WO2015008580A1 - 化合物、発光材料および有機発光素子 - Google Patents
化合物、発光材料および有機発光素子 Download PDFInfo
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- WO2015008580A1 WO2015008580A1 PCT/JP2014/066501 JP2014066501W WO2015008580A1 WO 2015008580 A1 WO2015008580 A1 WO 2015008580A1 JP 2014066501 W JP2014066501 W JP 2014066501W WO 2015008580 A1 WO2015008580 A1 WO 2015008580A1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Definitions
- the present invention relates to a compound useful as a light emitting material and an organic light emitting device using the compound.
- organic light emitting devices such as organic electroluminescence devices (organic EL devices)
- organic electroluminescence devices organic electroluminescence devices
- various efforts have been made to increase the light emission efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials, and the like constituting the organic electroluminescence element.
- studies on organic electroluminescence devices using compounds containing a bicarbazole structure have been found, and several proposals have been made so far.
- Patent Document 1 describes that a compound having a bicarbazole structure as described below is used as a hole transport material.
- a compound having a bicarbazole structure as described below is used as a hole transport material.
- an organic electroluminescence element capable of being driven at a low voltage and having a long lifetime can be obtained.
- Patent Document 1 describes a compound containing a bicarbazole structure, but does not describe any structure in which two nitrogen atoms of a 3,3′-bicarbazole skeleton are substituted with cyanobenzene.
- said compound is used as a positive hole transport material, and it is not described at all about using such a compound as a luminescent material, or its usefulness.
- Patent Document 2 describes that a compound represented by the following general formula is used as a host material of a light emitting layer.
- a 1 and A 2 represent an aromatic hydrocarbon group or a heterocyclic group
- a 3 represents a monocyclic hydrocarbon group or a monocyclic heterocyclic group
- m represents an integer of 0 to 3
- 1 to X 8 and Y 1 to Y 8 represent N or CR a
- R a represents a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group, a silyl group, or a halogen atom.
- Some examples of compounds included in the general formula include those having a 3,3′-bicarbazole skeleton, but no data showing the usefulness of the compound represented by the general formula as a light-emitting material is described. It has not been.
- Patent Document 1 proposes to use a compound having a bicarbazole structure as a hole transport material of an organic electroluminescence element
- Patent Document 2 proposes to use it as a host material. The use of such a compound as a light emitting material has not been studied and there is no suggestion about its usefulness.
- the present inventors proceeded with studies on using a compound containing a bicarbazole structure as a light emitting material. Further, among the compounds containing a bicarbazole structure, studies have been conducted for the purpose of providing a compound having high emission efficiency.
- the present inventors succeeded in synthesizing a compound having a structure in which two nitrogen atoms of a 3,3′-bicarbazole skeleton are substituted with cyanobenzene. At the same time, it was revealed for the first time that these compounds are useful as light emitting materials. In addition, it was found that such a compound is useful as a delayed fluorescent material, and it has been clarified that an organic light-emitting device having high emission efficiency can be provided at low cost. Based on these findings, the present inventors have provided the following present invention as means for solving the above problems.
- General formula (1) ADA [In the general formula (1), D represents the following formula: Wherein the hydrogen atom in the structure may be substituted with a substituent, and two A are represented by the following formula: (Wherein the hydrogen atom in the structure may be substituted with a substituent other than a cyano group, and n represents an integer of 1 to 5). ] [2] The compound according to [1], wherein two A's in the general formula (1) have the same structure. [3] The compound according to [1] or [2], which is represented by the following general formula (2). [In the general formula (2), R 1 to R 5 each independently represents a hydrogen atom or a substituent, and at least one represents a cyano group.
- R 6 to R 10 each independently represents a hydrogen atom or a substituent, and at least one of them represents a cyano group.
- R 11 to R 17 and R 21 to R 27 each independently represents a hydrogen atom or a substituent.
- R 2 , R 4 , R 7 and R 9 represent a cyano group [the compound according to any one of 3 to 5].
- a group other than R 1 to R 5 and R 6 to R 10 other than a cyano group represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
- R 11 to R 17 and R 21 to R 27 represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, according to any one of [3] to [6] Compound.
- R 1 to R 5 and R 6 to R 10 other than those representing a cyano group represent a hydrogen atom
- R 11 to R 17 and R 21 to R 27 represent hydrogen.
- a light-emitting material comprising the compound according to any one of [1] to [8].
- D represents the following formula: Wherein the hydrogen atom in the structure may be substituted with a substituent, and two A are represented by the following formula: (Wherein the hydrogen atom in the structure may be substituted with a substituent other than a cyano group, and n represents an integer of 1 to 5).
- An organic light-emitting device having a light-emitting layer containing the light-emitting material according to [9] on a substrate.
- the organic light-emitting device according to [11] which emits delayed fluorescence.
- the compound containing the bicarbazole structure of the present invention is useful as a light emitting material.
- the compounds of the present invention include those that emit delayed fluorescence.
- An organic light emitting device using the compound of the present invention as a light emitting material can realize high luminous efficiency.
- FIG. 2 is an emission spectrum of the thin film type organic photoluminescence device of Example 1.
- 2 is a transient attenuation curve of the thin film type organic photoluminescence device of Example 1.
- FIG. 2 is an emission spectrum of the organic electroluminescence device of Example 2.
- FIG. 4 is a current density-external quantum efficiency characteristic of the organic electroluminescence element of Example 2.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be 1 H, or a part or all of them are 2 H. (Deuterium D) may be used.
- D represents the bivalent group containing the structure represented by a following formula.
- the hydrogen atom present in the above structure may be substituted with a substituent.
- the number of substituents is not particularly limited, and the substituents may not be present. When two or more substituents are present, these substituents may be the same as or different from each other.
- substituents examples 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 20 trialkylsilylalkyl groups, 5 to 20 trialkylsilylalkenyl groups, and 5 to 20 trialkylsilylalkynyl groups.
- those that can be substituted with a substituent may be further substituted.
- 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. Or it is an unsubstituted heteroaryl group.
- Further preferred substituents are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, 3 to 12 substituted or unsubstituted heteroaryl groups.
- the alkyl group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and tert-butyl. Group, pentyl group, hexyl group and isopropyl group.
- the alkoxy group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group. A group, a pentyloxy group, a hexyloxy group, and an isopropyloxy group.
- the aryl group that can be employed as the substituent may be a single ring or a condensed ring, and specific examples thereof include a phenyl group and a naphthyl group.
- the heteroaryl group may be a single ring or a condensed ring, and specific examples thereof include a pyridyl group, a pyridazyl group, a pyrimidyl group, a triazyl group, a triazolyl group, and a benzotriazolyl group.
- These heteroaryl groups may be a group bonded through a hetero atom or a group bonded through a carbon atom constituting a heteroaryl ring.
- A represents a group having a structure represented by the following formula.
- the hydrogen atom present in the above structure may be substituted with a substituent other than a cyano group.
- the number of substituents is not particularly limited, and the substituents may not be present. When two or more substituents are present, these substituents may be the same as or different from each other.
- Examples of the substituent that can replace a hydrogen atom present in the structure 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, and an alkylthio group having 1 to 20 carbon atoms.
- substituents that can be substituted with a substituent may be further substituted. More preferred substituents are a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and 3 to 3 carbon atoms.
- substituted or unsubstituted heteroaryl groups 1 to 10 carbon atoms substituted or unsubstituted dialkylamino groups, 12 to 40 carbon atoms substituted or unsubstituted diarylamino groups, 12 to 40 carbon atoms substituted or unsubstituted A substituted carbazolyl group; More preferred substituents are a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted or unsubstituted group having 1 to 10 carbon atoms.
- the two A in the general formula (1) may be the same or different from each other, but are preferably the same.
- the whole molecule is preferably line symmetric or point symmetric.
- Ordinary luminescent materials have an AD structure in which A acting as an acceptor and D acting as a donor are combined.
- the compound represented by the general formula (1) has a structure of ADA, and two A acting as an acceptor are bonded to D acting as a donor.
- a and D when two or more A's are bonded, there is a general concern that the function as an acceptor cancels and there is a risk that the molecule does not function effectively as a luminescent material.
- a and D in accordance with the present invention, a light emitting material having high luminous efficiency and excellent effects can be provided. This is presumably because the HOMO and LUMO spreads were controlled at the molecular level to satisfy the preferable conditions for the light-emitting material.
- the compound represented by the general formula (1) is preferably a compound having a structure represented by the following general formula (2).
- R 1 to R 5 each independently represents a hydrogen atom or a substituent, and at least one represents a cyano group.
- R 6 to R 10 each independently represents a hydrogen atom or a substituent, and at least one of them represents a cyano group.
- R 11 to R 17 and R 21 to R 27 each independently represents a hydrogen atom or a substituent.
- R 1 to R 5 and R 6 to R 10 for example, when R 5 and R 6 are cyano groups, R 4 and R 7 are cyano groups. When it is a group, a case where R 3 and R 8 are cyano groups can be mentioned.
- R 1 to R 5 represent a cyano group
- at least two of R 6 to R 10 represent a cyano group.
- two or three of R 1 to R 5 represent a cyano group
- two or three of R 6 to R 10 represent a cyano group.
- R 1 to R 5 and R 6 to R 10 as a combination of positions where two positions are each substituted with a cyano group, for example, when R 4 , R 5 , R 6 and R 7 are cyano groups, R 3 , R 4 , R 7 and R 8 are cyano groups, R 1 , R 3 , R 6 and R 8 are cyano groups, R 1 , R 5 , R 6 and R 10 are cyano groups In some cases, R 2 , R 4 , R 7 and R 9 are cyano groups, and R 2 , R 5 , R 7 and R 10 are cyano groups.
- R 1 to R 5 and R 6 to R 10 combinations of positions where each of three positions is substituted with a cyano group include, for example, R 1 , R 3 , R 5 , R 6 , R 8 and R 10.
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are cyano groups
- R 2 , R 3 , R 4 , R 7 , R 8 and R 9 are cyano groups. The case where it is a group can be mentioned.
- R 1 , R 5 , R 6 and R 10 represent a cyano group
- R 2 , R 4 , R 7 and R 9 represent a cyano group.
- Luminous efficiency can be further improved by positioning the cyano group in the ortho position with respect to the bonding position between the two nitrogen atoms of the 3,3′-bicarbazole skeleton and cyanobenzene.
- R 1 to R 5 and R 6 to R 10 preferably represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms other than those representing a cyano group.
- R 11 to R 17 and R 21 to R 27 preferably represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
- R 1 to R 5 and R 6 to R 10 other than those representing a cyano group preferably represent a hydrogen atom
- R 11 to R 17 and R 21 to R 27 represent a hydrogen atom. Is more preferable.
- the molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, more preferably 1000 or less, and even more preferably 800 or less.
- the lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).
- the compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.
- a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light emitting material.
- a polymer obtained by previously polymerizing a polymerizable group in the structure represented by the general formula (1) and polymerizing the polymerizable group as a light emitting material.
- a repeating unit is prepared by preparing a monomer containing a polymerizable functional group in either A or D of the general formula (1) and polymerizing the monomer alone or copolymerizing with another monomer. It is conceivable to obtain a polymer having the above and use the polymer as a light emitting material.
- dimers and trimers are obtained by reacting compounds having a structure represented by the general formula (1) and used as a luminescent material.
- Examples of the polymer having a repeating unit containing a structure represented by the general formula (1) include a polymer containing a structure represented by the following general formula (4) or (5).
- Q represents a group including the structure represented by the general formula (1)
- L 1 and L 2 represent a linking group.
- the linking group preferably has 0 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 2 to 10 carbon atoms. And preferably has a structure represented by - linking group -X 11 -L 11.
- X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
- L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
- R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
- it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms.
- An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
- the linking group represented by L 1 and L 2 is A or D of the structure of the general formula (1) constituting Q, R 1 to R 5 and R 6 to R 10 of the structure of the general formula (2) It can be bonded to any of those other than those representing a cyano group, or any of R 11 to R 17 and R 21 to R 27 .
- Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
- repeating unit examples include structures represented by the following formulas (6) to (9).
- a hydroxy group is introduced into either A or D of the structure of the general formula (1), and the following compound is used as a linker: It can be synthesized by reacting to introduce a polymerizable group and polymerizing the polymerizable group.
- the polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or other structures may be used. It may be a polymer containing repeating units.
- the repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene. It is not limited to the repeating units exemplified.
- the compound represented by the general formula (1) can be synthesized by combining known reactions. For example, it can be synthesized according to the following scheme. For the explanation of D and A in the above formula, the corresponding description in the general formula (1) can be referred to.
- X in the above formula represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom and an iodine atom are preferable.
- the compound represented by the general formula (2) can be synthesized by the following scheme. However, the scheme described below shows a synthesis method when R 1 and R 6 , R 2 and R 7 , R 3 and R 8 , R 4 and R 9 , and R 5 and R 10 are the same. is there.
- R 1 to R 5 , R 6 to R 10 , R 11 to R 17 and R 21 to R 27 in the above formula the corresponding description in the general formula (2) can be referred to.
- X in the above formula represents a halogen atom.
- the reactions in the above two schemes apply known reactions, and known reaction conditions can be appropriately selected and used. The details of the above reaction can be referred to the synthesis examples described below.
- the compound represented by the general formula (1) can also be synthesized by combining other known synthesis reactions.
- the compound represented by the general formula (1) of the present invention is useful as a light emitting material of an organic light emitting device. For this reason, the compound represented by General formula (1) of this invention can be effectively used as a luminescent material for the light emitting layer of an organic light emitting element.
- the compound represented by the general formula (1) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence. That is, the present invention relates to a delayed phosphor having a structure represented by the general formula (1), an invention using a compound represented by the general formula (1) as a delayed phosphor, and a general formula (1).
- An invention of a method for emitting delayed fluorescence using the represented compound is also provided.
- An organic light emitting device using such a compound as a light emitting material emits delayed fluorescence and has a feature of high luminous efficiency. The principle will be described below by taking an organic electroluminescence element as an example.
- the organic electroluminescence element carriers are injected into the light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light.
- 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used.
- the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high.
- delayed fluorescent materials after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit fluorescence.
- a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful.
- excitons in the excited singlet state emit fluorescence as usual.
- excitons in the excited triplet state absorb heat generated by the device and cross between the excited singlets to emit fluorescence.
- the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised.
- the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.
- the compound represented by the general formula (1) of the present invention as a light-emitting material of a light-emitting layer, excellent organic light-emitting devices such as an organic photoluminescence device (organic PL device) and an organic electroluminescence device (organic EL device) Can be provided.
- the compound represented by the general formula (1) of the present invention may have a function of assisting light emission of another light emitting material included in the light emitting layer as a so-called assist dopant. That is, the compound represented by the general formula (1) of the present invention contained in the light emitting layer includes the lowest excitation singlet energy level of the host material contained in the light emitting layer and the lowest excitation of other light emitting materials contained in the light emitting layer.
- the organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate.
- the organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode.
- the organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer.
- 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.
- FIG. 1 A specific example of the structure of an organic electroluminescence element is shown in FIG.
- 1 is a substrate
- 2 is an anode
- 3 is a hole injection layer
- 4 is a hole transport layer
- 5 is a light emitting layer
- 6 is an electron transport layer
- 7 is a cathode.
- each member and each layer of an organic electroluminescent element are demonstrated.
- substrate and a light emitting layer corresponds also to the board
- the organic electroluminescence device of the present invention is preferably supported on a substrate.
- the substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements.
- a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.
- an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
- electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
- conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
- an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
- a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
- wet film-forming methods such as a printing system and a coating system, can also be used.
- the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
- cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
- electrode materials include 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, rare earth metals and the like.
- a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture
- Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
- the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
- the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
- the emission luminance is advantageously improved.
- a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.
- the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material. As a luminescent material, the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used. In order for the organic electroluminescence device and the organic photoluminescence device of the present invention to exhibit high luminous efficiency, it is important to confine singlet excitons and triplet excitons generated in the light emitting material in the light emitting material.
- a host material in addition to the light emitting material in the light emitting layer.
- the host material an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used.
- singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted.
- high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention.
- the organic light emitting device or organic electroluminescent device of the present invention light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
- the amount of the compound of the present invention, which is a light emitting material is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
- the host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
- the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission, and includes a hole injection layer and an electron injection layer, Further, it may be present between the cathode and the light emitting layer or the electron transport layer.
- the injection layer can be provided as necessary.
- the blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer.
- the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
- a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
- the blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer.
- the term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
- the hole blocking layer has a function of an electron transport layer in a broad sense.
- the hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
- the material for the hole blocking layer the material for the electron transport layer described later can be used as necessary.
- the electron blocking layer has a function of transporting holes in a broad sense.
- the electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .
- the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
- the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
- the layer when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer.
- a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided.
- an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided.
- the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.
- the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
- the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
- hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
- An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.
- the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
- the electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
- Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
- a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- the compound represented by the general formula (1) may be used not only for the light emitting layer but also for layers other than the light emitting layer.
- the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different.
- the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. .
- the method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.
- the preferable material which can be used for an organic electroluminescent element is illustrated concretely.
- the material that can be used in the present invention is not limited to the following exemplary compounds. Moreover, even if it is a compound illustrated as a material which has a specific function, it can also be diverted as a material which has another function.
- R and R 2 to R 7 each independently represent a hydrogen atom or a substituent.
- n represents an integer of 3 to 5.
- the organic electroluminescent device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
- the excited triplet energy is unstable and is converted into heat and the like, and the lifetime is short and it is immediately deactivated.
- the excited triplet energy of a normal organic compound it can be measured by observing light emission under extremely low temperature conditions.
- the organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer.
- the organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention.
- organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
- source meter manufactured by Keithley: 2400 series
- semiconductor parameter analyzer manufactured by Agilent Technologies: E5273A
- optical power meter measuring device manufactured by Newport: 1930C
- optical spectrometer Ocean Optics, USB2000
- spectroradiometer Topcon, SR-3
- streak camera Haamamatsu Photonics C4334
- 3,3′-Bi-9H-carbazole (3.00 g, 9.03 mmol) and potassium carbonate (4.98 g, 36.0 mmol) were placed in a 200 mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen.
- 78.0 mL of N, N-dimethylformamide was added, and the mixture was stirred at room temperature for 2 hours under a nitrogen stream.
- To this mixture was added 2.93 g (18.0 mmol) of 5-fluoroisophthalonitrile, followed by stirring at 70 ° C. for 20 hours under a nitrogen atmosphere. After stirring, the solvent in this mixture was removed by distillation under reduced pressure.
- Example 1 Production and evaluation of thin film type organic photoluminescence device
- Compound 1 and DPEPO were vapor-deposited from different vapor deposition sources on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of 10 -4 Pa or less.
- a thin film having a concentration of 1 of 10% by weight was formed to a thickness of 100 nm to obtain a thin film type organic photoluminescence device.
- a thin-film organic photoluminescence device using Compound 2 instead of Compound 1 was also produced.
- the emission spectrum of each of these thin film type organic photoluminescence elements is shown in FIG.
- damping curve of the thin film type organic photoluminescent element using the compound 1 and the thin film type organic photoluminescent element using the compound 2 is shown in FIG.
- This transient decay curve shows the result of measuring the luminescence lifetime obtained by measuring the process in which the emission intensity is deactivated by applying excitation light to the compound.
- the light emission intensity decays in a single exponential manner. This means that if the vertical axis of the graph is semi-log, it will decay linearly.
- Example 2 Production and Evaluation of Organic Electroluminescence Element
- ITO indium tin oxide
- Lamination was performed at 0 ⁇ 10 ⁇ 4 Pa.
- ⁇ -NPD was formed to a thickness of 30 nm on ITO
- mCP was formed to a thickness of 10 nm.
- Compound 1 and DPEPO were co-evaporated from different vapor deposition sources to form a 20 nm thick layer as a light emitting layer. At this time, the concentration of Compound 1 was 10% by weight.
- DPEPO is formed to a thickness of 10 nm
- TPBi is formed to a thickness of 30 nm
- lithium fluoride (LiF) is vacuum-deposited to 0.5 nm
- aluminum (Al) is then deposited to a thickness of 100 nm.
- a cathode was formed, and an organic electroluminescence element was obtained.
- An organic electroluminescence device using Compound 2 instead of Compound 1 was also produced.
- the emission spectrum of each of these organic electroluminescence elements is shown in FIG.
- FIG. 5 shows the current density-external quantum efficiency characteristics of the organic electroluminescent device using Compound 1 and the organic electroluminescent device using Compound 2.
- the compound of the present invention is useful as a luminescent material. For this reason, the compound of this invention is effectively used as a luminescent material for organic light emitting elements, such as an organic electroluminescent element. Since the compounds of the present invention include those that emit delayed fluorescence, it is also possible to provide an organic light emitting device with high luminous efficiency. For this reason, this invention has high industrial applicability.
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Abstract
Description
一般式(1)
A-D-A
[一般式(1)において、Dは下記式:
[2]一般式(1)の2つのAが同一の構造を有することを特徴とする[1]に記載の化合物。
[3]下記一般式(2)で表されることを特徴とする[1]または[2]に記載の化合物。
[4]一般式(2)において、R1~R5のうち、少なくとも2つはシアノ基を表し、R6~R10のうち、少なくとも2つはシアノ基を表すことを特徴とする[3]に記載の化合物。
[5]一般式(2)において、R1、R5、R6およびR10はシアノ基を表すことを特徴とする[3]または[4]に記載の化合物。
[6]一般式(2)において、R2、R4、R7およびR9はシアノ基を表すことを特徴とする[3~5のいずれか1項に記載の化合物。
[7]一般式(2)において、R1~R5およびR6~R10のうち、シアノ基を表すもの以外は、水素原子または炭素数1~10の置換もしくは無置換のアルキル基を表し、R11~R17およびR21~R27は水素原子または炭素数1~10の置換もしくは無置換のアルキル基を表すことを特徴とする[3]~[6]のいずれか1項に記載の化合物。
[8]一般式(2)において、R1~R5およびR6~R10のうち、シアノ基を表すもの以外は、水素原子を表し、R11~R17およびR21~R27は水素原子を表すことを特徴とする[3]~[7]のいずれか1項に記載の化合物。
[9][1]~[8]のいずれか1項に記載の化合物からなる発光材料。
[10]下記一般式(1)で表される構造を有する遅延蛍光体。
一般式(1)
A-D-A
[一般式(1)において、Dは下記式:
[11][9]に記載の発光材料を含む発光層を基板上に有することを特徴とする有機発光素子。
[12]遅延蛍光を放射することを特徴とする[11]に記載の有機発光素子。
[13]有機エレクトロルミネッセンス素子であることを特徴とする[11]または[12]に記載の有機発光素子。
本発明の化合物は、下記一般式(1)で表される構造を有することを特徴とする。
一般式(1)
A-D-A
R1~R5およびR6~R10において、各々1箇所がシアノ基で置換される位置の組み合わせとしては、例えば、R5とR6がシアノ基である場合、R4とR7がシアノ基である場合、R3とR8がシアノ基である場合を挙げることができる。
R1~R5およびR6~R10において、各々2箇所がシアノ基で置換される位置の組み合わせとしては、例えば、R4、R5、R6およびR7がシアノ基である場合、R3、R4、R7およびR8がシアノ基である場合、R1、R3、R6およびR8がシアノ基である場合、R1、R5、R6およびR10がシアノ基である場合、R2、R4、R7およびR9がシアノ基である場合、R2、R5、R7およびR10がシアノ基である場合を挙げることができる。
また、R1~R5およびR6~R10において、各々3箇所がシアノ基で置換される位置の組み合わせとしては、例えば、R1、R3、R5、R6、R8およびR10がシアノ基である場合、R3、R4、R5、R6、R7およびR8がシアノ基である場合、R2、R3、R4、R7、R8およびR9がシアノ基である場合を挙げることができる。
一般式(1)で表される化合物は、分子量にかかわらず塗布法で成膜してもよい。塗布法を用いれば、分子量が比較的大きな化合物であっても成膜することが可能である。
例えば、一般式(1)で表される構造中にあらかじめ重合性基を存在させておいて、その重合性基を重合させることによって得られる重合体を、発光材料として用いることが考えられる。具体的には、一般式(1)のAかDのいずれかに重合性官能基を含むモノマーを用意して、これを単独で重合させるか、他のモノマーとともに共重合させることにより、繰り返し単位を有する重合体を得て、その重合体を発光材料として用いることが考えられる。あるいは、一般式(1)で表される構造を有する化合物どうしを反応させることにより、二量体や三量体を得て、それらを発光材料として用いることも考えられる。
一般式(4)および(5)において、R101、R102、R103およびR104は、各々独立に置換基を表す。好ましくは、炭素数1~6の置換もしくは無置換のアルキル基、炭素数1~6の置換もしくは無置換のアルコキシ基、ハロゲン原子であり、より好ましくは炭素数1~3の無置換のアルキル基、炭素数1~3の無置換のアルコキシ基、フッ素原子、塩素原子であり、さらに好ましくは炭素数1~3の無置換のアルキル基、炭素数1~3の無置換のアルコキシ基である。
L1およびL2で表される連結基は、Qを構成する一般式(1)の構造のAかD、一般式(2)の構造のR1~R5およびR6~R10のうちシアノ基を表すもの以外、またはR11~R17およびR21~R27のいずれかに結合することができる。1つのQに対して連結基が2つ以上連結して架橋構造や網目構造を形成していてもよい。
一般式(1)で表される化合物は、既知の反応を組み合わせることによって合成することができる。例えば、以下のスキームにしたがって合成することが可能である。
一般式(1)で表される化合物のうち、例えば一般式(2)で表される化合物は以下のスキームにより合成することが可能である。ただし、以下に記載するスキームは、R1とR6、R2とR7、R3とR8、R4とR9、R5とR10が同一である場合の合成法を示すものである。
上記の2つのスキームにおける反応は、公知の反応を応用したものであり、公知の反応条件を適宜選択して用いることができる。上記の反応の詳細については、後述の合成例を参考にすることができる。また、一般式(1)で表される化合物は、その他の公知の合成反応を組み合わせることによっても合成することができる。
本発明の一般式(1)で表される化合物は、有機発光素子の発光材料として有用である。このため、本発明の一般式(1)で表される化合物は、有機発光素子の発光層に発光材料として効果的に用いることができる。一般式(1)で表される化合物の中には、遅延蛍光を放射する遅延蛍光材料(遅延蛍光体)が含まれている。すなわち本発明は、一般式(1)で表される構造を有する遅延蛍光体の発明と、一般式(1)で表される化合物を遅延蛍光体として使用する発明と、一般式(1)で表される化合物を用いて遅延蛍光を発光させる方法の発明も提供する。そのような化合物を発光材料として用いた有機発光素子は、遅延蛍光を放射し、発光効率が高いという特徴を有する。その原理を、有機エレクトロルミネッセンス素子を例にとって説明すると以下のようになる。
有機フォトルミネッセンス素子は、基板上に少なくとも発光層を形成した構造を有する。また、有機エレクトロルミネッセンス素子は、少なくとも陽極、陰極、および陽極と陰極の間に有機層を形成した構造を有する。有機層は、少なくとも発光層を含むものであり、発光層のみからなるものであってもよいし、発光層の他に1層以上の有機層を有するものであってもよい。そのような他の有機層として、正孔輸送層、正孔注入層、電子阻止層、正孔阻止層、電子注入層、電子輸送層、励起子阻止層などを挙げることができる。正孔輸送層は正孔注入機能を有した正孔注入輸送層でもよく、電子輸送層は電子注入機能を有した電子注入輸送層でもよい。具体的な有機エレクトロルミネッセンス素子の構造例を図1に示す。図1において、1は基板、2は陽極、3は正孔注入層、4は正孔輸送層、5は発光層、6は電子輸送層、7は陰極を表す。
以下において、有機エレクトロルミネッセンス素子の各部材および各層について説明する。なお、基板と発光層の説明は有機フォトルミネッセンス素子の基板と発光層にも該当する。
本発明の有機エレクトロルミネッセンス素子は、基板に支持されていることが好ましい。この基板については、特に制限はなく、従来から有機エレクトロルミネッセンス素子に慣用されているものであればよく、例えば、ガラス、透明プラスチック、石英、シリコンなどからなるものを用いることができる。
有機エレクトロルミネッセンス素子における陽極としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物およびこれらの混合物を電極材料とするものが好ましく用いられる。このような電極材料の具体例としてはAu等の金属、CuI、インジウムチンオキシド(ITO)、SnO2、ZnO等の導電性透明材料が挙げられる。また、IDIXO(In2O3-ZnO)等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極材料を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は(100μm以上程度)、上記電極材料の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。あるいは、有機導電性化合物のように塗布可能な材料を用いる場合には、印刷方式、コーティング方式等湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を10%より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω/□以下が好ましい。さらに膜厚は材料にもよるが、通常10~1000nm、好ましくは10~200nmの範囲で選ばれる。
一方、陰極としては、仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物およびこれらの混合物を電極材料とするものが用いられる。このような電極材料の具体例としては、ナトリウム、ナトリウム-カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性および酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極材料を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω/□以下が好ましく、膜厚は通常10nm~5μm、好ましくは50~200nmの範囲で選ばれる。なお、発光した光を透過させるため、有機エレクトロルミネッセンス素子の陽極または陰極のいずれか一方が、透明または半透明であれば発光輝度が向上し好都合である。
また、陽極の説明で挙げた導電性透明材料を陰極に用いることで、透明または半透明の陰極を作製することができ、これを応用することで陽極と陰極の両方が透過性を有する素子を作製することができる。
発光層は、陽極および陰極のそれぞれから注入された正孔および電子が再結合することにより励起子が生成した後、発光する層であり、発光材料を単独で発光層に使用しても良いが、好ましくは発光材料とホスト材料を含む。発光材料としては、一般式(1)で表される本発明の化合物群から選ばれる1種または2種以上を用いることができる。本発明の有機エレクトロルミネッセンス素子および有機フォトルミネッセンス素子が高い発光効率を発現するためには、発光材料に生成した一重項励起子および三重項励起子を、発光材料中に閉じ込めることが重要である。従って、発光層中に発光材料に加えてホスト材料を用いることが好ましい。ホスト材料としては、励起一重項エネルギー、励起三重項エネルギーの少なくとも何れか一方が本発明の発光材料よりも高い値を有する有機化合物を用いることができる。その結果、本発明の発光材料に生成した一重項励起子および三重項励起子を、本発明の発光材料の分子中に閉じ込めることが可能となり、その発光効率を十分に引き出すことが可能となる。もっとも、一重項励起子および三重項励起子を十分に閉じ込めることができなくても、高い発光効率を得ることが可能な場合もあるため、高い発光効率を実現しうるホスト材料であれば特に制約なく本発明に用いることができる。本発明の有機発光素子または有機エレクトロルミネッセンス素子において、発光は発光層に含まれる本発明の発光材料から生じる。この発光は蛍光発光および遅延蛍光発光の両方を含む。但し、発光の一部或いは部分的にホスト材料からの発光があってもかまわない。
ホスト材料を用いる場合、発光材料である本発明の化合物が発光層中に含有される量は0.1重量%以上であることが好ましく、1重量%以上であることがより好ましく、また、50重量%以下であることが好ましく、20重量%以下であることがより好ましく、10重量%以下であることがさらに好ましい。
発光層におけるホスト材料としては、正孔輸送能、電子輸送能を有し、かつ発光の長波長化を防ぎ、なおかつ高いガラス転移温度を有する有機化合物であることが好ましい。
注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、正孔注入層と電子注入層があり、陽極と発光層または正孔輸送層の間、および陰極と発光層または電子輸送層との間に存在させてもよい。注入層は必要に応じて設けることができる。
阻止層は、発光層中に存在する電荷(電子もしくは正孔)および/または励起子の発光層外への拡散を阻止することができる層である。電子阻止層は、発光層および正孔輸送層の間に配置されることができ、電子が正孔輸送層の方に向かって発光層を通過することを阻止する。同様に、正孔阻止層は発光層および電子輸送層の間に配置されることができ、正孔が電子輸送層の方に向かって発光層を通過することを阻止する。阻止層はまた、励起子が発光層の外側に拡散することを阻止するために用いることができる。すなわち電子阻止層、正孔阻止層はそれぞれ励起子阻止層としての機能も兼ね備えることができる。本明細書でいう電子阻止層または励起子阻止層は、一つの層で電子阻止層および励起子阻止層の機能を有する層を含む意味で使用される。
正孔阻止層とは広い意味では電子輸送層の機能を有する。正孔阻止層は電子を輸送しつつ、正孔が電子輸送層へ到達することを阻止する役割があり、これにより発光層中での電子と正孔の再結合確率を向上させることができる。正孔阻止層の材料としては、後述する電子輸送層の材料を必要に応じて用いることができる。
電子阻止層とは、広い意味では正孔を輸送する機能を有する。電子阻止層は正孔を輸送しつつ、電子が正孔輸送層へ到達することを阻止する役割があり、これにより発光層中での電子と正孔が再結合する確率を向上させることができる。
励起子阻止層とは、発光層内で正孔と電子が再結合することにより生じた励起子が電荷輸送層に拡散することを阻止するための層であり、本層の挿入により励起子を効率的に発光層内に閉じ込めることが可能となり、素子の発光効率を向上させることができる。励起子阻止層は発光層に隣接して陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。すなわち、励起子阻止層を陽極側に有する場合、正孔輸送層と発光層の間に、発光層に隣接して該層を挿入することができ、陰極側に挿入する場合、発光層と陰極との間に、発光層に隣接して該層を挿入することができる。また、陽極と、発光層の陽極側に隣接する励起子阻止層との間には、正孔注入層や電子阻止層などを有することができ、陰極と、発光層の陰極側に隣接する励起子阻止層との間には、電子注入層、電子輸送層、正孔阻止層などを有することができる。阻止層を配置する場合、阻止層として用いる材料の励起一重項エネルギーおよび励起三重項エネルギーの少なくともいずれか一方は、発光材料の励起一重項エネルギーおよび励起三重項エネルギーよりも高いことが好ましい。
正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層または複数層設けることができる。
正孔輸送材料としては、正孔の注入または輸送、電子の障壁性のいずれかを有するものであり、有機物、無機物のいずれであってもよい。使用できる公知の正孔輸送材料としては例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、カルバゾール誘導体、インドロカルバゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体およびピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、また導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられるが、ポルフィリン化合物、芳香族第3級アミン化合物およびスチリルアミン化合物を用いることが好ましく、芳香族第3級アミン化合物を用いることがより好ましい。
電子輸送層とは電子を輸送する機能を有する材料からなり、電子輸送層は単層または複数層設けることができる。
電子輸送材料(正孔阻止材料を兼ねる場合もある)としては、陰極より注入された電子を発光層に伝達する機能を有していればよい。使用できる電子輸送層としては例えば、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタンおよびアントロン誘導体、オキサジアゾール誘導体等が挙げられる。さらに、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子輸送材料として用いることができる。さらにこれらの材料を高分子鎖に導入した、またはこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。
一方、りん光については、本発明の化合物のような通常の有機化合物では、励起三重項エネルギーは不安定で熱等に変換され、寿命が短く直ちに失活するため、室温では殆ど観測できない。通常の有機化合物の励起三重項エネルギーを測定するためには、極低温の条件での発光を観測することにより測定可能である。
1H NMR(500MHz,CDCl3,δ):8.45(d,J=1.5Hz,2H),8.26(d,J=7.8Hz,2H),8.22(d,1.5Hz,4H),8.02(t,1.4Hz,2H),7.83(dd,J=8.5Hz,1.8Hz,2H),7.54-7.51(m,4H),7.45-7.42(m,4H)
元素分析:計算値(C40H20N6):C82.18;H3.45;N14.37%;
実測値:C82.07;H3.51;N14.34%
1H NMR(500MHz,Acetone-d6,δ):8.70(d,J=1.4Hz,2H),8.53(d,J=8.0Hz,4H),8.42(d,7.7Hz,2H),8.14(t,8.0Hz,2H),7.93(dd,J=8.5Hz,1.8Hz,2H),7.52(t,J=7.5Hz,2H),7.44-7.41(m,4H),7.30(d,8.2Hz,2H)
13C NMR(125MHz,Acetone-d6,δ):143.30,142.06,140.83,139.97,136.28,131.75,127.70,127.27,125.60,125.11,122.33,121.90,120.41,116.46,115.26,110.97,110.75.
元素分析:計算値(C40H20N6):C82.18;H3.45;N14.37%
実測値:C82.23;H3.52;N14.39%
石英基板上に真空蒸着法にて、真空度10-4Pa以下の条件にて化合物1とDPEPOとを異なる蒸着源から蒸着し、化合物1の濃度が10重量%である薄膜を100nmの厚さで形成して薄膜型有機フォトルミネッセンス素子とした。
化合物1の代わりに、化合物2を用いた薄膜型有機フォトルミネッセンス素子も作製した。
これらの各薄膜型有機フォトルミネッセンス素子の発光スペクトルを図2に示す。
また、化合物1を用いた薄膜型有機フォトルミネッセンス素子と化合物2を用いた薄膜型有機フォトルミネッセンス素子の過渡減衰曲線を図3に示す。この過渡減衰曲線は、化合物に励起光を当てて発光強度が失活してゆく過程を測定した発光寿命測定結果を示すものである。通常の一成分の発光(蛍光もしくはリン光)では発光強度は単一指数関数的に減衰する。これは、グラフの縦軸がセミlog である場合には、直線的に減衰することを意味している。図3に示す化合物1の過渡減衰曲線では、観測初期にこのような直線的成分(蛍光)が観測されているが、数μ秒以降には直線性から外れる成分が現れている。これは遅延成分の発光であり、初期の成分と加算される信号は、長時間側に裾をひくゆるい曲線になる。このように発光寿命を測定することによって、化合物1は蛍光成分のほかに遅延成分を含む発光体であることが確認された。
膜厚100nmのインジウム・スズ酸化物(ITO)からなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度5.0×10-4Paで積層した。まず、ITO上にα-NPDを30nmの厚さに形成し、次いでmCPを10nmの厚さに形成した。次に、化合物1とDPEPOを異なる蒸着源から共蒸着し、20nmの厚さの層を形成して発光層とした。この時、化合物1の濃度は10重量%とした。次に、DPEPOを10nmの厚さに形成し、TPBiを30nmの厚さに形成し、さらにフッ化リチウム(LiF)を0.5nm真空蒸着し、次いでアルミニウム(Al)を100nmの厚さに蒸着することにより陰極を形成し、有機エレクトロルミネッセンス素子とした。
化合物1の代わりに、化合物2を用いた有機エレクトロルミネッセンス素子も作製した。
これらの各有機エレクトロルミネッセンス素子の発光スペクトルを図4に示す。
また、化合物1を用いた有機エレクトロルミネッセンス素子と化合物2を用いた有機エレクトロルミネッセンス素子の電流密度-外部量子効率特性を図5に示す。仮に発光量子効率が100%の蛍光材料を用いてバランスの取れた理想的な有機エレクトロルミネッセンス素子を試作したとすると、光取り出し効率が20~30%であれば、蛍光発光の外部量子効率は5~7.5%となる。この値が一般に、蛍光材料を用いた有機エレクトロルミネッセンス素子の外部量子効率の理論限界値とされている。図5から明らかなように、化合物1を用いた本発明の有機エレクトロルミネッセンス素子は、理論限界値を超える高い外部量子効率を実現している点で極めて優れている。
2 陽極
3 正孔注入層
4 正孔輸送層
5 発光層
6 電子輸送層
7 陰極
Claims (13)
- 一般式(1)の2つのAが同一の構造を有することを特徴とする請求項1に記載の化合物。
- 一般式(2)において、R1~R5のうち、少なくとも2つはシアノ基を表し、R6~R10のうち、少なくとも2つはシアノ基を表すことを特徴とする請求項3に記載の化合物。
- 一般式(2)において、R1、R5、R6およびR10はシアノ基を表すことを特徴とする請求項3または4に記載の化合物。
- 一般式(2)において、R2、R4、R7およびR9はシアノ基を表すことを特徴とする請求項3~5のいずれか1項に記載の化合物。
- 一般式(2)において、R1~R5およびR6~R10のうち、シアノ基を表すもの以外は、水素原子または炭素数1~10の置換もしくは無置換のアルキル基を表し、R11~R17およびR21~R27は水素原子または炭素数1~10の置換もしくは無置換のアルキル基を表すことを特徴とする請求項3~6のいずれか1項に記載の化合物。
- 一般式(2)において、R1~R5およびR6~R10のうち、シアノ基を表すもの以外は、水素原子を表し、R11~R17およびR21~R27は水素原子を表すことを特徴とする請求項3~7のいずれか1項に記載の化合物。
- 請求項1~8のいずれか1項に記載の化合物からなる発光材料。
- 請求項9に記載の発光材料を含む発光層を基板上に有することを特徴とする有機発光素子。
- 遅延蛍光を放射することを特徴とする請求項11に記載の有機発光素子。
- 有機エレクトロルミネッセンス素子であることを特徴とする請求項11または12に記載の有機発光素子。
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CN105037247A (zh) * | 2015-06-26 | 2015-11-11 | 南京工业大学 | 一类联咔唑衍生物的合成及在有机电致发光中应用 |
WO2016017684A1 (ja) * | 2014-07-31 | 2016-02-04 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、発光性薄膜、表示装置及び照明装置 |
JP2017054972A (ja) * | 2015-09-10 | 2017-03-16 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス素子、表示装置、照明装置、π共役系化合物、及び発光性薄膜 |
WO2020076796A1 (en) | 2018-10-09 | 2020-04-16 | Kyulux, Inc. | Novel composition of matter for use in organic light-emitting diodes |
WO2021157593A1 (ja) | 2020-02-04 | 2021-08-12 | 株式会社Kyulux | 組成物、膜、有機発光素子、発光組成物を提供する方法およびプログラム |
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Also Published As
Publication number | Publication date |
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EP3023414A1 (en) | 2016-05-25 |
KR20160034335A (ko) | 2016-03-29 |
KR102045609B1 (ko) | 2019-11-15 |
US10461261B2 (en) | 2019-10-29 |
TWI645014B (zh) | 2018-12-21 |
CN105531261A (zh) | 2016-04-27 |
JPWO2015008580A1 (ja) | 2017-03-02 |
TW201512368A (zh) | 2015-04-01 |
US20160164000A1 (en) | 2016-06-09 |
CN105531261B (zh) | 2018-10-19 |
JP6326050B2 (ja) | 2018-05-16 |
EP3023414B1 (en) | 2020-03-11 |
EP3023414A4 (en) | 2017-03-15 |
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