formulas (3) to (7) is not particularly limited. It is also preferable that all are unsubstituted (that is, hydrogen atoms). When there are two or more substituents in each of formulas (3) to (7), those substituents may be the same or different.
  • the substituent is preferably any one of R 22 to R 24 and R 27 to R 29 in the general formula (3).
  • R 23 and R 28 are more preferable, R 32 to R 37 are preferable in the general formula (4), and R 42 to R 37 are preferable in the general formula (5). It is preferably any one of R 47 , and if it is the general formula (6), it is preferably any one of R 52 , R 53 , R 56 , R 57 and R 62 to R 64 , and the general formula (7) In this case, it is preferably any one of R 82 to R 87 , R 89 and R 90 .
  • L 1 to L 5 represent a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • * Represents a bonding position to the carbon atom (C) in the general formulas (1a) to (1c).
  • L 1 to L 5 are preferably a single bond or a substituted or unsubstituted arylene group.
  • the first compound is often a compound known as a compound that emits delayed fluorescence.
  • Examples of such compounds include paragraphs 0008 to 0048 and 0095 to 0133 of WO 2013/154064, paragraphs 0007 to 0047 and 0073 to 0085 of WO 2013/011954, and paragraphs 0007 to 0033 and 0059 to 0066 of WO 2013/011955.
  • JP 2013-253121 A JP 2013-253121 A, WO 2013/133359 A, WO 2014/034535 A, WO 2014/115743 A, WO 2014/122895 A, WO 2014/126200 A.
  • JP 2013/136758 WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO2014/168101, WO2015/008580, WO2014/203840 JP 2013-253121 A, WO 2013/133359 A, WO 2014/034535 A, WO 2014/115743 A, WO 2014/122895 A, WO 2014/126200 A.
  • WO2014/136758 WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO2014/168101, WO2015/008580, WO2014/203840 JP 2013-253121 A, WO 2013/133359 A, WO 2014/034535 A, WO 2014/115743
  • the vapor deposition source used in the present invention contains a second compound in addition to the first compound.
  • the second compound is a compound that satisfies the formula (2).
  • E S1 (1)> E S1 (2) Formula (2) In the above equation, E S1 (1) is the lowest excited singlet energy level of the first compound, and E S1 (2) is the lowest excited singlet energy level of the second compound.
  • the difference between E S1 (1) and E S1 (2) [E S1 (1)-E S1 (2)] is, for example, 0.1 eV or more, 0.2 eV or more, 0.3 eV or more, 0.5 eV or more. , 1.2 eV or less, 1.0 eV or less, 0.8 eV or less, 0.6 eV or less.
  • the excited singlet energy of the first compound is easily transferred to the second compound in the obtained film, and the excitation generated by the intersystem crossing of the first compound is excited. Energy in the singlet state can be efficiently used for light emission of the second compound.
  • the second compound is preferably a fluorescent material.
  • the “fluorescent material” in the present invention means an organic material that emits fluorescence when a solution sample such as toluene or dichloromethane or a vapor deposition film sample is irradiated with excitation light at 20° C.
  • fluorescence is light emitted upon deactivation from the excited singlet state to the ground singlet state.
  • the fluorescent material in the present invention may be one that emits phosphorescence together with fluorescence, but in that case, the fluorescence intensity is preferably 9 times or more the phosphorescence intensity.
  • a compound having a fluorescence emission lifetime ( ⁇ ) of less than 200 ns (nanosecond) may be adopted, or a delayed fluorescent material having a fluorescence emission lifetime ( ⁇ ) of 200 ns (nanosecond) or more is adopted. You may.
  • the description of the fluorescence emission lifetime ( ⁇ ) the description of the fluorescence emission lifetime ( ⁇ ) in the (first compound) column can be referred to.
  • the delayed fluorescent material preferably satisfies the following relational expression.
  • ⁇ E ST (2) is the difference between the lowest excited singlet energy level E S1 (2) of the second compound and the lowest excited triplet energy level E T1 (2) of the second compound.
  • the second compound may be selected from the compounds T1 to T57 as long as the relationship between the above formulas (1) and (2) is satisfied.
  • the emission wavelength of the second compound is not particularly limited and can be appropriately selected depending on the application of the obtained film.
  • the second compound is a near infrared region (750 to 2500 nm) or a red region (620 to 750 nm) or It is preferable to have a maximum emission wavelength in the green region (495 to 570 nm) and the blue region (450 to 495 nm).
  • the second compound contained in the vapor deposition source may be one type or two or more types.
  • the second compounds have different structures of the compounds constituting the second compound, and the emission wavelength and emission color, and the lowest excited singlet energy level E S1 and the lowest excited triplet energy level E T1 may be different.
  • Examples of the second compound include anthracene derivative, tetracene derivative, naphthacene derivative, pyrene derivative, perylene derivative, chrysene derivative, rubrene derivative, coumarin derivative, pyran derivative, stilbene derivative, fluorene derivative, anthryl derivative, pyrromethene derivative, terphenyl derivative, and terphenyl derivative.
  • a phenylene derivative a fluoranthene derivative, an amine derivative, a quinacridone derivative, an oxadiazole derivative, a malononitrile derivative, a pyran derivative, a carbazole derivative, a julolidine derivative, a thiazole derivative, and a compound having a mother skeleton of these derivatives.
  • the mother skeleton of these derivatives may or may not have a substituent.
  • specific examples of the compound that can be used as the second compound will be illustrated. However, the compound that can be used as the second compound in the present invention should not be limitedly interpreted by these specific examples.
  • Et represents an ethyl group.
  • a compound containing a cyanobenzene skeleton as the second compound.
  • the evaporation rate (weight reduction rate) during vapor deposition is the same as that of the first compound and the second compound.
  • it is easy to produce a good quality film for the reason that it is easy to match.
  • the compound containing a cyanobenzene skeleton used for the second compound is more preferably a compound containing a dicyanobenzene skeleton, and further preferably a compound containing a 1,4-dicyanobenzene skeleton (terephthalonitrile skeleton). preferable.
  • the compound containing a cyanobenzene skeleton used for the second compound may emit delayed fluorescence.
  • the description of the general formula (1b) in the (first compound) column and specific examples (compounds T1 to T21) can be referred to.
  • the combination of the first compound and the second compound used for the vapor deposition source is not particularly limited.
  • the first compound and the second compound contained in the vapor deposition source may be one kind or two or more kinds, but are preferably one kind of compound.
  • all of the first compounds satisfy the formula (1), and all the second compounds are expressed by the formula (). 1) is satisfied.
  • E S1 of the most lowest excited singlet energy level E S1 (2) is higher compound in a second compound (2) is the most lowest excited singlet energy in the first compound and lower than E S1 (1) of the level E S1 (1) is lower compound.
  • the two or more kinds of the first compound and the second compound are not particularly limited, and for example, a combination that forms an exciplex may be included in the two or more kinds of compounds.
  • a combination of two or more first compounds forming an exciplex is included, the combination of the first compounds forming the exciplex is the lowest excited singlet energy level E S1 (Ex) and the lowest of the exciplex.
  • the excited triplet energy level E T1 (Ex) preferably satisfies the formula (1) in which E S1 (1) and E T1 (1) are replaced. That is, the energy difference ⁇ E ST (Ex) between E S1 (Ex) and E T1 (Ex) of the first compound is preferably 0.3 eV or less.
  • the combination of the second compounds forming the exciplex is the lowest excited singlet energy level E S1 (Ex) of the exciplex. It is preferable to satisfy the expression (2) in which E S1 (2) is replaced with. That is, it is preferable that E S1 (Ex) of the second compound is lower than E S1 (1) of the first compound.
  • the second compound E S1 (Ex) is preferably lower than the first compound E S1 (Ex).
  • the energy levels E S1 (Ex) and E T1 (Ex) of the exciplex can be determined according to the above-mentioned ⁇ E ST calculation method, using a film composed of a set of compounds forming the exciplex as a measurement sample. it can.
  • the combination of the first compound and the second compound that can be used for the vapor deposition source refer to Table 1 listed in the section “Film containing the first compound and the second compound”.
  • the combination of the first compound and the second compound that can be used in the present invention should not be limitedly interpreted by these specific examples.
  • the vapor deposition source may include only the first compound and the second compound as vapor deposition materials, or may include other vapor deposition materials.
  • Other vapor deposition materials include host materials and dopants.
  • the host material it is preferable that the lowest excited singlet energy level E S1 is used higher than the lowest excited singlet energy level E S1 of the first compound and the second compound, its lowest excited singlet energy
  • the level E S1 is higher than the lowest excited singlet energy level E S1 of the first compound and the second compound, and the lowest excited triplet energy level E T1 is the lowest excited triplet energy level of the first compound. It is more preferred to use a position higher than the position E T1 .
  • the host material is preferably an organic compound having a hole transporting ability and an electron transporting ability, preventing the emission from having a long wavelength and having a high glass transition temperature.
  • the host material may be one kind or two or more kinds.
  • the host materials have different structures of the compounds constituting the host materials, the lowest excited singlet energy level E S1 and the lowest excited triplet energy level. E T1 and the like may be different.
  • the compound that can be used as the host material the host materials exemplified in the section (Application of the present invention) can be referred to.
  • the compounds that can be used as the host material in the present invention should not be limitedly interpreted by these specific examples.
  • the compound that can be used as the dopant is, for example, a light-emitting body having a lower minimum excited singlet energy level E S1 than the first compound and the second compound.
  • a dopant receives energy from the first compound and the second compound in the excited singlet state and from the first compound and the second compound which are in the excited singlet state due to reverse intersystem crossing from the excited triplet state. When it transits to the excited singlet state and then returns to the ground state, it emits fluorescence.
  • the luminescent material used as the dopant is not particularly limited as long as it can emit energy by receiving energy from the first compound and the second compound as described above, and the luminescence may be fluorescence or delayed fluorescence, It may be phosphorescent.
  • the luminescent material used as the dopant emits fluorescence when returning from the lowest excited singlet energy level E S1 to the ground singlet energy level E S0 .
  • Two or more kinds of dopants may be used.
  • a desired color can be emitted by using two or more kinds of dopants having different emission colors together.
  • anthracene derivative, tetracene derivative, naphthacene derivative, pyrene derivative, perylene derivative, chrysene derivative, rubrene derivative, coumarin derivative, pyran derivative, stilbene derivative, fluorene derivative, anthryl derivative, pyrromethene derivative, terphenyl derivative, terphenylene derivative , A fluoranthene derivative, an amine derivative, a quinacridone derivative, an oxadiazole derivative, a malononitrile derivative, a pyran derivative, a carbazole derivative, a julolidine derivative, a thiazole derivative, and a compound having a mother skeleton of these derivatives can be used.
  • the mother skeleton of these derivatives may or may not have a substituent.
  • the dopant may include two or more of these skeletons.
  • the specific examples of the dopant the specific examples of the compound that can be used for the second compound, which are shown in the above section of (Second compound), can be referred to.
  • the respective contents of the first compound, the second compound and other vapor deposition materials in the vapor deposition source can be appropriately selected according to the composition of the target film and the conditions of co-evaporation.
  • the content rate of the first compound in the vapor deposition source is preferably higher than the content rate of the second compound, and is preferably 50% by weight or more based on the total amount of the first compound and the second compound. It is more preferably at least wt%, further preferably at least 95 wt%, and preferably at most 99.9 wt%.
  • the content of the second compound in the vapor deposition source is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the total amount of the first compound and the second compound, and 0. It is more preferably 0.5% by weight or more, preferably 50% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.
  • the content of the host material is preferably 15% by weight or more, more preferably 50% by weight or more, and 65% by weight or more with respect to the total amount of the vapor deposition material. Is more preferable.
  • the content of the host material in the vapor deposition source is preferably 99.9% by weight or less, more preferably 99% by weight or less, and 90% by weight with respect to the total vapor deposition material. The following is more preferable.
  • the content of the first compound in the vapor deposition source is preferably 5 wt% or more, more preferably 10 wt% or more, and 20 wt% with respect to the total amount of the vapor deposition material.
  • the upper limit is preferably 80% by weight or less, and more preferably 50% by weight or less, based on the total amount of the vapor deposition material.
  • the content of the second compound in the vapor deposition source is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, based on the total amount of the vapor deposition material. Is more preferably 0.5% by weight or more, and the upper limit is preferably 50% by weight or less, more preferably 10% by weight or less, and more preferably 5% by weight with respect to the total amount of the vapor deposition material. It is more preferable that the amount is not more than 3%, and it is further preferable that the amount is 3% by weight or less.
  • the vapor deposition source used in the present invention contains both the first compound and the second compound, and may be one in which each material is contained in the same container or one in which each material is held by the same holding material. Good.
  • a mixed powder obtained by mixing the powder of the first compound and the powder of the second compound, or these powders and other materials used as necessary. What mixed powder mixed powder is housed in the same container, compression molded product obtained by compression molding of these mixed powders, first compound and second compound are heated and melted and mixed, and then solidified by cooling.
  • the solids include solids obtained by heating, melting these materials and other vapor deposition materials used as needed, mixing them by heating, and solidifying by cooling.
  • the compression molded body and the solid obtained by heating and melting may be housed in a container as a vapor deposition source.
  • a crucible or the like which is usually used in a vapor deposition device can be used.
  • FIG. 2 shows an example of a vacuum vapor deposition apparatus used for this co-evaporation.
  • the vacuum vapor deposition apparatus shown in FIG. 2 includes a chamber 100 that is a pressure resistant container, a vapor deposition source 101 installed in the chamber 100, and a substrate holding unit 102 disposed inside the chamber 100 so as to face the vapor deposition source 101. ..
  • the vapor deposition source 101 is configured by accommodating a vapor deposition material 101a containing both a first compound and a second compound in a crucible 101b.
  • the vacuum vapor deposition apparatus is provided with a vacuum pump for bringing the chamber 100 into a vacuum state and a heating device for heating the vapor deposition source.
  • the substrate 10 for forming a film is mounted on the substrate holding unit 102 so that the film formation surface faces the evaporation source 101 side.
  • the base material 10 can be appropriately selected depending on the intended use of the obtained film, and for example, a substrate made of glass, transparent plastic, quartz, silicon or the like can be used. Further, the base material may be a substrate on which a functional film is formed.
  • the functional film constituting the base material for example, in the case of finally manufacturing a specific element, in the element, a film or a laminated film arranged between the film formed here and the substrate may be mentioned. be able to.
  • the element to be manufactured is an organic electroluminescence element
  • an electrode layer, a carrier injection layer, a carrier transport layer and the like can be cited as the functional film constituting the base material.
  • the inside of the chamber 100 is evacuated to heat the vapor deposition source 101.
  • the vapor deposition material 101a is melted, vaporized, or sublimated, and the vaporized or sublimated particles are attached and deposited on the surface of the base material 10.
  • the vapor deposition source contains both the first compound and the second compound, these materials can be stably deposited on the surface of the base material and a good film can be formed.
  • the degree of vacuum in the chamber 100 when forming the film is preferably 10 ⁇ 2 Pa or less, more preferably 10 ⁇ 4 Pa or less, and further preferably 10 ⁇ 5 Pa or less. preferable.
  • the film formation rate of the film is not particularly limited, but is preferably 0.01 to 30 ⁇ /s, more preferably 0.1 to 20 ⁇ /s, and further preferably 1 to 10 ⁇ /s. ..
  • the heating temperature of the vapor deposition source 101 and the film formation rate may be kept constant during film formation, or may be changed with time.
  • the composition corresponding to the composition ratio of the multiple compounds contained in the vapor deposition source is set. It is preferable because a film having a specific ratio can be formed. Then, if a plurality of compounds are mixed at the same composition ratio as that of the film to be realized and used as the vapor deposition source, a film having a desired composition ratio can be easily formed.
  • the specific source is obtained by using a vapor deposition source in which the first compound and the second compound are mixed at a desired composition ratio. If co-evaporation is performed at a temperature, a film having a desired composition ratio can be formed.
  • a specific temperature can be determined by performing thermogravimetric analysis of the first compound and the second compound in advance. For example, how the weight reduction rate W (unit: %) of the compound changes when the temperature T (unit: °C) of the compound is increased at a constant temperature rising rate for the first compound and the second compound, respectively. It can be determined by making a graph.
  • the rate of temperature increase is preferably selected within the range of 5 to 20° C./minute, and can be set to, for example, 10° C./minute.
  • the weight reduction rate W referred to here is expressed as 0% before the start of thermogravimetric analysis and as -100% when the weight becomes 0.
  • T WT the temperature at which the first compound and the second compound have the same weight loss rate is specified and is used as the temperature during co-deposition. That is, when the thermogravimetric analysis graph of the first compound (vertical axis W, horizontal axis T) and the thermogravimetric analysis graph of the second compound (vertical axis W, horizontal axis T) are overlapped, at the intersection point where the two curves intersect.
  • the temperature can be specified as T WT and used as the temperature during co-deposition.
  • T WT temperature at which the dW/dT of the first compound and the second compound are the same is specified and is used as the temperature during co-deposition.
  • T GR temperature at which the dW/dT of the first compound and the second compound are the same is specified and is used as the temperature during co-deposition.
  • These temperatures T WT and T GR are preferably specified as temperatures within the range of ⁇ 5% ⁇ W ⁇ 95%, and are specified as temperatures within the range of ⁇ 90% ⁇ W ⁇ 10%. It is more preferable that the temperature be within the range of ⁇ 80% ⁇ W ⁇ 20%.
  • the temperature T (co-deposition) at the time of co-deposition does not have to be exactly the temperature T WT or the temperature T GR itself, but depending on the intended use of the film to be formed, T WT -10°C ⁇ T (co-deposition). It may be ⁇ T WT +10° C. or T GR ⁇ 10° C. ⁇ T (co-deposition) ⁇ T GR +10° C., or T WT ⁇ 5° C. ⁇ T (co-deposition) ⁇ T WT +5° C. or T GR ⁇ It may be 5° C. ⁇ T (co-deposition) ⁇ T GR +5° C.
  • the vacuum vapor deposition apparatus used for co-vapor deposition in the present invention is not limited to the above configuration, and the configuration of each part constituting the vacuum vapor deposition apparatus may be replaced with any that can exhibit the same function. Alternatively, an arbitrary configuration can be added.
  • the vacuum vapor deposition apparatus includes a crucible that accommodates the second first compound and the second second compound, separately from the crucible 101b, and the vapor deposition source 102 and the second first compound or the second second compound.
  • the vapor deposition may be performed from two vapor deposition sources including a compound, or may include a vapor deposition source 102, a vapor deposition source including a second first compound, and a second second compound.
  • the vapor deposition source may be configured to perform co-deposition from three vapor deposition sources, or the vapor deposition source 102 and two vapor deposition sources including both the second first compound and the second second compound. May be configured to co-deposit.
  • the vapor deposition source 102 it is possible to use a vapor deposition source containing a host material or a vapor deposition source containing a dopant, or to increase the vapor deposition sources for the first compound and the second compound.
  • the descriptions in the columns of (first compound) and (second compound) can be referred to. .
  • the second first compound and the second second compound may each be of one type or of two or more types.
  • the vacuum vapor deposition apparatus may include a rotating device in the substrate holding unit 102 that rotates the substrate 10 at a predetermined speed with a predetermined position of the substrate 10 as a rotation center while holding the substrate 10 horizontally. By rotating the substrate 10 by the rotating device during the co-deposition, the film thickness distribution of the formed film can be made uniform.
  • the vacuum vapor deposition device may include a shutter that blocks evaporation of the vapor deposition material, a film thickness meter that measures the film thickness of the film formed, and the like.
  • the film formed by the present invention is a film containing the first compound and the second compound.
  • the film formed in the present invention may be composed of only the first compound and the second compound, or may contain other materials. Other materials include host materials and dopants.
  • the film containing another material can be formed by including another material in the vapor deposition source in addition to the first compound and the second compound.
  • the first compound, the second compound, the host material and the dopant, and specific examples see the descriptions and preferred ranges of the first compound, the second compound, the host material and the dopant used for the vapor deposition source, and specific examples. can do.
  • the first compound, the second compound, and the host material and the dopant used as necessary, which are contained in the film may be one kind or two or more kinds, respectively.
  • the film preferably contains more of the first compound than the second compound.
  • the content of the first compound in the film is preferably 50% by weight or more, more preferably 80% by weight or more, and further preferably 95% by weight or more.
  • the content of the first compound in the film is preferably 99.9% by weight or less, more preferably 99% by weight or less, and further preferably 95% by weight or less.
  • the content of the second compound in the film is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.5% by weight or more.
  • the content of the second compound in the film is preferably less than 10% by weight, more preferably less than 5% by weight, still more preferably less than 3% by weight.
  • the content of the host material is preferably 15% by weight or more, more preferably 50% by weight or more, and further preferably 65% by weight or more.
  • the content of the host material in the film is preferably 99.9% by weight or less, more preferably 99% by weight or less, and further preferably 90% by weight or less.
  • the content of the first compound in the film is preferably 1% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, Further, the upper limit is preferably 99.9% by weight or less, more preferably 80% by weight or less, and further preferably 50% by weight or less.
  • the content of the second compound in the film is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and 0.5% by weight or more. More preferably, the upper limit is less than 50% by weight, more preferably less than 10% by weight, further preferably 5% by weight or less, further preferably 3% by weight or less. Is more preferable.
  • the content of the dopant in the film is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and 0.1% by weight or more. More preferable.
  • the content of the dopant in the film is preferably less than 50% by weight, more preferably less than 10% by weight, further preferably less than 5% by weight, and more preferably 3% by weight or less. Even more preferable.
  • the ratio of the total amount of the first compound and the second compound in the film is preferably 10% by weight or more, and more preferably 20% by weight or more. More preferably, it is more preferably 50% by weight or more.
  • the upper limit is preferably less than 85% by weight.
  • the content of the first compound or the second compound in the film can be measured by liquid chromatography (LC) or nuclear magnetic resonance (NMR). Further, the content rates of these materials can be controlled by the content rate of each material in the vapor deposition source, the degree of vacuum of the vacuum vapor deposition apparatus, the heating temperature of the vapor deposition source, the film forming rate, and the like.
  • the film formed by the manufacturing method of the present invention emits light by irradiation with excitation light or current injection. Light emission occurs from the second compound contained in the film, and light emission from the first compound or the host material may occur. Also, if the film further comprises a dopant, light emission will result from the second compound and the dopant.
  • the emitted light may be normal fluorescence only, delayed fluorescence only, or may include fluorescence and delayed fluorescence, but preferably delayed fluorescence. That is, the film formed by the manufacturing method of the present invention preferably emits delayed fluorescence.
  • the fact that the film emits delayed fluorescence means that the inverse triplet crossing from the excited triplet state to the excited singlet state surely occurs in the film.
  • the energy is converted into excited singlet energy, and can be effectively used for fluorescence emission of the first compound and the second compound.
  • the emission of delayed fluorescence in the film can be observed by the emission decay measurement after the completion of photoexcitation in the absence of oxygen such as under nitrogen atmosphere or under vacuum.
  • delayed fluorescence the description in the column of (First compound) can be referred to.
  • the film formed by the present invention should not be limitedly interpreted by these specific examples.
  • Table 1 the number with T (T number) shown in the horizontal row shows the number of the compound used in the first compound, and the number with F shown in the vertical column (F number) shows that of the compound used in the second compound.
  • the numbers at the positions where the columns of the respective numbers intersect indicate the numbers of the membranes containing the compound of the corresponding T number as the first compound and the compound of the corresponding F number as the second compound.
  • preferred membranes are compound T1 and compound F88, compound T2 and compound F88, compound T3 and compound F88, compound T4 and compound F20, compound T4 and compound F21, compound T4 and compound F34, compound T5 and compound F20.
  • the method for producing an organic semiconductor element of the present invention has a step of forming a layer by the method for producing a film of the present invention.
  • the description in the section ⁇ Membrane production method> can be referred to.
  • the organic semiconductor element manufactured by the manufacturing method of the present invention is not particularly limited as long as it has a layer containing the first compound and the second compound.
  • organic electroluminescent elements organic electroluminescent devices
  • organic photoluminescent elements organic photoluminescent devices
  • semiconductor laser elements organic light emitting elements such as light storing elements, organic thin film solar cells, organic field effect transistors
  • organic thermoelectric elements organic piezoelectric elements.
  • a light emitting layer containing a first compound and a second compound can be formed by the method for producing a film of the present invention.
  • the layer is formed with good film quality, and excellent characteristics can be obtained. Show.
  • the method for forming the layers other than the layer containing the first compound and the second compound is not particularly limited, and may be formed by either a dry process or a wet process.
  • the light emitting layer contains the first compound and the second compound, and may further contain the host material.
  • the organic light emitting device comprises a light emitting layer.
  • the light emitting layer comprises a compound of formula (I) as a light emitting material.
  • the organic light emitting device is an organic photoluminescent device (organic PL device).
  • the organic light emitting device is an organic electroluminescent device (organic EL device).
  • the compounds of formula (I) assist (as a so-called co-dopant) the light emission of other emissive materials comprised in the emissive layer.
  • the compound of formula (I) comprised in the emissive layer has a lowest excited singlet energy level in the emissive layer and a lowest excited singlet energy level of the host material comprised in the emissive layer. It is included between the lowest excited singlet energy level of the other luminescent material included.
  • the organic photoluminescent device comprises at least one light emitting layer.
  • the organic electroluminescent device comprises at least an anode, a cathode, and an organic layer between the anode and the cathode.
  • the organic layer comprises at least a light emitting layer.
  • the organic layer comprises only a light emitting layer.
  • the organic layer comprises one or more organic layers in addition to the light emitting layer.
  • organic layers include hole transport layers, hole injection layers, electron barrier layers, hole barrier layers, electron injection layers, electron transport layers and exciton barrier layers.
  • the hole transport layer may be a hole injection transport layer having a hole injection function
  • the electron transport layer may be an electron injection transport layer having an electron injection function. Good. An example of an organic electroluminescent device is shown in FIG.
  • the organic electroluminescent device of the present invention is carried by a substrate, which substrate is not particularly limited and is commonly used in organic electroluminescent devices such as glass, transparent plastics, quartz and silicon. Any material formed by the above method may be used.
  • the anode of the organic electroluminescent device is made of metals, alloys, conductive compounds or combinations thereof.
  • the metal, alloy or conductive compound has a high work function (4 eV or higher).
  • the metal is Au.
  • the conductive transparent material is selected from CuI, indium tin oxide (ITO), SnO 2 and ZnO.
  • an amorphous material that can form a transparent conductive film such as IDIXO (In 2 O 3 —ZnO), is used.
  • the anode is a thin film. In some embodiments, the thin film is made by evaporation or sputtering.
  • the film is patterned by photolithographic methods. In some embodiments, if the pattern does not need to be highly accurate (eg, about 100 ⁇ m or more), the pattern may be formed using a mask having a shape suitable for vapor deposition or sputtering on the electrode material. In some embodiments, wet film forming methods such as printing and coating are used when a coating material such as an organic conductive compound can be applied. In some embodiments, when the emitted light passes through the anode, the anode has a transparency of greater than 10%, and the anode has a sheet resistance of hundreds of ohms or less per unit area. In some embodiments, the thickness of the anode is 10-1,000 nm. In some embodiments, the thickness of the anode is 10-200 nm. In some embodiments, the thickness of the anode will vary depending on the material used.
  • the cathode is made of an electrode material such as a low work function metal (4 eV or less) (referred to as an electron injection metal), an alloy, a conductive compound or a combination thereof.
  • the electrode material is sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al 2 O 3 ) mixtures, indium, lithium-aluminum mixtures and rare earth elements.
  • a mixture of an electron-injecting metal and a second metal that is a stable metal with a higher work function than the electron-injecting metal is used.
  • the mixture is selected from a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al 2 O 3 ) mixture, a lithium-aluminum mixture and aluminum.
  • the mixture improves electron injection properties and resistance to oxidation.
  • the cathode is manufactured by forming the electrode material as a thin film by vapor deposition or sputtering.
  • the cathode has a sheet resistance of less than a few hundred ohms per unit area.
  • the thickness of the cathode is 10 nm to 5 ⁇ m.
  • the thickness of the cathode is 50-200 nm.
  • any one of the anode and cathode of the organic electroluminescent device is transparent or translucent to transmit emitted light.
  • transparent or translucent electroluminescent devices enhance light radiance.
  • the cathode is formed of a conductive transparent material as described above for the anode to form a transparent or semi-transparent cathode.
  • the device includes an anode and a cathode, both transparent or translucent.
  • the light emitting layer is a layer in which holes and electrons injected from the anode and the cathode are recombined to form excitons.
  • the layer emits light.
  • only luminescent material is used as the luminescent layer.
  • the light emitting layer comprises a light emitting material and a host material.
  • the emissive material is one or more compounds of formula (I).
  • singlet excitons and triplet excitons generated in the emissive material are confined within the emissive material to improve the light emission efficiency of the organic electroluminescent and organic photoluminescent devices.
  • a host material is used in the light emitting layer in addition to the light emitting material.
  • the host material is an organic compound.
  • the organic compound has an excited singlet energy and an excited triplet energy, at least one of which is higher than those of the luminescent materials of the present invention.
  • the singlet excitons and triplet excitons generated in the luminescent material of the present invention are confined in the molecules of the luminescent material of the present invention.
  • the singlet and triplet excitons are well confined to enhance light emission efficiency.
  • the singlet excitons and triplet excitons are not well confined, i.e., a host with high light emission efficiency that can be used in the present invention, even though high light emission efficiency is still obtained.
  • the material is not particularly limited.
  • light emission occurs at the emissive material in the emissive layer of the device of the present invention.
  • the emitted light comprises both fluorescence and delayed fluorescence.
  • the emitted light comprises emitted light from a host material.
  • the emitted light comprises emitted light from a host material.
  • the emitted light comprises emitted light from a compound of formula (I) and emitted light from a host material.
  • TADF molecules and host materials are used.
  • TADF is a co-dopant.
  • the amount of the compound of the present invention as a light emitting material contained in the light emitting layer is 0.1% by weight or more. In some embodiments, when using a host material, the amount of the compound of the present invention as a light emitting material contained in the light emitting layer is 1% by weight or more. In some embodiments, when using a host material, the amount of the compound of the present invention as a light emitting material contained in the light emitting layer is 50% by weight or less.
  • the amount of the compound of the present invention as a light emitting material contained in the light emitting layer is 20% by weight or less. In some embodiments, when using a host material, the amount of the compound of the present invention as a light emitting material contained in the light emitting layer is 10% by weight or less. In some embodiments, the host material of the light emitting layer is an organic compound having a hole transport function and an electron transport function. In some embodiments, the host material of the light emitting layer is an organic compound that prevents the wavelength of emitted light from increasing. In some embodiments, the host material of the light emitting layer is an organic compound having a high glass transition temperature.
  • the injection layer is the layer between the electrode and the organic layer. In some embodiments, the injection layer reduces drive voltage and enhances light radiance. In some embodiments, the injection layer comprises a hole injection layer and an electron injection layer. The injection layer can be arranged between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. In some embodiments, an injection layer is present. In some embodiments, there is no injection layer.
  • the barrier layer is a layer capable of preventing charges (electrons or holes) and/or excitons existing in the light emitting layer from diffusing to the outside of the light emitting layer.
  • the electron barrier layer is between the emissive layer and the hole transport layer and blocks electrons from passing through the emissive layer to the hole transport layer.
  • the hole blocking layer is between the emissive layer and the electron transport layer and blocks holes from passing through the emissive layer to the electron transport layer.
  • the barrier layer prevents excitons from diffusing out of the light emitting layer.
  • the electron barrier layer and the hole barrier layer comprise exciton barrier layers.
  • the term “electron barrier layer” or “exciton barrier layer” includes layers that have both the function of an electron barrier layer and the function of an exciton barrier layer.
  • Hole blocking layer functions as an electron transport layer. In some embodiments, the hole blocking layer blocks holes from reaching the electron transport layer during electron transport. In some embodiments, the hole blocking layer enhances the probability of electron and hole recombination in the light emitting layer.
  • the material used for the hole blocking layer may be the same material as described above for the electron transport layer.
  • Electron barrier layer transports holes. In some embodiments, the electron barrier layer blocks electrons from reaching the hole transport layer during hole transport. In some embodiments, the electron barrier layer increases the probability of electron-hole recombination in the light-emitting layer.
  • Exciton barrier layer prevents excitons generated through recombination of holes and electrons in the light emitting layer from diffusing to the charge transport layer. In some embodiments, the exciton barrier layer enables effective confinement of excitons in the light emitting layer. In some embodiments, the light emitting efficiency of the device is improved. In some embodiments, the exciton barrier layer is adjacent to the emissive layer on either or both the anode and cathode sides. In some embodiments, when the exciton barrier layer is on the anode side, the layer may be between and adjacent to the hole transport layer and the light emitting layer.
  • the layer when the exciton barrier layer is on the cathode side, the layer is between the light emitting layer and the cathode and may be adjacent to the light emitting layer. In some embodiments, a hole injection layer, an electron barrier layer or similar layer is present between the anode and the exciton barrier layer adjacent to the light emitting layer on the anode side. In some embodiments, a hole injection layer, an electron barrier layer, a hole barrier layer or similar layer is present between the cathode and the exciton barrier layer adjacent to the cathode side light emitting layer. In some embodiments, the exciton barrier layer comprises excited singlet energy and excited triplet energy, at least one of which is higher than the excited singlet energy and excited triplet energy of the emissive material, respectively.
  • the hole transport layer contains a hole transport material.
  • the hole transport layer is a monolayer.
  • the hole transport layer has multiple layers.
  • the hole transport material has one of a hole injection or transport property and an electron barrier property.
  • the hole transport material is an organic material.
  • the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolones.
  • the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound.
  • Electron transport layer contains an electron transport material.
  • the electron transport layer is a monolayer.
  • the electron transport layer has multiple layers.
  • the electron transport material need only function to transport the electrons injected from the cathode to the light emitting layer.
  • the electron transport material also functions as a hole blocking material.
  • Examples of electron transport layers that can be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethanes, anthrone derivatives, oxadienes.
  • the electron transport material is a thiadiazole inducer or quinoxaline derivative. In some embodiments, the electron transport material is a polymeric material.
  • compounds of formula (I) are included in the emissive layer of devices of the invention. In some embodiments, the compound of formula (I) is included in the light emitting layer and at least one other layer. In some embodiments, compounds of formula (I) are selected for each layer. In some embodiments, the compounds of formula (I) are the same. In some embodiments, each compound of formula (I) is different.
  • the compound represented by the formula (I) can be used in the above-mentioned injection layer, barrier layer, hole barrier layer, electron barrier layer, exciton barrier layer, hole transport layer and electron transport layer.
  • the method for forming a film of the layer is not particularly limited, and the layer can be manufactured by either a dry process or a wet process.
  • the host material is selected from the group consisting of:
  • the compounds of the invention are incorporated into devices.
  • devices include, but are not limited to, OLED bulbs, OLED lamps, television displays, computer monitors, cell phones and tablets.
  • an electronic device includes an OLED having an anode, a cathode, and at least one organic layer that includes a light emitting layer between the anode and the cathode, the light emitting layer comprising a host material and a compound of formula (I ) Compound.
  • the emissive layer of an OLED further comprises a fluorescent material in which the compound of formula (I) converts triplets to singlets for fluorescent emitters.
  • the compositions described herein can be incorporated into various photosensitive or photoactivated devices, such as OLEDs or optoelectronic devices.
  • the composition may be useful in facilitating charge or energy transfer within a device and/or as a hole transport material.
  • the device include an organic light emitting diode (OLED), an organic integrated circuit (OIC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), and an organic solar cell. (O-SC), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQD), luminescent fuel cells (LEC) or organic laser diodes (O-lasers).
  • an electronic device includes an OLED that includes an anode, a cathode, and at least one organic layer that includes a light emitting layer between the anode and the cathode, the light emitting layer comprising a host material and a light emitting material. And a OLED driver circuit.
  • the device comprises different color OLEDs.
  • the device comprises an array that includes a combination of OLEDs.
  • the combination of OLEDs is a three color combination (eg, RGB).
  • the combination of OLEDs is a combination of colors that are neither red, green, nor blue (eg, orange and yellow-green).
  • the combination of OLEDs is a combination of two colors, four colors or more.
  • the device is A circuit board having a first surface having a mounting surface and an opposite second surface, the circuit board defining at least one opening; At least one OLED on the mounting surface, the at least one OLED including an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode, the light emitting layer comprising: At least one OLED having a light emitting configuration, comprising a host material and a compound of formula (I) which is a light emitting material; A housing for the circuit board, At least one connector disposed at an end of the housing, the housing and the connector defining at least one connector package suitable for mounting to a lighting fixture.
  • the OLED light comprises multiple OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, some of the light emitted in the first direction is polarized and emitted in the second direction. In some embodiments, a reflector is used to polarize the light emitted in the first direction.
  • compounds of formula (I) can be used in screens or displays.
  • the compound of formula (I) is deposited on the substrate using a process such as, but not limited to, vacuum evaporation, deposition, vapor deposition or chemical vapor deposition (CVD).
  • the substrate is a photoplate structure useful in a two-sided etch that provides pixels with unique aspect ratios.
  • the screen also called a mask
  • the corresponding artwork pattern design allows for the placement of very steep narrow tie bars between pixels in the vertical direction, as well as large, wide beveled openings in the horizontal direction.
  • the preferred material for the vapor deposition mask is Invar.
  • Invar is a metal alloy cold-rolled into a long thin sheet at an iron mill. Invar cannot be electrodeposited onto the spin mandrel as a nickel mask.
  • a suitable and low cost method for forming open areas in the deposition mask is by wet chemical etching.
  • the screen or display pattern is a pixel matrix on the substrate.
  • the screen or display pattern is processed using lithography (eg, photolithography and e-beam lithography).
  • the screen or display pattern is processed using wet chemical etching.
  • the screen or display pattern is processed using plasma etching.
  • OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels.
  • each cell panel on the mother panel has a thin film transistor (TFT) having an active layer and source/drain electrodes formed on a base material, a flattening film applied to the TFT, a pixel electrode and a light emitting layer.
  • TFT thin film transistor
  • the counter electrode and the encapsulation layer are sequentially formed over time, and then cut from the mother panel.
  • OLED displays are generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels.
  • each cell panel on the mother panel has a thin film transistor (TFT) having an active layer and source/drain electrodes formed on a base material, a flattening film applied to the TFT, a pixel electrode and a light emitting layer.
  • TFT thin film transistor
  • the counter electrode and the encapsulation layer are sequentially formed over time, and then cut from the mother panel.
  • OLED organic light emitting diode
  • the barrier layer is an inorganic film formed of, for example, SiNx, and the edges of the barrier layer are covered with an organic film formed of polyimide or acrylic.
  • the organic film helps the mother panel to be softly cut into cell panel units.
  • the thin film transistor (TFT) layer has a light emitting layer, a gate electrode, and source/drain electrodes.
  • Each of the plurality of display units may include a thin film transistor (TFT) layer, a flattening film formed on the TFT layer, and a light emitting unit formed on the flattening film.
  • the applied organic film is formed of the same material as the material of the flattening film, and is formed simultaneously with the formation of the flattening film.
  • the light emitting unit is connected to the TFT layer by a passivation layer, a planarizing film in between, and an encapsulation layer that covers and protects the light emitting unit.
  • the organic film is not connected to the display unit or the encapsulation layer.
  • Each of the organic film and the flattening film may include one of polyimide and acrylic.
  • the barrier layer may be an inorganic film.
  • the base substrate may be formed of polyimide. The method further comprises attaching a carrier substrate formed of a glass material to another surface of the base substrate before forming the barrier layer on the one surface of the base substrate formed of polyimide, Separating the carrier substrate from the base substrate prior to cutting along the interface portion.
  • the OLED display is a flexible display.
  • the passivation layer is an organic film disposed on the TFT layer for coating the TFT layer.
  • the planarization film is an organic film formed on the passivation layer.
  • the planarizing film is formed of polyimide or acrylic, similar to the organic film formed on the edges of the barrier layer.
  • the planarizing film and the organic film are formed simultaneously during the manufacture of the OLED display.
  • the organic film may be formed at the edges of the barrier layer, whereby a portion of the organic film is in direct contact with the base substrate and the remaining portion of the organic film is , Contacting the barrier layer while surrounding the edge of the barrier layer.
  • the light emitting layer comprises a pixel electrode, a counter electrode, and an organic light emitting layer disposed between the pixel electrode and the counter electrode.
  • the pixel electrode is connected to the source/drain electrodes of the TFT layer.
  • a suitable voltage is formed between the pixel electrode and the counter electrode, which causes the organic light emitting layer to emit light, which results in an image. Is formed.
  • the image forming unit including the TFT layer and the light emitting unit is referred to as a display unit.
  • the encapsulation layer that covers the display unit and prevents permeation of external moisture may be formed in a thin film encapsulation structure in which organic films and inorganic films are alternately stacked.
  • the encapsulation layer has a thin film encapsulation structure in which a plurality of thin films are stacked.
  • the organic film applied to the interface portion is spaced apart from each of the plurality of display units.
  • the organic film is formed in such a way that a portion of the organic film is in direct contact with the base substrate and the remaining portion of the organic film surrounds the edges of the barrier layer while being in contact with the barrier layer.
  • the OLED display is flexible and uses a flexible base substrate formed of polyimide.
  • the base substrate is formed on a carrier substrate formed of glass material and then the carrier substrate is separated.
  • the barrier layer is formed on the surface of the base substrate opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell panel. For example, the base substrate is formed on all surfaces of the mother panel, while the barrier layer is formed according to the size of each cell panel, thereby forming a groove in the interface portion between the barrier layers of the cell panel. Each cell panel can be cut along the groove.
  • the method of manufacturing further comprises cutting along the interface portion, wherein a groove is formed in the barrier layer, at least a portion of the organic film is formed in the groove, and the groove is formed. Does not penetrate the base substrate.
  • a TFT layer for each cell panel is formed, and a passivation layer, which is an inorganic film, and a planarization film, which is an organic film, are disposed on and cover the TFT layer.
  • the planarization film made of, for example, polyimide or acrylic is formed, the groove of the interface portion is covered with the organic film made of, for example, polyimide or acrylic. This prevents the organic film from being cracked by absorbing the generated impact when each cell panel is cut along the groove at the interface portion.
  • the groove of the interface portion between the barrier layers is covered with an organic film to absorb the shock that can be transmitted to the barrier layer without the organic film, so that each cell panel is softly cut and the barrier layer is cut. It may prevent cracking.
  • the organic film and the planarization film that cover the interface groove are spaced from each other. For example, when the organic film and the flattening film are connected to each other as one layer, external moisture may enter the display unit through the flattening film and the portion where the organic film remains.
  • the organic film and the planarization film are spaced from each other such that the organic film is spaced from the display unit.
  • the display unit is formed by forming a light emitting unit and the encapsulation layer is disposed on the display unit to cover the display unit.
  • the carrier base material carrying the base base material is separated from the base base material.
  • the carrier substrate is separated from the base substrate due to the difference in coefficient of thermal expansion between the carrier substrate and the base substrate.
  • the mother panel is cut into cell panels. In some embodiments, the mother panel is cut along the interface between the cell panels using a cutter.
  • the grooves of the interface along which the mother panel is cut are covered with an organic film so that the organic film absorbs shock during cutting.
  • the barrier layer can be prevented from cracking during cutting.
  • the method reduces the reject rate of a product and stabilizes its quality.
  • Another embodiment is a barrier layer formed on a base substrate, a display unit formed on the barrier layer, an encapsulation layer formed on the display unit, and an organic layer applied to the edge of the barrier layer. And a OLED display having a film.
  • acyl is known in the art and refers to a group of the general formula hydrocarbyl C(O)-, preferably alkyl C(O)-.
  • acylamino is known in the art and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula hydrocarbyl C(O)NH-.
  • alkoxy refers to an alkyl group to which is attached an oxygen atom. Representative alkoxy groups include methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, tert-butoxy group and the like.
  • alkoxyalkyl refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl.
  • alkenyl refers to an aliphatic group containing at least one double bond and includes “unsubstituted alkenyl” and “substituted alkenyl”, with the latter being one of the alkenyl groups.
  • alkenyl moiety having a substituent that replaces a hydrogen atom on one or more carbon atoms.
  • straight or branched chain alkenyl groups unless otherwise defined, have 1 to about 20, preferably 1 to about 10 carbon atoms. Such substituents may be present on one or more carbon atoms with or without one or more double bonds.
  • substituents include all that may be contained in an alkyl group, as will be described later, as long as the stability is not impaired.
  • substitution of an alkenyl group with one or more alkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups is meant to be included.
  • alkyl group or “alkane” is a fully saturated, linear or branched, non-aromatic hydrocarbon. Typically, straight or branched chain alkyl groups, unless otherwise defined, have from 1 to about 20, preferably 1 to about 10 carbon atoms. In some embodiments, the alkyl group has 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms.
  • linear or branched alkyl groups examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, pentyl. Groups and octyl groups.
  • alkyl as used throughout the specification, examples and claims shall include "unsubstituted alkyl” and "substituted alkyl", the latter of which in the hydrocarbon backbone. Refers to an alkyl moiety having a substituent that replaces hydrogen on one or more substitutable carbon atoms.
  • substituents include, for example, halogen (eg, fluoro group), hydroxyl group, carbonyl group (eg, carboxyl, alkoxycarbonyl, formyl or acyl group), thiocarbonyl group (eg, thioester, thioacetate or thioformate group).
  • alkoxy group alkoxy group, phosphoryl group, phosphate group, phosphonate group, phosphinate group, amino group, amide group, amidine group, imine group, cyano group, nitro group, azido group, sulfhydryl group, alkylthio group, sulfate group, sulfonate group, Mention may be made of sulfamoyl groups, sulfonamide groups, sulfonyl groups, heterocyclyl groups, aralkyl groups or aromatic or heteroaromatic moieties.
  • the substituents on the substituted alkyl group are selected from C 1-6 alkyl groups, C 3-6 cycloalkyl groups, halogens, carbonyl groups, cyano groups or hydroxy groups. In a more preferred embodiment, the substituents on the substituted alkyl group are selected from fluoro groups, carbonyl groups, cyano groups or hydroxyl groups. It will be appreciated by those skilled in the art that the substituted moieties on the hydrocarbon chain may themselves be optionally substituted.
  • the substituent of the substituted alkyl includes a substituted and unsubstituted amino group, azido group, imino group, amide group, phosphoryl group (including phosphonate group and phosphinate group), sulfonyl group (sulfate group, sulfonamide group). , Including a sulfamoyl group and a sulfonate group) and a silyl group, and an ether, an alkylthio group, a carbonyl group (including a ketone group, an aldehyde group, a carboxylate group and an ester), —CF 3 and —CN. . Typical substituted alkyl groups will be described later.
  • the cycloalkyl group may be further substituted with an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an aminoalkyl group, an alkyl group substituted with a carbonyl group, —CF 3 , or —CN.
  • C xy when used in connection with a chemical moiety (eg, an acyl group, an acyloxy group, an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group) has x to y carbon atoms in the chain. Is meant to include groups including.
  • Cx-y alkyl group refers to a substituted or unsubstituted saturated hydrocarbon group, which is a straight chain alkyl group or a branched chain alkyl group containing x to y carbon atoms in the chain. And also includes haloalkyl groups.
  • Preferred haloalkyl groups include trifluoromethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group and pentafluoroethyl group.
  • the C 0 alkyl group represents a hydrogen atom when the group is present at the terminal position, and a bond when the group is present inside.
  • the terms "C2 -y alkenyl group” and “C2 -y alkynyl group” are substituted or unsubstituted unsaturated aliphatic groups similar in length and substitutability to the above alkyl groups, provided that , Each refer to a group having at least one double or triple bond.
  • alkylamino used in the present invention refers to an amino group substituted with at least one alkyl group.
  • alkylthio used in the present invention refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-.
  • arylthio refers to a thiol group substituted with an alkyl group and may be represented by the general formula arylS—.
  • alkynyl refers to an aliphatic group containing at least one triple bond and is meant to include "unsubstituted alkynyl” and "substituted alkynyl", for the latter alkynyl Refers to an alkynyl moiety having a substituent that replaces hydrogen on one or more carbon atoms of the group. Typically, unless otherwise defined, straight or branched chain alkynyl groups have 1 to about 20, preferably 1 to about 10 carbon atoms. Such substituents may be present on one or more carbon atoms with or without one or more triple bonds.
  • substituents include all that may be contained in an alkyl group, as will be described later, as long as the stability is not impaired.
  • substitution of an alkynyl group with one or more alkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups is meant to be included.
  • amide refers to Wherein R A independently represents hydrogen or a hydrocarbyl group, or two R A together with the N atom to which they are attached have 4 to 8 atoms in the ring structure.
  • amine and “amino” are well known in the art and refer to unsubstituted and substituted amines and salts thereof, such as Wherein R A independently represents hydrogen or a hydrocarbyl group, or two R A together with the N atom to which they are attached have 4 to 8 atoms in the ring structure.
  • aminoalkyl used in the present invention refers to an alkyl group substituted with an amino group.
  • aralkyl as used in the present invention refers to an alkyl group substituted with an aryl group.
  • aryl as used in the present invention includes substituted or unsubstituted monocyclic aromatic groups in which each atom of the ring is a carbon atom.
  • the ring is a 6 or 20 membered ring, more preferably a 6 membered ring.
  • aryl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbon atoms are shared by two adjacent rings, at least one of which is aromatic.
  • the other ring may be, for example, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heteroaryl group and/or a heterocyclyl group.
  • aryl group examples include benzene, naphthalene, phenanthrene, phenol and aniline.
  • the term "carbamate” is known in the art, Wherein R A independently represents hydrogen or a hydrocarbyl group (eg, an alkyl group), or both R A together with a common atom have from 4 to 8 ring structures. Form a heterocycle having atoms of.
  • carbocycle and “carbocyclic” as used in the present invention refer to a saturated or unsaturated ring in which each atom of the ring is a carbon atom.
  • the carbocyclic group has 3 to 20 carbon atoms.
  • carbocycle includes both aromatic and non-aromatic carbocycles.
  • Non-aromatic carbocycles include cycloalkane rings saturated with all carbon atoms and cycloalkene rings containing at least one double bond.
  • Carbocycles include 5-7 membered monocyclic rings and 8-12 membered bicyclic rings. Each ring of the bicyclic carbocycle may be selected from saturated, unsaturated and aromatic rings.
  • Carbocycle includes bicyclic molecules in which one, two, or three or more atoms are shared by the two rings.
  • the term "fused carbocycle” refers to a bicyclic carbocycle in which each ring shares two adjacent atoms with another ring.
  • Each ring of the fused carbocycle may be selected from saturated, unsaturated and aromatic rings.
  • the aromatic ring eg, phenyl (Ph) group
  • a saturated or unsaturated ring eg, cyclohexane, cyclopentane or cyclohexene. Any combination of saturated, unsaturated and aromatic bicyclic rings is included in the definition of carbocyclic group, as valency permits.
  • Typical "carbocycles” are cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2. 0]oct-3-ene, naphthalene and adamantane.
  • fused carbocycles are decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4,5,6,7-tetrahydro-1H-indene and bicyclo[4 .1.0]hepta-3-ene.
  • the “carbocycle” may be substituted at any one or more positions that can carry a hydrogen atom.
  • a “cycloalkyl” group is a fully saturated cyclic hydrocarbon.
  • “Cycloalkyl” includes monocyclic and bicyclic rings. Preferably, the cycloalkyl group has 3 to 20 carbon atoms. Typically, monocyclic cycloalkyl groups have 3 to about 10 carbon atoms, and more typically, 3 to 8 carbon atoms unless otherwise defined.
  • the second ring of the bicyclic cycloalkyl group may be selected from saturated, unsaturated and aromatic rings. Cycloalkyl groups include bicyclic molecules in which one, two, three or more atoms are shared by two rings.
  • fused cycloalkyl refers to a bicyclic cycloalkyl in which each ring shares two adjacent atoms with another ring.
  • the second ring of the fused bicyclic cycloalkyl may be selected from saturated, unsaturated and aromatic rings.
  • a "cycloalkenyl” group is a cyclic hydrocarbon containing one or more double bonds.
  • Carbocyclylalkyl refers to an alkyl group substituted with a carbocyclic group.
  • carbonate as used in the present invention refers to --OCO 2 -R A group, wherein, -R A represents a hydrocarbyl group.
  • carboxy used in the present invention refers to a group represented by the formula —CO 2 H.
  • esteer as used in the present invention refers to a —C(O)OR A group, where R A represents a hydrocarbyl group.
  • ether as used in the present invention refers to a group in which a hydrocarbyl group is linked to another hydrocarbyl group via an oxygen atom.
  • the ether substituent of a hydrocarbyl group can be hydrocarbyl-O-.
  • the ether may be symmetrical or asymmetrical.
  • Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle.
  • Ethers include "alkoxyalkyl” groups and may be represented by the general formula alkyl-O-alkyl.
  • halo and “halogen” as used in the present invention mean a halogen atom and includes chlorine, fluorine, bromine and iodine.
  • heteroalkyl and “heteroaralkyl” as used herein refer to an alkyl group substituted with a hetaryl group.
  • heteroalkyl refers to a saturated or unsaturated chain of carbon atoms and at least one heteroatom, wherein the two heteroatoms are not adjacent.
  • heteroaryl and heterotaryl include substituted or unsubstituted, preferably 5-20 membered, more preferably 5-6 membered, aromatic monocyclic ring structures in which the ring structure includes: It includes at least one heteroatom, preferably 1 to 4 heteroatoms, more preferably 1 or 2 heteroatoms.
  • heteroaryl and “hetaryl” also include polycyclic ring systems having two or more cyclic rings in which two or more carbon atoms are shared by two adjacent rings, and at least one of the rings.
  • heterocycle One is a heterocycle and the other may be, for example, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heteroaryl group and/or a heterocyclyl group.
  • Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine.
  • heteroatom as used in the present invention means an atom of any element other than a carbon atom or a hydrogen atom. Preferred heteroatoms are nitrogen, oxygen and sulfur atoms.
  • heterocyclyl refers to a substituted or unsubstituted non-aromatic ring structure, preferably a 3-20 membered ring, more preferably a 3-7 membered ring, the ring structure of which Includes at least one heteroatom, preferably 1 to 4 heteroatoms, more preferably 1 or 2 heteroatoms.
  • heterocyclyl and “heterocycle” also include polycyclic ring systems having two or more cyclic rings in which two or more carbon atoms are shared by two adjacent rings, and at least one of the rings
  • One is heterocyclic and the other ring may be, for example, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heteroaryl group and/or a heterocyclyl group.
  • heterocyclyl group include piperidine, piperazine, pyrrolidine, morpholine, lactone, lactam and the like.
  • heterocyclylalkyl used in the present invention refers to an alkyl group substituted with a heterocyclic group.
  • hydrocarbyl refers to a group attached through a carbon atom, which carbon atom has no ⁇ O or ⁇ S substituent.
  • the hydrocarbyl group may optionally include heteroatoms.
  • Hydrocarbyl groups include, but are not limited to, alkyl groups, alkenyl groups, alkynyl groups, alkoxyalkyl groups, aminoalkyl groups, aralkyl groups, aryl groups, aralkyl groups, carbocyclyl groups, cycloalkyl groups, carbocyclylalkyl groups, heteroaralkyl groups.
  • a heteroaryl group bonded via a carbon atom a heterocyclyl group bonded via a carbon atom, a heterocyclylalkyl group or a hydroxyalkyl group. That is, groups such as a methyl group, an ethoxyethyl group, a 2-pyridyl group and a trifluoromethyl group are hydrocarbyl groups, but an acetyl group (having an ⁇ O substituent on a carbon atom to which it is attached) and an ethoxy group (having a carbon atom). But not via an oxygen atom).
  • hydroxyalkyl refers to an alkyl group substituted with a hydroxy group.
  • lower when used in connection with a chemical moiety such as an acyl group, an acyloxy group, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group is a group in which 6 or less non-hydrogen atoms are present in a substituent group. Means that.
  • the "lower alkyl group” refers to an alkyl group having 6 or less carbon atoms. In some embodiments, the alkyl group has 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms.
  • the acyl, acyloxy, alkyl, alkenyl, alkynyl or alkoxy substituents as defined in this invention are present alone or in combination with other substituents (eg hydroxyalkyl and aralkyl groups).
  • substituents eg hydroxyalkyl and aralkyl groups.
  • each is a lower acyl, a lower acyloxy, a lower alkyl, a lower alkenyl, a lower alkynyl or a lower alkoxy group.
  • polycyclyl is formed from two or more, such as, for example, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups and/or heterocyclyl groups, It refers to a ring in which two adjacent rings share two or more atoms, in which case the ring is, for example, a “fused ring”.
  • Each ring present in the polycycle may be substituted or unsubstituted.
  • each ring that makes up the polycycle contains 3-10, preferably 5-7, atoms in the ring.
  • poly(metaphenylene oxide) refers generically to a 6-membered aryl or 6-membered heteroaryl moiety. Typical poly(metaphenylene oxide)s are described as the first to twentieth aspects of the present disclosure.
  • sil refers to a silicon moiety with three hydrocarbyl moieties attached.
  • substituted refers to moieties having a substituent that replaces a hydrogen on one or more carbon atoms in the backbone.
  • substitution depends on the valence of the atom to be replaced and the substituent, and the substitution stabilizes the compound (For example, changes such as transfer, cyclization, and removal do not occur spontaneously).
  • the part which may be substituted includes all the suitable substituents described in the present specification, for example, an acyl group, an acylamino group, an acyloxy group, an alkoxy group, an alkoxyalkyl group, an alkenyl group, an alkyl group, an alkylamino group.
  • substituted shall include all substituents which may be present on an organic compound.
  • the possible substituents mentioned above include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic, organic Included are compound substituents.
  • the abovementioned possible substituents can be one or more, the same or different, for suitable organic compounds.
  • a heteroatom such as nitrogen, has a hydrogen substituent and/or any substituent described herein that may be present in an organic compound that meets the valence of the heteroatom. May be.
  • Substituents include any substituents described herein, such as halogen, hydroxyl, carbonyl (eg carboxyl, alkoxycarbonyl, formyl or acyl), thiocarbonyl (eg thioester, thioacetate or thioformate).
  • substituents described herein such as halogen, hydroxyl, carbonyl (eg carboxyl, alkoxycarbonyl, formyl or acyl), thiocarbonyl (eg thioester, thioacetate or thioformate).
  • alkoxy group alkoxy group, phosphoryl group, phosphate group, phosphonate group, phosphinate group, amino group, amide group, amidine group, imine group, cyano group, nitro group, azido group, sulfhydryl group, alkylthio group, sulfate group, Included are sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclyl, aralkyl or aromatic or heteroaromatic moieties.
  • the substituents on the substituted alkyl group are selected from C 1-6 alkyl groups, C 3-6 cycloalkyl groups, halogens, carbonyl groups, cyano groups, hydroxy groups. In a more preferred embodiment, the substituents on the substituted alkyl group are selected from fluoro groups, carbonyl groups, cyano groups or hydroxyl groups. Those skilled in the art will appreciate that the substituents may themselves be optionally substituted. Unless otherwise specified as "unsubstituted,” references herein to chemical moieties are understood to include substituted modifications. For example, a reference to an "aryl" group or moiety implicitly includes substituted and unsubstituted modifications.
  • sulfonate is known in the art, it refers to a SO 3 H group, or a pharmaceutically acceptable salt thereof.
  • sulfone is known in the art and refers to a —S(O) 2 —R A group, where R A represents a hydrocarbyl group.
  • thioether as used in the present invention is an ether equivalent in which oxygen is replaced by sulfur.
  • symmetric molecule refers to a molecule that is a symmetric group or a symmetric compound.
  • symmetrical group refers to a molecule that is bilaterally symmetric according to the theory of molecular symmetry for groups.
  • symmetrical compound refers to a molecule selected such that no regioselective synthetic strategy is required.
  • donor refers to a molecular fragment that can be used in an organic light emitting diode and has the property of, upon excitation, supplying an electron from its highest occupied molecular orbital to an acceptor.
  • the donor has an ionization potential of -6.5 eV or higher.
  • acceptor refers to a molecular fragment that can be used in organic light emitting diodes and has the property of accepting an electron from an excited donor into its lowest unoccupied orbital.
  • the receptor has an electron affinity of -0.5 eV or less.
  • bridge or linking group refers to a molecular fragment that can be included in a molecule that covalently bonds between an acceptor and a donor moiety. The bridge may be further conjugated, for example, with an acceptor moiety, a donor moiety, or both.
  • the bridging moiety can limit the acceptor and donor moieties to a specific conformational configuration, which results in a ⁇ -conjugated moiety of the donor and acceptor moieties. Thought to prevent.
  • suitable bridging moieties include phenyl, ethenyl and ethynyl moieties.
  • multivalent refers to the binding of a molecular fragment to at least two other molecular fragments.
  • the bridge part is multi-valued.
  • " refers to the bond site between two atoms.
  • HTL Hole transport layer
  • EML adjacent emitting layer
  • HTL compounds include, but are not limited to, di(p-tolyl)aminophenyl]cyclohexane (TAPC), N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4, 4-diamine (TPD), and N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine (NPB, ⁇ -NPD) Can be mentioned.
  • TAPC di(p-tolyl)aminophenyl]cyclohexane
  • TPD N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4, 4-diamine
  • NPB N,N'-diphenyl-N,N'-bis(1-naphthyl)-(1,1'-biphenyl)-4,4'-
  • the host material may be bipolar or unipolar and may be used alone or in combination of two or more host materials.
  • the visual-electrical properties of the host material may differ depending on which type of dopant (phosphorescent or fluorescent) is used.
  • the assisting host material should have a good spectral overlap between the absorption of the dopant and the emission of the host in order to induce a good Foerster transfer to the dopant.
  • the assisting host material should have a high triplet energy to confine the triplet of the dopant.
  • any atom not specified as a particular isotope is included as any stable isotope of that atom.
  • isotope enrichment ratio means a ratio between an isotope amount and a specific isotope amount in nature.
  • the compounds of the invention are at least 3500 (52.5% deuterium atoms), at least 4000 (60% deuterium), at least 4500 (67.5% deuterium), at least 5000 (75%). % Deuterium), at least 5500 (82.5% deuterium), at least 6000 (90% deuterium), at least 6333.3 (95% deuterium), at least 6466.7 (97% deuterium). ), at least 6600 (99% deuterium) or at least 6633.3 (99.5% deuterium) isotope enrichment (for each deuterium atom content).
  • isotopic substitute refers to a species that differs only in isotopic composition from a particular compound of the invention.
  • the term "compound” when referring to a compound of the invention refers to a collection of molecules having the same chemical structure, except that there may be isotopic variations between the constituent atoms of the molecule.
  • a compound represented by a particular chemical structure containing a given deuterium atom will have a hydrogen atom at one or more positions of the given deuterium within the structure. May have some isotopic substitutions.
  • the relative amounts of such isotopic substituents in the compounds of the invention such as the isotopic purity of the deuteration reagents used to prepare the compounds, and the efficiency of deuterium uptake in the various synthetic steps for preparing the compounds. Depends on many factors.
  • the relative amounts of such isotopic substitutes are less than 49.9% of the compound in total. In other embodiments, the relative amount of such isotopic substitutions is less than 47.5%, less than 40%, less than 32.5%, less than 25%, less than 17.5%, 10% of the total compounds. Less than 5%, less than 3%, less than 1%, or less than 0.5%.
  • D and d refer to deuterium. “Substituted with deuterium” means that one or more hydrogen atoms have been replaced by the corresponding number of deuterium atoms.
  • Example 1 Preparation and evaluation of organic electroluminescence device using compound T1 as first compound and compound F88 as second compound Indium tin oxide (100 nm thick) was formed using the vacuum vapor deposition apparatus shown in FIG. An organic layer was laminated by a vacuum deposition method on a glass substrate on which an anode made of (ITO) was formed. First, HAT-CN was formed to a thickness of 10 nm, tris-PCz was formed thereon to a thickness of 15 nm, and mCBP was formed thereon to a thickness of 5 nm.
  • mTRZ1DPBF was formed thereon with a thickness of 10 nm
  • mTRZ1DPBF and Liq (weight ratio 7:3) were formed thereon with a thickness of 40 nm.
  • Liq was formed thereon to a thickness of 2 nm, and then aluminum (Al) was evaporated to a thickness of 100 nm to form a cathode, to obtain an organic electroluminescence device.
  • Example 2 to 21 Preparation and evaluation of organic electroluminescent device using other compound as first compound and second compound First compound (material satisfying formula (1)) and second compound (material satisfying formula (1)) used for vapor deposition material A fluorescent material satisfying the formula (2) is changed to the compound powder shown in Table 2, and coevaporation is performed in the same manner as in Example 1 to form a film.
  • Example 22 Evaluation of Thermal Properties of Compound T9 (Compound 1) and Compound T10 (Compound 2) and Preparation of Membrane Using a thermogravimetric differential thermal analysis (TG-DTA) apparatus (TG-DTA2400SA manufactured by Bruker) 5 mg each of the compound T9 (4CzIPN-Me) and the compound T10 (4CzTPN) were weighed, and thermogravimetric analysis was performed under vacuum at 1 Pa at a heating rate of 10° C./min. Changes in temperature T and weight loss rate W of compound T9 at this time are shown in FIG. 3, and changes in temperature T and weight loss rate W of compound T10 are shown in FIG. From FIG. 3 and FIG.
  • TG-DTA thermogravimetric differential thermal analysis
  • the temperature at which the respective weights of compound T9 and compound T10 are reduced to ⁇ 50% (T WT ) and the temperature at which dW/dT of compound T9 and compound T10 are the same (T GR ) are both It was confirmed to be 351°C.
  • the powder of the compound T9 and the powder of the compound T10 were put in a menor mortar so that the weight ratio was 95:5, and kneaded for about 10 minutes. 100 mg of the mixture was placed in the crucible of the vacuum vapor deposition device shown in FIG. In this state, the temperature was raised to 351° C. to form a film on the substrate.
  • the formed film has a weight ratio of compound T9 and compound T10 of 95:5.
  • Example 23 Preparation and evaluation of organic electroluminescent device using compound T8 as first compound, compound T10 as second compound, and mCBP as host material.
  • compound T8 was 2.71 eV
  • T10 was 2.48 eV.
  • an organic layer was laminated by a vacuum vapor deposition method on a glass substrate on which an anode made of indium tin oxide (ITO) having a film thickness of 100 nm was formed.
  • ITO indium tin oxide
  • HAT-CN was formed to a thickness of 10 nm
  • tris-PCz was formed thereon to a thickness of 25 nm
  • mCBP was formed thereon to a thickness of 5 nm.
  • 183 mg of the powder of compound T8 and 18.8 mg of the powder of compound T10 were kneaded in a Menort mortar for about 10 minutes, and 100 mg of the mixture was placed in the crucible of the vacuum vapor deposition apparatus shown in FIG.
  • mCBP was put in another crucible (not shown) in the vacuum vapor deposition apparatus. In this state, co-evaporation was performed so that the weight ratio of mCBP and the mixture was 45:55 to form a light emitting layer having a thickness of 30 nm.
  • the vapor deposition rate of the mixture of the compound T8 and the compound T10 was 0.28 ⁇ /s.
  • SF3TRZ was formed thereon with a thickness of 10 nm
  • SF3TRZ and Liq (weight ratio 7:3) were formed thereon with a thickness of 40 nm.
  • Liq was formed thereon to a thickness of 2 nm
  • aluminum (Al) was evaporated to a thickness of 100 nm to form a cathode, to obtain an organic electroluminescence device.
  • the same organic electroluminescence device as above was further fabricated twice without additionally filling the crucible of the vacuum vapor deposition device with the material.
  • Example 24 Preparation and evaluation of organic electroluminescence device in which vapor deposition rate of mixture of first compound and second compound was changed. Other than changing vapor deposition rate of mixture to 2.80 ⁇ /s when forming a light emitting layer. An organic electroluminescence device was produced in the same manner as in Example 23.
  • Table 3 shows the external quantum efficiency and CIE chromaticity coordinates when the organic electroluminescent elements produced in Examples 23 and 24 were made to emit light at a luminance of 1000 cd/m 2 .
  • the four organic electroluminescent devices produced in Examples 23 and 24 all showed high external quantum efficiency despite the fact that the amount of the mixture filled in the crucible during vapor deposition and the vapor deposition rate were different. , Their external quantum efficiency and emission color were similar. From this, it was confirmed that the organic electroluminescence device can be stably manufactured with good characteristics by using the vapor deposition source containing both the first compound and the second compound.
  • Example 25 Preparation and evaluation of organic electroluminescence device using compound T8 as first compound, compound T10 as second compound, mCBP as host material, and compound F71 as luminescent dopant When forming a light emitting layer, compound F71 was further added.
  • mCBP a mixture of compound T8 and compound T10, and compound F71 were co-evaporated, and an organic electroluminescence device was produced in the same manner as in Example 23.
  • mCBP:mixture:compound F71 (weight ratio) was set to 44.5:55:0.5.
  • Example 26 Preparation and evaluation of organic electroluminescence device in which compounding ratio of light emitting layer forming material was changed When forming a light emitting layer, mCBP:mixture:compound F71 (weight ratio) was 84.5:15:0.5.
  • An organic electroluminescence device was produced in the same manner as in Example 25, except that the co-evaporation was carried out. After completion of the organic electroluminescence element production through the above steps, the same organic electroluminescence element as described above was produced once more without additionally filling the crucible of the vacuum vapor deposition device with the material.
  • Table 4 shows the external quantum efficiency and CIE chromaticity coordinates when the organic electroluminescent devices produced in Examples 25 and 26 were made to emit light at 1 mA/cm 2 .
  • Example 26 As shown in Table 4, the two organic electroluminescent devices produced in Example 26 exhibited similar external quantum efficiencies, although the mixture filling amount in the crucible during vapor deposition was different. Further, Example 25 in which the compounding ratio of the mixture was increased to 50% by weight or more showed higher external quantum efficiency than Example 26. From this, by using a mixture containing both Compound 1 and Compound 2 as a vapor deposition source, it becomes possible to stably manufacture an organic electroluminescent device, and by increasing the compounding ratio of the mixture, the external quantum efficiency can be increased. Was confirmed to be improved.
  • the film containing the first compound and the second compound has high luminous efficiency, and the film manufacturing method of the present invention can stably form such a film. Therefore, by using the method for producing a film of the present invention in the step of producing an organic semiconductor element, it is possible to obtain an organic semiconductor element having excellent characteristics such as luminous efficiency. Therefore, the present invention has high industrial applicability.

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Abstract

Dans la présente invention, un film est formé par réalisation d'un codépôt à partir d'une source de dépôt contenant à la fois un premier composé qui satisfait ΔEST(1)≤0.3eV et un second composé qui satisfait ES 1(1)>ES 1(2). ΔEST(1) est la différence entre l'état d'énergie singulet excité minimale ES 1(1) du premier composé et de l'état d'énergie de triplet excité minimale du premier composé. ES 1(2) est l'état d'énergie singulet excité minimale du second composé.
PCT/JP2019/046923 2018-11-30 2019-11-29 Procédé de fabrication de film, procédé de fabrication d'élément semi-conducteur organique et élément semi-conducteur organique WO2020111277A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022009790A1 (fr) * 2020-07-06 2022-01-13 株式会社Kyulux Elément luminescent organique
WO2022168825A1 (fr) * 2021-02-04 2022-08-11 株式会社Kyulux Élément électroluminescent organique, procédé de conception de composition lumineuse et programme
US11482681B2 (en) 2018-07-27 2022-10-25 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence element, organic electroluminescence element, and electronic device
WO2023017856A1 (fr) * 2021-08-13 2023-02-16 出光興産株式会社 Poudre mélangée, procédé de fabrication d'un élément électroluminescent organique qui utilise une poudre mélangée, et composition de dépôt en phase vapeur
WO2023063163A1 (fr) * 2021-10-14 2023-04-20 出光興産株式会社 Poudre mélangée pour élément électroluminescent organique, son procédé de production, procédé de fabrication d'élément électroluminescent organique au moyen de ladite poudre mélangée, procédé de sélection de composé dans ladite poudre mélangée, et composition pour dépôt sous vide
JP7456997B2 (ja) 2019-03-25 2024-03-27 日鉄ケミカル＆マテリアル株式会社 有機電界発光素子用溶融混合物、及び有機電界発光素子

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4223853A1 (fr) * 2022-02-04 2023-08-09 Samsung Display Co., Ltd. Dispositifs électroluminescents organiques

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014182898A (ja) * 2013-03-18 2014-09-29 Idemitsu Kosan Co Ltd 有機エレクトロルミネッセンス素子の製造方法、有機エレクトロルミネッセンス素子、および電子機器
JP2015179817A (ja) * 2013-08-14 2015-10-08 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP2016019002A (ja) * 2014-07-09 2016-02-01 ユニバーサル ディスプレイ コーポレイション 有機エレクトロルミネッセンス材料及びデバイス
WO2016042997A1 (fr) * 2014-09-17 2016-03-24 新日鉄住金化学株式会社 Element electroluminescent organique
JP2016076700A (ja) * 2014-10-06 2016-05-12 ユニバーサル ディスプレイ コーポレイション 有機エレクトロルミネッセンス材料及びデバイス
US20160149139A1 (en) * 2014-11-25 2016-05-26 Universal Display Corporation Organic electroluminescent materials and devices
WO2017146191A1 (fr) * 2016-02-24 2017-08-31 出光興産株式会社 Élément électroluminescent organique et dispositif électronique
JP2018501660A (ja) * 2014-12-31 2018-01-18 北京維信諾科技有限公司 有機エレクトロルミネッセンス素子
EP3291319A1 (fr) * 2016-08-30 2018-03-07 Novaled GmbH Procédé de préparation d'une couche semi-conductrice organique
WO2018133836A1 (fr) * 2017-01-20 2018-07-26 昆山工研院新型平板显示技术中心有限公司 Dispositif électroluminescent organique et son procédé de fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6513565B2 (ja) 2013-03-29 2019-05-22 株式会社Ｋｙｕｌｕｘ 有機エレクトロルミネッセンス素子
JP6482782B2 (ja) * 2014-07-18 2019-03-13 国立大学法人九州大学 有機発光素子
CN108666433A (zh) 2018-05-16 2018-10-16 云谷（固安）科技有限公司 有机电致发光装置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014182898A (ja) * 2013-03-18 2014-09-29 Idemitsu Kosan Co Ltd 有機エレクトロルミネッセンス素子の製造方法、有機エレクトロルミネッセンス素子、および電子機器
JP2015179817A (ja) * 2013-08-14 2015-10-08 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP2016019002A (ja) * 2014-07-09 2016-02-01 ユニバーサル ディスプレイ コーポレイション 有機エレクトロルミネッセンス材料及びデバイス
WO2016042997A1 (fr) * 2014-09-17 2016-03-24 新日鉄住金化学株式会社 Element electroluminescent organique
JP2016076700A (ja) * 2014-10-06 2016-05-12 ユニバーサル ディスプレイ コーポレイション 有機エレクトロルミネッセンス材料及びデバイス
US20160149139A1 (en) * 2014-11-25 2016-05-26 Universal Display Corporation Organic electroluminescent materials and devices
JP2018501660A (ja) * 2014-12-31 2018-01-18 北京維信諾科技有限公司 有機エレクトロルミネッセンス素子
WO2017146191A1 (fr) * 2016-02-24 2017-08-31 出光興産株式会社 Élément électroluminescent organique et dispositif électronique
EP3291319A1 (fr) * 2016-08-30 2018-03-07 Novaled GmbH Procédé de préparation d'une couche semi-conductrice organique
WO2018133836A1 (fr) * 2017-01-20 2018-07-26 昆山工研院新型平板显示技术中心有限公司 Dispositif électroluminescent organique et son procédé de fabrication

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11482681B2 (en) 2018-07-27 2022-10-25 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence element, organic electroluminescence element, and electronic device
JP7456997B2 (ja) 2019-03-25 2024-03-27 日鉄ケミカル＆マテリアル株式会社 有機電界発光素子用溶融混合物、及び有機電界発光素子
WO2022009790A1 (fr) * 2020-07-06 2022-01-13 株式会社Kyulux Elément luminescent organique
WO2022168825A1 (fr) * 2021-02-04 2022-08-11 株式会社Kyulux Élément électroluminescent organique, procédé de conception de composition lumineuse et programme
WO2023017856A1 (fr) * 2021-08-13 2023-02-16 出光興産株式会社 Poudre mélangée, procédé de fabrication d'un élément électroluminescent organique qui utilise une poudre mélangée, et composition de dépôt en phase vapeur
WO2023063163A1 (fr) * 2021-10-14 2023-04-20 出光興産株式会社 Poudre mélangée pour élément électroluminescent organique, son procédé de production, procédé de fabrication d'élément électroluminescent organique au moyen de ladite poudre mélangée, procédé de sélection de composé dans ladite poudre mélangée, et composition pour dépôt sous vide

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CN113170549A (zh) 2021-07-23

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