Patent Application
20250160201
This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0152743 filed in the Korean Intellectual Property Office on Nov. 7, 2023, the entire contents of which are incorporated herein by reference.
The present specification relates to a composition for an organic material layer of an organic light emitting device and an organic light emitting device including the same.
A light emitting device is a kind of self-emitting type display device, and has an advantage in that the viewing angle is wide, the contrast is excellent, and the response speed is fast.
An organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to an organic light emitting device having the structure, electrons and holes injected from the two electrodes combine with each other in an organic thin film to make a pair, and then, emit light while being extinguished. The organic thin film may be composed of a single layer or multiple layers, if necessary.
A material for the organic thin film may have a light emitting function, if necessary. For example, as the material for the organic thin film, it is also possible to use a compound, which may itself constitute a light emitting layer alone, or it is also possible to use a compound, which may serve as a host or a dopant of a host-dopant-based light emitting layer. In addition, as a material for the organic thin film, it is also possible to use a compound, which may play a role such as a hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection.
In order to improve the performance, life time, or efficiency of the organic light emitting device, there is a continuous need for developing a material for an organic thin film.
The present specification has been made in an effort to provide a composition for an organic material layer of an organic light emitting device and an organic light emitting device including the same.
An exemplary embodiment of the present specification provides a composition for an organic material layer of an organic light emitting device, the composition including: a heterocyclic compound represented by the following Chemical Formula a; and a heterocyclic compound represented by the following Chemical Formula B.
In Chemical Formulae A and B,
Another exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode; a second electrode provided to face the first electrode; and an organic material layer having one or more layers provided between the first electrode and the second electrode, in which one or more layers of the organic material layer include the above-described composition for an organic material layer of an organic light emitting device.
The composition for an organic material layer according to an exemplary embodiment of the present application can be used as a material for an organic material layer of an organic light emitting device. In particular, the composition for an organic material layer is characterized by including a combination of a heterocyclic compound represented by Chemical Formula A and a heterocyclic compound represented by Chemical Formula B. More specifically, the composition for an organic material layer is characterized by including heterocyclic compound represented by Chemical Formula A as a P-type host material and a heterocyclic compound represented by Chemical Formula B as an N-type host material.
It can be confirmed that when a heterocyclic compound represented by Chemical Formula A, which can be used as a unipolar P-type host material with excellent hole mobility, and a compound represented by Chemical Formula B, which can be used as a unipolar N-type host material with excellent electron mobility, are mixed at a suitable ratio and the resulting mixture is used as a material for a device, the efficiency and life time of the device are improved. Such a combination has an effect of improving device characteristics compared to other combinations of compositions such as existing single materials and premixed compositions of two or more materials.
Accordingly, when the composition organic material layer is used for an organic light emitting device, the driving voltage of the device can be lowered, the light efficiency of the device can be improved, the thermal stability of the compound can be improved, and the life time characteristics of the device can be improved.
Hereinafter, the present specification will be described in more detail.
When one part “includes” one constituent element in the present specification, unless otherwise specifically described, this does not mean that another constituent element is excluded, but means that another constituent element may be further included.
In the present specification,
of a chemical formula means a position to be bonded.
The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is changed into another substituent, and a position to be substituted is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent may be substituted, and when two or more are substituted, the two or more substituents may be the same as or different from each other.
In the present specification, “substituted or unsubstituted” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a C1 to C60 alkyl group; a C2 to C60 alkenyl group; a C2 to C60 alkynyl group; a C3 to C60 cycloalkyl group; a C2 to C60 heterocycloalkyl group; a C6 to C60 aryl group; a C2 to C60 heteroaryl group; a silyl group; a phosphine oxide group; and an amine group, or with a substituent to which two or more substituents selected among the exemplified substituents are linked.
In the present specification, “when a substituent is not indicated in the structure of a chemical formula or compound” means that a hydrogen atom is bonded to a carbon atom. However, since deuterium (2H) or tritium corresponds to an isotope of hydrogen, it may be interpreted as a concept included in hydrogen, as long as it is not explicitly excluded.
That is, in the present application, deuterium exhibits an effect equivalent to that of hydrogen in terms of driving voltage, light emitting efficiency, and life time, or exhibits improved effects in some evaluation criteria, according to Chem. Commun., 2014, 50, 14870, and since the effect falls within the scope that a person with ordinary skill in the art may predict may have the equivalent effect without conducting specific experiments, deuterium, an isotope of hydrogen, is interpreted as a concept included in hydrogen, as long as it is not explicitly excluded.
According to an exemplary embodiment of the present specification, “when a substituent is not indicated in the structure of a chemical formula or compound” may mean that all the positions that may be reached by the substituent are hydrogen; or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be deuterium which is an isotope, and in this case, the content of deuterium may be 0% to 100%.
According to an exemplary embodiment of the present specification, in “the case where a substituent is not indicated in the structure of a chemical formula or compound”, when the content of deuterium is 0%, the content of hydrogen is 100%, and all the substituents do not explicitly exclude deuterium such as hydrogen, hydrogen and deuterium may be mixed and used in the compound.
According to an exemplary embodiment of the present specification, deuterium is one of the isotopes of hydrogen, is an element that has a deuteron composed of one proton and one neutron as a nucleus, and may be represented by hydrogen-2, and the element symbol may also be expressed as D or 2H.
According to an exemplary embodiment of the present specification, the isotope means an atom with the same atomic number (Z), but different mass numbers (A), and may also be interpreted as an element which has the same number of protons, but different number of neutrons.
According to an exemplary embodiment of the present specification, when the total number of substituents of a basic compound is defined as T1 and the number of specific substituents among the substituents is defined as T2, the content T % of the specific substituent may be defined as T2/T1×100=T %.
That is, when taking a phenyl group represented by
as an example, herein, a deuterium content of 20% may be represented by 20% when the total number of substituents that the phenyl group can have is 5 (T1 in the formula) and the number of deuteriums among the substituents is 1 (T2 in the formula). That is, a deuterium content of 20% in the phenyl group may be represented by the following structural formula.
Further, according to an exemplary embodiment of the present specification, “a phenyl group having a deuterium content of 0%” may mean a phenyl group that does not include a deuterium atom, that is, has five hydrogen atoms.
In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group includes a straight-chain or branched-chain having 1 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, an n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, a 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, a 5-methylhexyl group, and the like, but are not limited thereto.
In the present specification, the alkenyl group includes a straight-chain or branched-chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples thereof include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group; a 2-butenyl group; a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl) vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl) vinyl-1-yl group, a stilbenyl group, a styrenyl group and the like, but are not limited thereto.
In the present specification, the alkynyl group includes a straight-chain or branched-chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.
In the present specification, an alkoxy group may be straight-chained, branched, or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, and the like, but are not limited thereto.
In the present specification, the cycloalkyl group includes a monocycle or polycycle having 3 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, the polycycle means a group in which a cycloalkyl group is directly linked to or fused with another cyclic group. Here, another cyclic group may also be a cycloalkyl group, but may also be another kind of cyclic group, for example, a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but are not limited thereto.
In the present specification, the heterocycloalkyl group includes O, S, Se, N, or Si as a heteroatom, includes a monocycle or polycycle having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, the polycycle means a group in which a heterocycloalkyl group is directly linked to or fused with another cyclic group. Here, another cyclic group may also be a heterocycloalkyl group, but may also be another kind of cyclic group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.
In the present specification, the aryl group includes a monocycle or polycycle having 6 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, the polycycle means a group in which an aryl group is directly linked to or fused with another cyclic group. Here, another cyclic group may also be an aryl group, but may also be another kind of cyclic group, for example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, a fused cyclic group thereof, and the like, but are not limited thereto.
In the present specification, the terphenyl group may be selected from the following structures.
In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
When the fluorenyl group is substituted, the substituent may be selected from the following structures, but is not limited thereto.
In the present specification, the heteroaryl group includes S, O, Se, N, or Si as a heteroatom, includes a monocycle or a polycycle having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, the polycycle means a group in which a heteroaryl group is directly linked to or fused with another cyclic group. Here, another cyclic group may also be a heteroaryl group, but may also be another kind of cyclic group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The number of carbon atoms of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a diazinyl group, an oxazinyl group, a thiazinyl group, a dioxynyl a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a quinazolinyl group, naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridinyl group, a diaza naphthalenyl group, a triazaindene group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl group, a dibenzosilole group, spirobi(dibenzosilole), a dihydrophenazinyl group, a phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, an indolinyl group, a 10,11-dihydro-dibenzo[b, f]azepin group, a 9,10-dihydroacridinyl group, a phenanthrazinyl group, a phenothiathiazinyl group, a phthalazinyl group, a naphthylidinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, a 2,3-dihydrobenzo[b]thiophene group, a 2,3-dihydrobenzofuran group, a 5,10-dihydrodibenzo[b,e][1,4]azasilinyl group, a pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group, a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, a 5,11-dihydroindeno[1,2-b]carbazolyl group, and the like, but are not limited thereto.
In the present specification, when the substituent is a carbazole group, it means being bonded to nitrogen or carbon of carbazole.
In the present specification, when a carbazole group is substituted, an additional substituent may be substituted with the nitrogen or carbon of the carbazole.
In the present specification, a benzocarbazole group may be any one of the following structures.
In the present specification, a dibenzocarbazole group may be any one of the following structures.
In the present specification, a naphthobenzofuran group may be any one of the following structures.
In the present specification, a naphthobenzothiophene group may be any one of the following structures.
In the present specification, a silyl group includes Si and is a substituent to which the Si atom is directly linked a radical, as and is represented by —Si(R101)(R102)(R103), and R101 to R103 are the same as or different from each other, and may be each independently a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group.
Specific examples of the silyl group include
(a trimethylsilyl group),
(a triethylsilyl group),
(a t-butyldimethylsilyl group),
(a vinyldimethylsilyl group),
(a propyldimethylsilyl group),
(a triphenylsilyl group),
(a diphenylsilyl group),
(a phenylsilyl group) and the like, but are not limited thereto.
In the present specification, the phosphine oxide group is represented by —P(═O)(R104)(R105), and R104 and R105 are the same as or different from each other, and may be each independently a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. Specifically, the phosphine oxide group may be substituted with an alkyl group or an aryl group, and the above-described example may be applied to the alkyl group and the aryl group. Examples of the phosphine oxide a group include dimethylphosphine oxide group, a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, and the like, but are not limited thereto.
In the present specification, the amine group is represented by —N(R106)(R107), and R106 and R107 are the same as or different from each other, and may be each independently a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. The amine group may be selected from the group consisting of —NH2; a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.
In the present specification, the above-described examples of the aryl group may be applied to an arylene group except for a divalent arylene group.
In the present specification, the above-described examples of the heteroaryl group may be applied to a heteroarylene group except for a divalent heteroarylene group.
In the present specification, an “adjacent” group may mean a substituent substituting an atom directly linked to an atom substituted by the corresponding substituent, a substituent sterically most closely positioned to the corresponding substituent, or another substituent substituting an atom substituted by the corresponding substituent. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as groups which are “adjacent” to each other.
Hydrocarbon rings and hetero rings that adjacent groups may form include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic hetero ring and an aromatic hetero ring, and structures exemplified by the above-described cycloalkyl group, aryl group, heterocycloalkyl group and heteroaryl group may be each applied to the rings, except for those that are not monovalent groups.
Hereinafter, the composition for an organic material layer of an organic light emitting device according to the present specification will be described.
The composition for an organic material layer of an organic light emitting device according to an exemplary embodiment of the present specification includes a heterocyclic compound represented by the following Chemical Formula A.
In Chemical Formula A, the description of each substituent is as described above.
The heterocyclic compound represented by Chemical Formula A is a di-substituted naphthobenzofuran, in which a first substituent
enhances the electron and hole transport properties and a second substituent
enhances the hole transport properties, so that it is possible to exhibit excellent electron and hole transport properties as a whole.
When a heterocyclic compound represented by Chemical Formula A, which has excellent hole transport properties, is used together with a heterocyclic compound represented by Chemical Formula B, which has fast electron transport properties, the heterocyclic compound may act as a P-type host material to cause charge balance in an organic layer (particularly, a light emitting layer (EML)) and prevent degradation caused by the accumulation of electrons and holes, thereby exhibiting high efficiency and long life time.
The composition for an organic material layer of an organic light emitting device according to an exemplary embodiment of the present specification includes a heterocyclic compound represented by the following Chemical Formula B.
In Chemical Formula B, the description of each substituent is as described above.
The compound represented by Chemical Formula B is di-substituted as a tricyclic or more oxygen-containing fused heterocycle, and N-Het1 (represented by Structural Formula N and corresponding to triazine), a first substituent, enhances the electron transport properties, and Ar4, a second substituent, enhances the hole transport properties, and as a whole, the compound has excellent electron and hole transport properties, and thus, may exhibit high efficiency.
When a heterocyclic compound represented by Chemical Formula B, which has fast electron transport properties, is used together with a heterocyclic compound represented by Chemical Formula A, which has excellent hole transport properties, the heterocyclic compound may act as an N-type host material to cause charge balance in an organic layer (particularly, a light emitting layer (EML)) and prevent degradation caused by the accumulation of electrons and holes, thereby exhibiting high efficiency and long life time.
The compound according to exemplary embodiments may have low driving voltage, high light emitting efficiency, and/or long life time characteristics when used in an organic light emitting device.
According to an exemplary embodiment of the present specification, Chemical Formula A may be represented by any one of the following Chemical Formulae A-1 to A-3.
In Chemical Formulae A-1 to A-3,
According to an exemplary embodiment of the present specification, Chemical Formula A may be represented by any one of the following Chemical Formulae A-101 to A-104.
In Chemical Formulae A-101 to A-104,
According to an exemplary embodiment of the present specification, Chemical Formula B may be represented by any one of the following Chemical Formulae B-1 to B-11.
In Chemical Formulae B-1 to B-11,
According to an exemplary embodiment of the present specification, Chemical Formula B may be represented by any one of the following Chemical Formulae B-101 to B-132.
In Chemical Formulae B-101 to B-132,
According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and may be each independently a direct bond; a substituted or unsubstituted C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 heteroarylene group.
According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and may be each independently a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.
According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and may be each independently a direct bond; or a C6 to C30 arylene group unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and may be each independently a direct bond; a phenylene group unsubstituted or substituted with deuterium; a biphenylene group unsubstituted or substituted with deuterium; or a naphthylene group unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, Ar1, Ar2, and Ar4 are the same as or different from each other, and may be each independently a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
According to an exemplary embodiment of the present specification, Ar1, Ar2, and Ar4 are the same as or different from each other, and may be each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
According to an exemplary embodiment of the present specification, Ar1, Ar2, and Ar4 are the same as or different from each other, and may be each independently a C6 to C30 aryl group unsubstituted or substituted with a substituent selected from the group consisting of deuterium, an alkyl group, and an aryl group; or a C2 to C30 heteroaryl group unsubstituted or substituted with a substituent selected from the group consisting of deuterium, an alkyl group, and an aryl group.
According to an exemplary embodiment of the present specification, Ar1, Ar2, and Ar4 are the same as or different from each other, and may be each independently a phenyl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorenyl group; a phenanthrenyl group; a dibenzofuranyl group; a dibenzothiophenyl group; or a carbazolyl group, which may be each independently unsubstituted or substituted with a substituent selected from the group consisting of deuterium, an alkyl group, and an aryl group.
According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and may be each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C2 to C40 heterocycloalkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and may be each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.
According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and may be each independently hydrogen; or deuterium.
According to an exemplary embodiment of the present specification, R5 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C2 to C40 heterocycloalkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group, or two or more adjacent R5's may be bonded to each other to form a substituted or unsubstituted C6 to C40 hydrocarbon ring or a substituted or unsubstituted C2 to C40 hetero ring.
According to an exemplary embodiment of the present specification, R5 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group, or two or more adjacent R5's may be bonded to each other to form a substituted or unsubstituted C6 to C20 hydrocarbon ring or a substituted or unsubstituted C2 to C20 hetero ring.
According to an exemplary embodiment of the present specification, R5 is hydrogen; or deuterium, or two or more adjacent R5's may be bonded to each other to form a substituted or unsubstituted benzene ring.
According to an exemplary embodiment of the present specification, R5 is hydrogen; or deuterium, or two or more adjacent R5's may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and are each independently hydrogen; or deuterium, R5 is hydrogen; or deuterium, or two or more adjacent R5's may be bonded to t each other to form a benzene ring unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, Rk and Rk1 to Rk3 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
According to an exemplary embodiment of the present specification, Rk and Rk1 to Rk3 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
According to an exemplary embodiment of the present specification, Rk and Rk1 to Rk3 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.
According to an exemplary embodiment of the present specification, Rk and Rk1 to Rk3 are the same as or different from each other, and may be each independently hydrogen; deuterium; a C1 to C20 alkyl group unsubstituted or substituted with deuterium; a C6 to C20 aryl group unsubstituted or substituted with deuterium; or a C2 to C20 heteroaryl group unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, Rk and Rk1 to Rk3 are the same as or different from each other, and may be each independently hydrogen; deuterium; a methyl group unsubstituted or substituted with deuterium; an ethyl group unsubstituted or substituted with deuterium; or a phenyl group unsubstituted or substituted with deuterium.
According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and may be each independently a substituted or unsubstituted C6 to C40 substituted or unsubstituted C2 to C40 heteroaryl group; or a combination thereof.
According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and may be each independently a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; or a combination thereof.
According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and may be each independently a C6 to C30 aryl group unsubstituted or substituted with deuterium, an alkyl group, or an alkenyl group; a C2 to C30 heteroaryl group unsubstituted or substituted with deuterium, an alkyl group, or an alkenyl group; or a combination thereof.
According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and may be each independently a phenyl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorenyl group; a phenanthrenyl group; a dibenzofuranyl group; a dibenzothiophenyl group; or a carbazolyl group, which may be each independently unsubstituted or substituted with a substituent selected from the group consisting of deuterium, an alkyl group, an alkenyl, and an aryl group.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 1% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 10% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 20% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 30% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 60% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 80% to 100%.
According to an exemplary embodiment of the present specification, the deuterium contents of the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be the same as or different from each other, and may be each independently 0% or 90% to 100%.
According to an exemplary embodiment of the present specification, Chemical Formula A may be represented by any one of the following heterocyclic compounds.
According to an exemplary embodiment of the present specification, Chemical Formula B may be represented by any one of the following heterocyclic compounds.
It is possible to synthesize a compound having inherent characteristics of a substituent introduced by introducing various substituents into the structure(s) represented by Chemical Formulae A and/or B. For example, it is possible to synthesize a material which satisfies conditions required for each organic material layer by introducing a substituent usually used for a hole injection layer material, a hole transport layer material, a hole transport auxiliary layer material, a light emitting layer material, an electron transport layer material, an electron transport auxiliary layer material, and a charge generation layer material used during the manufacture of an organic light emitting device into the core structure.
In addition, it is possible to finely adjust an energy band gap by introducing various substituents into the structures of Chemical Formulae A and/or B, and meanwhile, it is possible to improve characteristics at the interface between organic materials and diversify the use of material.
According to an exemplary embodiment of the present specification, the molar ratio of the heterocyclic compound represented by Chemical Formula A to the heterocyclic compound represented by Chemical Formula B may be 0.1 to 3:0.1 to 2.
According to an exemplary embodiment of the present specification, the molar ratio of the heterocyclic compound represented by Chemical Formula A to the heterocyclic compound represented by Chemical Formula B may be 1 to 3:1 to 2.
In addition, the composition for an organic layer including the heterocyclic compound of Chemical Formula A and the heterocyclic compound of Chemical Formula B provides excellent thermal stability when used in an organic light emitting device, and such thermal stability may provide driving stability to organic light emitting devices in the future as well as improve life time characteristics.
Hereinafter, the organic light emitting device according to the present specification will be described.
Another exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode; a second electrode provided to face the first electrode; and an organic material layer having one or more layers provided between the first electrode and the second electrode, in which one or more layers of the organic material layer include the above-described composition for an organic material layer of an organic light emitting device.
According to an exemplary embodiment of the present specification, the organic material layer further includes a light emitting layer (emission layer), and the light emitting layer may include the composition for an organic light emitting device.
In another embodiment of the present specification, the light emitting layer may include the composition for an organic light emitting device as a host.
According to an exemplary embodiment of the present specification, the light emitting layer may include the composition for an organic light emitting device as a red host.
According to an exemplary embodiment of the present specification, the first electrode may be a positive electrode, and the second electrode may be a negative electrode.
According to an exemplary embodiment of the present specification, the first electrode may be a negative electrode, and the second electrode may be a positive electrode.
According to an exemplary embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the composition for an organic material layer of an organic light emitting device may be used as a material for the blue organic light emitting device.
According to an exemplary embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the composition for an organic material layer of an organic light emitting device may be used as a material for the green organic light emitting device.
According to an exemplary embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the composition for an organic material layer of an organic light emitting device may be used as a material for the red organic light emitting device.
The organic material layer of the organic light emitting device of the present specification may also have a single-layered structure, but may have a multi-layered structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present specification may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and may include less or more numbers of organic material layers.
According to an exemplary embodiment of the present specification, the organic material layer may include an iridium-based dopant.
According to an exemplary embodiment of the present specification, as the iridium-based dopant, Ir(ppy)3, which is a green phosphorescent dopant, may be used, but the iridium-based dopant is not limited thereto.
According to an exemplary embodiment of the present specification, as the iridium-based dopant, (piq)2(Ir)(acac), which is a red phosphorescent dopant, may be used, but the iridium-based dopant is not limited thereto.
In the organic light emitting device of the present specification, as a positive electrode material, materials having a relatively high work function may be used, and a transparent conductive oxide, a metal or a conductive polymer, and the like may be used. Specific examples of the positive electrode material include: a metal such as vanadium, chromium, copper, zinc, and gold, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of a metal and an oxide, such as ZnO:Al or SnO2:Sb; a conductive polymer such as poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and the like, but are not limited thereto.
In the organic light emitting device of the present specification, as a negative electrode material, materials having a relatively low work function may be used, and a metal, a metal oxide, or a conductive polymer, and the like may be used. Specific examples of the negative electrode material include: a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or an alloy thereof; a multi-layer structured material, such as LiF/Al or LiO2/Al; and the like, but are not limited thereto.
In the organic light emitting device of the present specification, as a hole injection material, a publicly-known hole injection material may also be used, and it is possible to use, for example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429 or starburst-type amine derivatives described in the document [Advanced Material, 6, p. 677 (1994)], for example, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4′,4″-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), which is a soluble conductive polymer, polyaniline/camphor sulfonic acid or polyaniline/poly(4-styrene-sulfonate), and the like.
In the organic light emitting device of the present specification, as a hole transport material, a pyrazoline derivative, an arylamine-based derivative, a stilbene derivative, a triphenyldiamine derivative, and the like may be used, and a low-molecular weight or polymer material may also be used.
In the organic light emitting device of the present specification, as an electron transport material, it is possible to use an oxadiazole derivative, anthraquinodimethane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof, anthraquinone and a derivative thereof, tetracyanoanthraquinodimethane and a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene and derivative thereof, a diphenoquinone derivative, a metal complex of 8-hydroxyquinoline and a derivative thereof, and the like, and a low-molecular weight material and a polymer material may also be used.
In the organic light emitting device of the present specification, as an electron injection material, for example, LiF is representatively used in the art, but the present application is not limited thereto.
In the organic light emitting device of the present specification, as a light emitting material, a red, green, or blue light emitting material may be further used, and if necessary, two or more light emitting materials may be mixed and used. In this case, two or more light emitting materials are deposited and used as an individual supply source, or pre-mixed to be deposited and used as one supply source. Further, a fluorescent material may also be used as the light emitting material, but may also be used as a phosphorescent material. As the light emitting material, it is also possible to use alone a material which emits light by combining holes and electrons each injected from a positive electrode and a negative electrode, but materials in which a host material and a dopant material are involved in light emission together may also be used.
When hosts of the light emitting material are mixed and used, the same series of hosts may also be mixed and used, and different series of hosts may also be mixed and used. For example, two or more types of materials selected from N-type host materials or P-type host materials may be used as a host material for a light emitting layer.
The organic light emitting device according to an exemplary embodiment of the present specification may be a top emission type, a bottom emission type, or a dual emission type according to the material to be used.
The heterocyclic compound according to an exemplary embodiment of the present specification may act even in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like, based on the principle similar to those applied to organic light emitting devices.
The organic light emitting device of the present specification may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.
According to
The organic light emitting device according to an exemplary embodiment of the present specification includes a first electrode; a first stack provided on the first electrode and including a first light emitting layer; a charge generation layer provided on the first stack; a second stack provided on the charge generation layer and including a second light emitting layer; and a second electrode provided on the second stack.
When the organic light emitting device according to an exemplary embodiment of the present specification has a two-stack structure as described above, one or more layers of the first light emitting layer (first stack light emitting layer) and the second light emitting layer (second stack light emitting layer) may include the composition for an organic light emitting device.
Furthermore, the first stack and the second stack may each independently further include one or more of the above-described hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, and the like.
The composition for an organic material layer of an organic light emitting device may be used when an organic material layer of an organic light emitting device is formed, and particularly, may be preferably used as a material for the light emitting layer.
The composition for an organic material layer may be in the form of a premix of the heterocyclic compound of Chemical Formula A and the heterocyclic compound of Chemical Formula B, may be mixed with a material in a powder state before the organic material layer of the organic light emitting device is formed, and may be mixed with a compound in a liquid state at a suitable temperature or higher. The composition is in a solid state at a temperature which is equal to or less than the melting point of each material, and may be maintained as a liquid phase when the temperature is adjusted.
The composition for an organic material layer may additionally include materials publicly known in the art such as solvents and additives.
In an exemplary embodiment of the present application, provided is a method for manufacturing an organic light emitting device, the method including: preparing a substrate; forming a first electrode on the substrate; forming an organic material layer having one or more layers on the first electrode; and forming a second electrode on the organic material layer, in which the forming of the organic material layer includes forming the organic material layer having one or more layers by using the composition for an organic material layer of an organic light emitting device according to an exemplary embodiment of the present specification.
According to an exemplary embodiment of the present specification, in the forming of the organic material layer, the heterocyclic compound represented by Chemical Formula A and the heterocyclic compound represented by Chemical Formula B may be formed using a thermal vacuum deposition method.
The organic light emitting device according to an exemplary embodiment of the present specification may be manufactured by typical manufacturing methods and materials of the organic light emitting device, except that the above-described composition for an organic material layer of an organic light emitting device is used to form an organic material layer.
Specifically, in the method of forming an organic material layer, when an organic light emitting device is manufactured, the organic material layer may be formed using the heterocyclic compound of Chemical Formula A and the heterocyclic compound of Chemical Formula B, not only by a vacuum deposition method but also by a solution coating method. Herein, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, a spray method, roll coating, and the like, but is not limited thereto.
Hereinafter, the present specification will be described in more detail through Examples, but these Examples are provided only for exemplifying the present application, and are not intended to limit the scope of the present application.
After 10.0 g (30.16 mmol) of 6-bromo-7-chloronaphtho[1,2-b]benzofuran (A), 9.09 g (31.67 mmol) of (9-phenyl-9H-carbazol-1-yl) boronic acid (B), 1.74 g (1.51 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), and 12.5 g (90.47 mmol) of K2CO3 were dissolved in 1,4-dioxane/H2O (100 ml/20 ml) in a 1 L two-neck flask, the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 14.15 g (yield 95%) of Intermediate A006-1 was obtained.
After 14.15 g (28.5 mmol) of Intermediate A006-1, 9.9 g (28.5 mmol) of 4-(phenanthren-9-yl)-N-phenylaniline (C), 1.3 g (1.4 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 1.37 g (2.86 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 8.26 g (85.95 mmol) of sodium tert-butoxide (NaOtBu) were put into a 5000 ml two-neck flask and dissolved in toluene (150 ml), the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 20.06 g (yield 87.2%, 83% when calculated based on starting materials) of Target Compound A006 was obtained.
The following target compound was synthesized in the same manner as in the method of preparing Compound A006, except that (A), (B), and (C) in the following Table 1 were used instead of (A), (B), and (C) in Preparation Example 1.
After 10.0 g (30.16 mmol) of 6-bromo-7-chloronaphtho[1,2-b]benzofuran (D), 9.69 g (30.16 mmol) of N-phenyl-[1,1′:4′,1″-terphenyl]-4-amine (E), 1.38 g (1.51 tris(dibenzylideneacetone)dipalladium(0) mmol) of (Pd2(dba)3), 1.44 g (3.02 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 8.69 g (90.47 mmol) of sodium tert-butoxide (NaOtBu) were dissolved in toluene (100 ml) in a 1 L two-neck flask, the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 15.36 g (yield 89%) of Intermediate A161-1 was obtained.
After 15.36 g (26.84 mmol) of Intermediate A161-1, 8.09 g (28.18 mmol) of (9-phenyl-9H-carbazol-1-yl) boronic acid (F), 1.23 g (1.34 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 1.28 g (2.68 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 3.2 g (80.52 mmol) of NaOH were put into a 500 ml two-neck flask and dissolved in 1,4-dioxane/H2O (100 ml/20 ml), the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 17.26 g (yield 82.5%, 73% when calculated based on starting materials) of Target Compound A161 was obtained.
The following compound was synthesized in the same manner as in the method of preparing Compound A161, except that (D), (E), and (F) in the following Table 2 were used instead of (D), (E), and (F) in Preparation Example 2.
After 10.0 g (30.16 mmol) of 6-bromo-7-chloronaphtho[1,2-b]benzofuran (G), 16.58 g (31.67 mmol) of N-([1,1′-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1′-biphenyl]-4-amine (H), 1.74 g (1.51 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), and 12.5 g (90.47 mmol) of K2CO3 were dissolved in 1,4-dioxane/H2O (100 ml/20 ml) in a 1 L two-neck flask, the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 17.87 g (yield 91.4%) of Intermediate A226-1 was obtained.
After 17.87 g (27.56 mmol) of Intermediate A226-1, 7.9 g (27.56 mmol) of (9-phenyl-9H-carbazol-1-yl) boronic acid (I), 1.26 g (1.38 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 1.31 g (2.76 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 3.31 g (28.69 mmol) of NaOH were put into a 500 ml two-neck flask and dissolved in 1,4-dioxane/H2O (150 ml/30 ml), the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 19.92 g (yield 84.5%, 74% when calculated based on starting materials) of Target Compound A226 was obtained.
The following target compound was synthesized in the same manner as in the method of preparing Compound A226, except that (G), (H), and (I) in the following Table 3 were used instead of (G), (H), and (I) in Preparation Example 3.
After 10.0 g (35.52 mM) of 1-bromo-3-chlorodibenzo[b,d]furan (J), 9.47 g (37.30 mM) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 1.3 g (1.78 mmol) of Pd(dppf)Cl2, and 10.46 g (106.56 mmol) of KOAc were dissolved in 1,4-dioxane (100 ml) in a 1 L two-neck flask, the resulting solution was refluxed for 2 hours. The reaction product was filtered, and then purified, and 10.32 g (yield 88.4%) of Intermediate B5-2 was obtained.
After 10.32 g (31.40 mmol) of Intermediate B5-2, 8.41 g (31.40 mmol) of (2-chloro-4,6-diphenyl-1,3,5-triazine (K), 1.81 g (1.57 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), and 13.02 g (94.20 mmol) of K2CO3 were dissolved in 1,4-dioxane/H2O (100 ml/20 ml) in a 500 ml two-neck flask, the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 11.63 g (yield 85.4%) of Target Compound B5-1 was obtained.
After 11.63 g (26.82 mmol) of Intermediate B5-1, 7.35 g (26.82 mmol) of [1,1′:4′,1″-terphenyl]-4-ylboronic acid (L), 1.23 g (1.34 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 1.28 g (2.68 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 3.22 g (80.45 mmol) of NaOH were put into a 500 ml two-neck flask and dissolved in 1,4-dioxane/H2O (100 ml/20 ml), the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 15.32 g (yield 91%, 69% when calculated based on starting materials) of Target Compound B5 was obtained.
The following compound was synthesized in the same manner as in the method of preparing Compound A161, except that (J), (K), and (L) in the following Table 4 were used instead of (J), (K), and (L) in Preparation Example 4.
After 10 g (30.31 mmol) of 5-bromo-7-chloronaphtho[1,2-b]benzofuran (M), 3.88 g (31.82 mmol) of phenylboronic acid (n), 1.75 g (1.52 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), and 12.57 g (90.96 mmol) of K2CO3 were put into a 500 mL two-neck flask and dissolved in 1,4-dioxane/H2O (100 ml/20 ml), the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 9.15 g (92%) of Target Compound B422-2 was obtained.
After 9.15 g (27.88 mmol) of Intermediate B422-2, 10.62 g (41.83 mmol) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 1.28 g (1.39 mmol) of Pd2(dba)3, 1.33 g (2.79 mmol) of Xphos, and 12.31 g (125.48 mmol) of KOAc were dissolved in 1,4-dioxane (100 ml) in a 1 L two-neck flask, the resulting solution was refluxed for 2 hours. The reaction product was filtered, and then purified, and 10.08 g (yield 86%) of Intermediate B442-1 was obtained.
After 10.08 g (23.98 mmol) of Intermediate B5-1, 7.6 g (23.98 mmol) of 2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3,5-triazine (0), 1.39 g (1.99 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), and 9.94 g (71.94 mmol) of K2CO3 were dissolved in 1,4-dioxane/H2O (100 ml/20 ml) in a 500 ml two-neck flask, the resulting solution was refluxed for 1 hour. The reaction product was purified by recrystallization with methanol, and 12.55 g (yield 91%, 72% when calculated based on starting materials) of Target Compound B422 was obtained.
The following compound was synthesized in the same manner as in the method of preparing Compound B422, except that (M), (N), and (O) in the following Table 5 were used instead of (M), (N), and (0) in Preparation Example 5.
The following Tables 6 and 7 are the 1H NMR and FD-MS data of the compounds, and it can be confirmed through the following data that the target compound was synthesized.
1H NMR(CDCl3, 400 MHz)
A glass substrate, in which indium tin oxide (ITO) was thinly coated to have a thickness of 1,500 Å, was ultrasonically washed with distilled water. When the washing with distilled water was finished, the glass substrate was ultrasonically washed with a solvent such as acetone, methanol, and isopropyl alcohol, dried and then subjected to ultraviolet ozone (UVO) treatment for 5 minutes using UV in an ultraviolet (UV) washing machine. Thereafter, the substrate was transferred to a plasma washing machine (PT), and then was subjected to plasma treatment in a vacuum state for an ITO work function and in order to remove a residual film, and was transferred to a thermal deposition apparatus for organic deposition.
As the common layers, the hole injection layer 4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and the hole transport layer N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) were formed on the ITO transparent electrode (positive electrode).
A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited to have a thickness of 500 Å by using a compound (premixed when two or more compounds were used) shown in the following Table 8 as a red host and (piq) 2 (Ir) (acac) as a red phosphorescent dopant to dope the host with (piq)2(Ir)(acac) in an amount of 3%.
Thereafter, BCP was deposited as a hole blocking layer to have a thickness of 60 Å, and Alq3 was deposited as an electron transport layer to have a thickness of 200 Å thereon. Finally, lithium fluoride (LiF) was deposited to have a thickness of 10 Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) negative electrode was deposited to have a thickness of 1,200 Å on the electron injection layer to form a negative electrode, thereby manufacturing an organic light emitting device.
Meanwhile, all the organic compounds required for manufacturing an OLED device were subjected to vacuum sublimed purification under 10-8 to 10-6 torr for each material, and used for the manufacture of OLED.
For the organic light emitting device manufactured as described above, electroluminescence (EL) characteristics were measured by M7000 manufactured by McScience Inc., and based on the measurement result thereof, T90 was measured by a life time measurement device (M6000) manufactured by McScience Inc., when the reference luminance was 6,000 cd/m2. T90 means the life time (unit: hour) that is the time it takes for the luminance to reach 90% relative to the initial luminance.
The characteristics of the organic light emitting device of the present invention are as shown in the following Table 8. The comparative compounds shown in the following Table 8 are as follows.
As can be seen from the results of Table 8 above, it could be confirmed that when the organic material layer of an organic light emitting device is deposited by mixing two types of heterocyclic compounds according to the present application (specifically, a heterocyclic compound of Chemical Formula A and a heterocyclic compound of Chemical Formula B), the efficiency or life time effect of the organic light emitting device is improved.
Specifically, according to Comparative Examples 1 to 92, when the heterocyclic compound of Chemical Formula A was used alone, a low efficiency of about 7 cd/A and a short life time of 11 or less hours were shown, and according to Comparative Examples 101 to 192, when the heterocyclic compound of Chemical Formula B was used alone, an efficiency of about 59 cd/A and a life time of 81 or less hours were shown.
Referring to Examples 1 to 206 in which a heterocyclic compound of Chemical Formula A was used in combination with a heterocyclic compound of Chemical Formula B, it can be confirmed that charge balance was achieved, and the device exhibited high efficiency and long life time characteristics, and in particular, the life time was increased by approximately 10-fold compared to Comparative Examples 1 to 92. These results suggest that the heterocyclic compound of Chemical Formula A has fast electron supply, and when combined with the heterocyclic compound of Chemical Formula B, it also balances the hole supply, thereby balancing the charge in the device and improving the life time and efficiency.
Meanwhile, in the case of Compounds K to N in Comparative Examples 93 to 96, only an arylamine group is substituted as a mono-substituted dibenzofuran or naphthobenzofuran, and such structures have smaller electronic properties than the heterocyclic compound of Chemical Formula A of the present application, so that when the compounds are combined with the heterocyclic compound of Chemical Formula B, low efficiency and short life time are observed as in Comparative Examples 201 to 219, suggesting that device characteristics deteriorate due to charge imbalance.
In the case of Compounds 0 to R in Comparative Examples 97 to 100, only an aryl group or a heteroaryl group is substituted as a mono-substituted naphthobenzofuran, and such a structure has weaker hole characteristics than the heterocyclic compound of Chemical Formula A, so that when the compounds are combined with the heterocyclic compound of Chemical Formula B, low efficiency and short life time are exhibited as in Comparative Examples 220 to 238, suggesting that device characteristics deteriorate due to charge imbalance.
Further, in the case of Compounds S to V in Comparative Examples 193 to 196, only triazine is substituted as mono-substituted dibenzofuran or naphthobenzofuran, and such structures have very high electron transport properties compared to the heterocyclic compound of Chemical Formula B, so that when the compounds are combined with the compound of Chemical Formula A, low efficiency and short life time are exhibited as in Comparative Examples 239 to 254, suggesting that device characteristics deteriorate due to charge imbalance because the electron mobility is too high compared to the hole mobility.
In addition, in the case of Compounds W to Z in Comparative Examples 197 to 200, only an aryl group or a heteroaryl group is substituted as a mono-substituted dibenzofuran or naphthobenzofuran, and such structures have remarkably lower electron transport properties than the heterocyclic compound of Chemical Formula B, so that when the compounds are combined with the heterocyclic compound of Chemical Formula A, low efficiency and short life time are exhibited as in Comparative Examples 255 to 269, suggesting that device characteristics deteriorate due to charge imbalance because the electron mobility is too low compared to the hole mobility.
Furthermore, since Compound B has high electronic properties, when the proportion of the heterocyclic compound of Chemical Formula B is higher than that of the heterocyclic compound of Chemical Formula A, the charge balance is further improved, so that the efficiency and life time characteristics may be further improved. As a result of the experiment, it can be confirmed that excellent efficiency and life time were obtained when the molar ratio of the heterocyclic compound of Chemical Formula A to the heterocyclic compound of Chemical Formula B was 3:1, 2:1, or 1.5:1.
The present invention is not limited to the Examples, but may be prepared in various forms, and a person with ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in another specific form without changing the technical spirit or essential feature of the present invention. Therefore, it should be understood that the above-described Examples are illustrative only: in all aspects and are not restrictive.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0152743 | Nov 2023 | KR | national |
