Patent Application
20240065015
This application claims priority to and the benefits of Korean Patent Application No. 10-2020-0180272, filed with the Korean Intellectual Property Office on Dec. 21, 2020, the entire contents of which are incorporated herein by reference.
The present specification relates to a heterocyclic compound and an organic light emitting device comprising the same.
An electroluminescent device is a type of self-emission type display device, and there are advantages in that it not only has a wide viewing angle and excellent contrast, but also has fast response speed.
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 the organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then emit light while being disappeared. The organic thin film may be composed of a single layer or multiple layers as needed.
A material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant based light emitting layer may also be used. In addition, compounds capable of performing the roles of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, etc. may also be used as a material of the organic thin film.
In order to improve the performance, lifespan, or efficiency of the organic light emitting device, the development of the material of the organic thin film is continuously required.
An object of the present specification is to provide a heterocyclic compound and an organic light emitting device comprising the same.
An embodiment of the present application provides a heterocyclic compound represented by Chemical Formula 1 below.
In Chemical Formula 1,
Furthermore, in an embodiment of the present application, there is provided an organic light emitting device comprising: a first electrode; a second electrode; and an organic material layer with one or more layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layer comprise the heterocyclic compound represented by Chemical Formula 1 above.
The heterocyclic compound described in the present specification may be used as a material of an organic material layer of an organic light emitting device. The heterocyclic compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. in the organic light emitting device.
Specifically, when the heterocyclic compound represented by Chemical Formula 1 above is used in the organic material layer of the organic light emitting device, it is possible to lower the driving voltage of the device, improve the light efficiency, and improve the lifespan characteristics of the device.
Hereinafter, the present specification will be described in more detail.
In the present specification, if a prescribed part “includes” a prescribed element, this means that another element can be further included instead of excluding other elements unless any particularly opposite description exists.
In the present specification, in the chemical formula means a bonding position.
The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more substituents are substituted, two or more substituents may be the same as or different from each other.
In the present specification, “substituted or unsubstituted” means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of: a C1-C60 linear or branched alkyl group; a C2-C60 linear or branched alkenyl group; a C2-C60 linear or branched alkynyl group; a C3-C60 monocyclic or polycyclic cycloalkyl group; a C2-C60 monocyclic or polycyclic heterocycloalkyl group; a C6-C60 monocyclic or polycyclic aryl group; a C2-C60 monocyclic or polycyclic heteroaryl group; a silyl group; a phosphine oxide group; and an amine group, or is substituted or unsubstituted with a substituent to which two or more substituents selected from the above-exemplified substituents are connected.
More specifically, in the present specification, “substituted or unsubstituted” may mean that it is substituted or unsubstituted with one or more substituents selected from the group consisting of: a monocyclic or polycyclic C6-C60 aryl group; and a monocyclic or polycyclic C2-C60 heteroaryl group.
In the present specification, the halogen may be fluorine, chlorine, bromine, or iodine.
In the present specification, the alkyl group may include a linear or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. 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 of the alkyl group may 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, an 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, an 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, an 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, an n-octyl group, a tert-octyl group, an 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a 2,2-dimethylheptyl group, an 1-ethyl-propyl group, an 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, a 5-methylhexyl group, etc., but the present application is not limited thereto.
In the present specification, a haloalkyl group refers to an alkyl group substituted with a halogen group, and specific examples of the haloalkyl group may include —CF3, —CF2CF3, etc., but the present application is not limited thereto.
In the present specification, the alkenyl group may include a linear or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. 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 of the alkenyl group may include a vinyl group, an 1-propenyl group, an isopropenyl group, an 1-butenyl group, a 2-butenyl group, a 3-butenyl group, an 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, an 1,3-butadienyl group, an allyl group, an 1-phenylvinyl-1-yl group, a 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, etc., but the present application is not limited thereto.
In the present specification, the alkynyl group may include a linear or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. 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, the alkoxy group may be a linear, branched, or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples of the alkoxy group may 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, etc., but the present application is not limited thereto.
In the present specification, the cycloalkyl group may include a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring refers to a group in which a cycloalkyl group is directly connected or condensed with other ring group. Here, although the other ring group may be a cycloalkyl group, it may also be a different type of ring group, for example, a heterocycloalkyl group, an aryl group, a heteroaryl group, or 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 of the cycloalkyl group may 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, etc., but the present application is not limited thereto.
In the present specification, the heterocycloalkyl group may contain O, S, Se, N, or Si as a heteroatom, may include a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring refers to a group in which a heterocycloalkyl group is directly connected or condensed with other ring group. Here, although the other ring group may be a heterocycloalkyl group, it may also be a different type of ring group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, or 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 may include a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which an aryl group is directly connected or condensed with other ring group. Here, although the other ring group may be an aryl group, it may also be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, or 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 may 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, condensed ring groups thereof, etc., but the present application is not limited thereto.
In the present specification, the terphenyl group may be selected from structures below.
In the present specification, when the substituent is a carbazole group, it means bonding with nitrogen or carbon of carbazole.
In the present specification, when the carbazole group is substituted, an additional substituent may be substituted for nitrogen or carbon of carbazole.
In the present specification, a benzocarbazole group may be any one of structures below.
In the present specification, a dibenzocarbazole group may be any one of structures below.
In the present specification, a naphthobenzofuran group may be any one of structures below.
In the present specification, a naphthobenzothiophene group may be any one of structures below.
In the present specification, the phosphine oxide group may be represented by —P(═O) R101R102, wherein R101 and R102 may be the same as or different from each other, and may be each independently a substituent consisting of at least one of hydrogen; heavy hydrogen; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heterocyclic group. The phosphine oxide group may specifically include a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, etc., but the present application is not limited thereto.
In the present specification, the silyl group may be a substituent which contains Si and to which the Si atom is directly connected as a radical, and may be represented by —SiR104R105R106, wherein R104 to R106 may be the same as or different from each other, and may be each independently a substituent consisting of at least one of hydrogen; heavy hydrogen; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heterocyclic group. Specific examples of the silyl group may 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, etc., the present application is not limited thereto.
Examples of the silyl group may 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), etc., the present application is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded to a fluorenyl group. Specifically, the spiro group may include any one of groups of structural formulas below.
In the present specification, the heteroaryl group may contain S, O, Se, N, or Si as a heteroatom, may include a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring refers to a group in which a heteroaryl group is directly connected or condensed with other ring group. Here, although the other ring group may be a heteroaryl group, it may also be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or 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 may 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 deoxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a quinozolilyl group, a naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridinyl group, a diazanaphthalenyl 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 dibenzosilol group, a spirobi (dibenzosilole) group, a dihydrophenazinyl group, a phenoxazinyl group, a phenantridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, a 10,11-dihydro-dibenzo[b,f]azepine group, a 9,10-dihydroacridinyl group, a phenanthrazinyl group, a phenothiazinyl group, a phthalazinyl group, a naphthylidinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, a 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, 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, etc., but the present application is not limited thereto.
In the present specification, the amine group may be selected from the group consisting of: a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; —NH2; 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 may 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, a 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, etc., but the present application is not limited thereto.
In the present specification, the arylene group means one having two bonding positions in the aryl group, that is, a divalent group. The description of the aryl group described above may be applied except that each of these is a divalent group. Further, the heteroarylene group means one having two bonding positions in the heteroaryl group, that is, a divalent group. The description of the heteroaryl group described above may be applied except that each of these is a divalent group.
In the present specification, the “adjacent” group may mean a substituent substituted on an atom directly connected to the atom in which the corresponding substituent is substituted, a substituent positioned to be sterically closest to the corresponding substituent, or another substituent substituted on the atom in which the corresponding substituent is substituted. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as groups “adjacent” to each other.
In the present specification, “when a substituent is not indicated in a chemical formula or compound structure” means that a hydrogen atom is bonded to a carbon atom. However, since heavy hydrogen (2H, deuterium) is an isotope of hydrogen, some hydrogen atoms may be heavy hydrogen.
In an embodiment of the present application, “when a substituent is not indicated in a chemical formula or compound structure” may mean that all positions which can come as a substituent are hydrogen or heavy hydrogen. That is, heavy hydrogen may be an isotope of hydrogen, and some hydrogen atoms may be heavy hydrogen that is an isotope, and the content of heavy hydrogen may be 0 to 100% at this time.
In an embodiment of the present application, “when a substituent is not indicated in a chemical formula or compound structure”, if heavy hydrogen is not explicitly excluded, such as the content of heavy hydrogen of 0%, the content of hydrogen of 100%, all of the substituents being hydrogen, etc., hydrogen and heavy hydrogen may be mixed and used in the compound.
In an embodiment of the present application, heavy hydrogen is an element having a deuteron consisting of one proton and one neutron as one of the isotopes of hydrogen as a nucleus, it may be expressed as hydrogen-2, and an element symbol may also be written as D or 2H.
In an embodiment of the present application, although isotopes meaning atoms which have the same atomic number (Z), but have different mass numbers (A) have the same number of protons, they may also be interpreted as elements with different numbers of neutrons.
In an embodiment of the present application, when the total number of substituents that a basic compound may have is defined as T1, and the number of specific substituents among them is defined as T2, the meaning of the content T % of the specific substituents may be defined as T2/T1-100=T %.
That is, as an example, the 20% content of heavy hydrogen in the phenyl group represented by
may be expressed as 20% when the total number of substituents that the phenyl group may have is 5 (T1 in Equation) and the number of heavy hydrogens among them is 1 (T2 in Equation). That is, it may be represented by the structural formula below that the content of heavy hydrogen in the phenyl group is 20%.
Further, in an embodiment of the present application, in the case of “a phenyl group having a heavy hydrogen content of 0%”, it may mean a phenyl group that does not contain a heavy hydrogen atom, that is, has 5 hydrogen atoms.
In an embodiment of the present application, there is provided a heterocyclic compound represented by Chemical Formula 1 below.
In Chemical Formula 1,
Since the heterocyclic compound represented by Chemical Formula 1 above has a steric arrangement by fixing a substituent to a specific position, and spatially separates Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) so that strong charge transfer is possible, high efficiency and increased lifespan of the organic light emitting device may be expected when it is used as an organic material in an organic light emitting device.
In an embodiment of the present application, L of Chemical Formula 1 above may be a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group.
In another embodiment, L may be a direct bond; a substituted or unsubstituted C6-C60 arylene group; or a substituted or unsubstituted C2-C60 heteroarylene group.
In another embodiment, L may be a direct bond; a substituted or unsubstituted C6-C40 arylene group; or a substituted or unsubstituted C2-C40 heteroarylene group.
In another embodiment, L may be a direct bond; a substituted or unsubstituted C6-C60 arylene group; or a substituted or unsubstituted C2-C20 heteroarylene group.
In another embodiment, L may be a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; a substituted or unsubstituted triphenylene group; a substituted or unsubstituted fluorenylene group; a substituted or unsubstituted naphthalenylene group; a substituted or unsubstituted anthracenylene group; a substituted or unsubstituted 9,10-dihydroanthracene group; a substituted or unsubstituted carbazole group; a substituted or unsubstituted dibenzothiophenylene group; a substituted or unsubstituted benzofuranylene group; a substituted or unsubstituted benzonaphthothiophenylene group; or a substituted or unsubstituted naphthobenzofuranylene group.
In an embodiment of the present application, m of Chemical Formula 1 above is an integer of 0 to 6, and when m is 2 or more, L in parentheses are the same as or different from each other.
In an embodiment of the present application, m is an integer of 1 to 6, and when m is 2 or more, L in parentheses are the same as or different from each other.
In an embodiment of the present application, m is 0.
In an embodiment of the present application, m is 1.
In an embodiment of the present application, m is 2.
In an embodiment of the present application, m is 3.
In an embodiment of the present application, m is 4.
In an embodiment of the present application, m is 5.
In an embodiment of the present application, m is 6.
In an embodiment of the present application, when m is 2 or more, L in parentheses are the same as or different from each other.
In an embodiment of the present application, n is an integer of 0 to 6, and when n is 2 or more, Z in parentheses are the same as or different from each other.
In an embodiment of the present application, n is an integer of 1 to 6, and when n is 2 or more, Z in parentheses are the same as or different from each other.
In an embodiment of the present application, n is 0.
In an embodiment of the present application, n is 1.
In an embodiment of the present application, n is 2.
In an embodiment of the present application, n is 3.
In an embodiment of the present application, n is 4.
In an embodiment of the present application, n is 5.
In an embodiment of the present application, n is 6.
In an embodiment of the present application, when n is 2 or more, Z in parentheses are the same as or different from each other.
In an embodiment of the present application, m and n are each independently an integer of 0 to 6, and m+n≥−1.
In an embodiment of the present application, m and n may be each independently an integer of 1 to 6, and when m and n are each 2 or more, the substituents in parentheses are the same as or different from each other.
In Chemical Formula 1 above, when a heterocyclic compound represented as a case in which L is not a direct bond, or m is not 0 is used as an organic material in an organic light emitting device, the efficiency and lifespan of the organic light emitting device are more excellent than a case in which L is a direct bond, or m is 0. This is considered to be since stronger charge transfer is possible by spatially further separating HOMO and LUMO since L is not a direct bond.
In an embodiment of the present application, X1 and X2 of Chemical Formula 1 above are each independently O; or S, and X1 and X2 may be different from each other.
In an embodiment of the present application, X1 is O, and X2 is S.
In an embodiment of the present application, X1 is S, and X2 is O.
In an embodiment of the present application, Z of Chemical Formula 1 above may be a substituted or unsubstituted C2-C60 heteroaryl group; or an amine group substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted C6-C4a aryl group and a substituted or unsubstituted C2-C40 heteroaryl group.
In an embodiment of the present application, Z may be a substituted or unsubstituted C2-C40 heteroaryl group; or an amine group substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted C2-C40 aryl group and a substituted or unsubstituted C2-C40 heteroaryl group.
In an embodiment of the present application, Z may be a substituted or unsubstituted C2-C20 heteroaryl group; or an amine group substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted C1-C20 aryl group and a substituted or unsubstituted C2-C20 heteroaryl group.
In an embodiment of the present application, Z of Chemical Formula 1 above may be a group represented by any one of Chemical Formulas 2 to 4 below.
In Chemical Formulas 2 to 4,
denotes a position bonded to Chemical Formula 1 above.
In an embodiment of the present application, L11 and L12 of Chemical Formula 2 above may be the same as or different from each other, and may be each independently a direct bond; a substituted or unsubstituted C6-C40 arylene group or a substituted or unsubstituted C2-C40 heteroarylene group.
In an embodiment of the present application, L11 and L12 may be the same as or different from each other, and may be each independently a direct bond; a substituted or unsubstituted C6-C20 arylene group; or a substituted or unsubstituted C2-C20 heteroarylene group.
In an embodiment of the present application, Z11 and Z12 of Chemical Formula 1 above may be the same as or different from each other, and may be each independently a substituted or unsubstituted C0-C40 aryl group or a substituted or unsubstituted C2-C40 heteroaryl group.
In an embodiment of the present application, Z11 and Z12 may be the same as or different from each other, and may be each independently a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C2-C20 heteroaryl group.
In an embodiment of the present application, Z11 and Z12 may be bonded to each other to form a substituted or unsubstituted C6-C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2-C60 heterocycle.
In an embodiment of the present application, Z11 and Z12 may be different.
In an embodiment of the present application, Z11 may be a substituted or unsubstituted C6-C40 aryl group, and Z12 may be a substituted or unsubstituted C2-C40 heteroaryl group.
In an embodiment of the present application, Z12 may be a substituted or unsubstituted C6-C40 aryl group, and Z11 may be a substituted or unsubstituted C2-C40 heteroaryl group.
In Chemical Formula 2 above, when a heterocyclic compound represented as a case in which one of Z11 and Z12 is an aryl group and the other is a heteroaryl group is used as an organic material in an organic light emitting device, the efficiency and lifespan of the organic light emitting device are more excellent than a case in which both Z11 and Z12 are aryl groups. This is considered to be since stronger charge transfer is possible by spatially further separating HOMO and LUMO since one of Z11 and Z12 is an aryl group and the other is a heteroaryl group.
In an embodiment of the present application, Chemical Formula 2 above may be represented by any one of Chemical Formulas 2-1 to 2-4 below.
In Chemical Formulas 2-1 to 2-4,
In an embodiment of the present application, L13 and L14 of Chemical Formula 2-1 above may be the same as or different from each other, and may be each independently a direct bond; and a substituted or unsubstituted C6-C40 arylene group or a substituted or unsubstituted C2-C40 heteroarylene group.
In an embodiment of the present application, L13 and L14 may be the same as or different from each other, and may be each independently a direct bond; a substituted or unsubstituted C6-C20 arylene group; or a substituted or unsubstituted C2-C20 heteroarylene group.
In an embodiment of the present application, Z13 and Z14 of Chemical Formula 2-1 above may be the same as or different from each other, and may be each independently a substituted or unsubstituted C6-C40 aryl group or a substituted or unsubstituted C2-C40 heteroaryl group.
In an embodiment of the present application, Z13 and Z14 may be the same as or different from each other, and may be each independently a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C2-C20 heteroaryl group.
In an embodiment of the present application, Chemical Formula 3 above may be represented by one of Chemical Formulas 3-1 to 3-4 below. Here,
denotes a position bonded to L1 of Chemical Formula 1 above.
In Chemical Formula 3-1, one or more of X11, X13, and X15 are N, and the rest are as defined in Chemical Formula 3,
In Chemical Formula 3-2, one or more of X11, X12, and X15 are N, and the rest are as defined in Chemical Formula 3,
In Chemical Formula 3-3, one or more of X11 to X13 are N, and the rest are as defined in Chemical Formula 3,
In Chemical Formula 3-4, one or more of X11, X12, and X15 are N, and the rest are as defined in Chemical Formula 3,
In an embodiment of the present application, Chemical Formula 3 above may be selected from structural formulas of Group A below.
Substituent of the structural formulas of Group A above are defined as in Chemical Formula 3 above.
In an embodiment of the present application, Chemical Formula 3-2 above may be represented by Chemical Formula 3-2-1 below.
The definitions of the substituents of Chemical Formula 3-2-1 above are as defined in Chemical Formula 3-2.
In an embodiment of the present application, Chemical Formula 3-3 above may be represented by Chemical Formula 3-3-1 below.
The definitions of the substituents of Chemical Formula 3-3-1 above are as defined in Chemical Formula 3-3.
In an embodiment of the present application, Chemical Formula 3-2 above may be represented by Chemical Formula 3-2-2 or 3-2-3 below.
In Chemical Formulas 3-2-2 and 3-2-3, R27 are the same as or different from each other and are selected from the group consisting of: hydrogen; heavy hydrogen; halogen; a cyano group; a substituted or unsubstituted C1-C60 alkyl group; a substituted or unsubstituted C2-C60 alkenyl group; a substituted or unsubstituted C2-C60 alkynyl group; a substituted or unsubstituted C1-C20 alkoxy group; a substituted or unsubstituted C3-C60 cycloalkyl group; a substituted or unsubstituted C2-C60 heterocycloalkyl group; a substituted or unsubstituted C6-C60 aryl group; a substituted or unsubstituted C2-C60 heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocycle, e is an integer of 0 to 7, and when e is 2 or more, R27 are the same as or different from each other.
In an embodiment of the present application, Chemical Formula 3-4 above may be represented by Chemical Formula 3-4-1 below.
The definitions of the substituents of Chemical Formula 3-4-1 above are as defined in Chemical Formula 3-4.
In an embodiment of the present application, R1 and R2 of Chemical Formula 1 above may be the same as or different from each other, and may be each independently hydrogen; heavy hydrogen; a halogen group; a cyano group; a substituted or unsubstituted C1-C30 alkyl group; or a substituted or unsubstituted C3-C30 cycloalkyl group.
In an embodiment of the present application, a and b are each independently an integer of 0 to 4, and when a and b are each 2 or more, the substituents in parentheses are the same as or different from each other.
In an embodiment of the present application, a is an integer of 0 to 4, and when a is 2 or more, R1 in parentheses are the same as or different from each other.
In an embodiment of the present application, b is an integer of 0 to 4, and when b is 2 or more, R2 in parentheses are the same as or different from each other.
In an embodiment of the present application, R1 and R2 of Chemical Formula 1 above are hydrogen.
In an embodiment of the present application, Chemical Formula above may be represented by Chemical Formula 1-1 or 1-2 below.
In Chemical Formulas 1-1 and 1-2, the definition of each substituent is the same as in Chemical Formula 1.
In an embodiment of the present application, Chemical Formula above provides a heterocyclic compound represented by any one of compounds below.
Further, compounds having intrinsic properties of the introduced substituents may be synthesized by introducing various substituents into the structure of Chemical Formula 1 above. For example, substances satisfying the conditions required for each organic material layer may be synthesized by introducing substituents mainly used for a hole injection layer material, a hole transport layer material, a light emitting layer material, an electron transport layer material, and a charge generation layer material used when manufacturing an organic light emitting device into the core structure.
Further, various substituents are introduced into the structure of Chemical Formula 1 above so that the energy band gap may be enabled to be finely controlled, whereas the properties at the interface between organic materials may be improved, and the use of the substances may be enabled to be diversified.
Meanwhile, the heterocyclic compound is excellent in thermal stability by having a high glass transition temperature (Tg). Such an increase in thermal stability becomes an important factor providing driving stability to the device.
The heterocyclic compound according to an embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds may be prepared first, and the compound of Chemical Formula 1 may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an embodiment of the present application may be prepared based on Preparation Examples to be described later.
Another embodiment of the present application provides an organic light emitting device comprising the heterocyclic compound represented by Chemical Formula 1 above. The “organic light emitting device” may be expressed by terms such as “an organic light emitting diode”, “an organic light emitting diode (OLED)”, “an OLED device”, “an organic electroluminescent device”. etc.
In an embodiment of the present application, there is provided an organic light emitting device comprising: a first electrode; a second electrode; and an organic material layer with one or more layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layer comprise the heterocyclic compound represented by Chemical Formula 1 above.
In an embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.
In another embodiment of the present application, the first electrode may be a cathode, and the second electrode may be an anode.
In an embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 above may be used as a material of the blue organic light emitting device.
In another embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 above may be used as a material of the green organic light emitting device.
In another embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 above may be used as a material of the red organic light emitting device.
Specific details of the heterocyclic compound represented by Chemical Formula 1 above are the same as described above.
The organic light emitting device of the present application may be manufactured by a conventional method and material for manufacturing an organic light emitting device except that an organic material layer with one or more layers is formed using the above-described heterocyclic compound.
The heterocyclic compound may be formed into an organic material layer by a solution application method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, or the like, but the present application is not limited thereto.
The organic material layer of the organic light emitting device of the present application may be formed in a single layer structure, but may be formed in a multilayer structure in which an organic material layer with two or more layers is laminated. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include an organic material layer with a smaller number of layers.
In the organic light emitting device of the present application, the organic material layer may include a light emitting layer, and the light emitting layer may comprise the heterocyclic compound. Since, when the heterocyclic compound is used in the light emitting layer, strong charge transfer is possible by spatially separating Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO), the driving voltage, efficiency, and lifespan of the organic light emitting device may become excellent.
The organic light emitting device of the present disclosure may further comprise one or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, a hole auxiliary layer, and a hole blocking layer.
According to
However, the present application is not limited to such a structure, and as shown in
As an organic light emitting device according to an embodiment of the present application, an organic light emitting device having a two-stack tandem structure is schematically shown in
At this time, the first electron blocking layer, the first hole blocking layer, the second hole blocking layer, etc. described in
An organic material layer comprising the heterocyclic compound represented by Chemical Formula 1 above may further comprise other materials as needed.
In the organic light emitting device according to an embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 above are exemplified below, but these are for illustration only and not for limiting the scope of the present application, and may be substituted with materials known in the art.
As an anode material, materials having a relatively high work function may be used, and transparent conductive oxides, metals, conductive polymers, or the like may be used. Specific examples of the anode material may include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals such as ZnO:Al or SnO2:Sb and oxides; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; etc., but the present application is not limited thereto.
As a cathode material, materials having a relatively low work function may be used, and metals, metal oxides, conductive polymers, or the like may be used. Specific examples of the cathode material may include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; a multilayer structure material such as LiF/Al or LiO2/Al; etc., but the present application is not limited thereto.
As a hole injection material, known hole injection materials may also be used, and for example, phthalocyanine compounds such as copper phthalocyanine, etc. disclosed in U.S. Pat. No. 4,356,429, or starburst-type amine derivatives disclosed in the literature [Advanced Material, 6, p.677 (1994)] such as Tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4′,4-Tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), and a soluble conductive polymer of polyaniline/dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/camphor sulfonic acid or polyaniline/poly(4-styrene sulfonate), etc. may be used.
As a hole transport material, pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular weight or high molecular weight materials may also be used.
As an electron transport material, metal complexes or the like of oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, and 8-hydroxyquinoline and its derivatives may be used, and high molecular weight materials as well as low molecular weight materials may also be used.
As an electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.
As a light emitting material, a red, green, or blue light emitting material may be used, and two or more light emitting materials may be mixed and used as needed. At this time, two or more light emitting materials may be deposited and used as individual sources, or may be premixed to be deposited and used as a single source. Further, as a light emitting material, a fluorescent material may be used, but a phosphorescent material may also be used. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used alone, but materials in which the host material and the dopant material involve together in light emission may also be used.
When mixing and using the host of the light emitting material, hosts of the same series may be mixed and used, or hosts of different series may also be mixed and used. For example, any two or more types of materials of n-type host materials or p-type host materials may be selected and used as a host material of the light emitting layer.
In the organic light emitting device of the present application, the organic material layer may include a light emitting layer, and the light emitting layer may comprise the heterocyclic compound as a host material of the light emitting material.
In the organic light emitting device of the present application, the light emitting layer may comprise two or more host materials, and at least one of the host materials may comprise the heterocyclic compound as a host material of the light emitting material.
In the organic light emitting device of the present application, two or more host materials may be pre-mixed and used as the light emitting layer, and at least one of the two or more host materials may include the heterocyclic compound as a host material of a light emitting material.
The pre-mixing means placing and mixing two or more host materials of the light emitting layer in one source of supply before depositing on the organic material layer.
In the organic light emitting device of the present application, the light emitting layer may comprise two or more host materials, the two or more host materials may each include one or more p-type host materials and n-type host materials, and at least one of the host materials may include the heterocyclic compound as a host material of the light emitting material. In this case, the driving voltage, efficiency and lifespan of the organic light emitting device may become excellent.
The organic light emitting device according to an embodiment of the present application may be a top emission type, a back emission type, or a double side emission type depending on materials used.
A heterocyclic compound according to an embodiment of the present application may act on a principle similar to that applied to an organic light emitting device even in an organic electronic device including an organic solar cell, an organic photoreceptor, an organic transistor, etc.
Hereinafter, the present specification will be described in more detail through Examples, but these are only for exemplifying the present application and not for limiting the scope of the present application.
44.2 g (179 mmol) of 4-bromodibenzofuran, 30.0 g (179 mmol) of 2-(methylthio)phenylboronic acid, 10.3 g (8.92 mmol) of Pd(PPh3)4, 56.8 g (536 mmol) of Na2CO3, 300 mL of toluene, 50 mL of ethanol, and 50 mL of H2O were put into a 1 L round-bottom flask and stirred at 125° C. for 16 hours (h). After completing the reaction, the temperature was lowered to room temperature, and the reaction product was extracted with distilled water, brine, and ethyl acetate (hereinafter referred to as EtOAc). The solution was dried over anhydrous MgSO4 and concentrated. The concentrated reaction product was purified by a hexane column to obtain 39.4 g (136 mmol) (76%) of Intermediate A-4.
39.4 g (136 mmol) of Intermediate A-4 was put into a 2 L round-bottom flask and dissolved in tetrahydrofuran (hereinafter referred to as THF) and acetic acid, and then 35 wt (18 mL) of hydrogen peroxide was slowly added dropwise. Stirring was performed at room temperature for 8 hours. After completing the reaction, the solvent was removed from the reaction product using a rotary evaporator, and the solvent-removed reaction product was extracted with DCM, brine, and distilled water. The solution was dried over anhydrous MgSO4 and concentrated. After performing concentration, 41.6 g (136 mmol) (100%) of Intermediate A-3 was obtained, and the next reaction was carried out immediately. DCM refers to dichloromethane (hereinafter referred to as DCM).
41.6 g (136 mmol) of Intermediate A-3 was put into a 1 L round-bottom flask, dissolved in 180 mL of Triflic acid, and then stirred at room temperature for 2 days. Thereafter, 420 mL of pyridine and 10 mL of an aqueous K2CO3 saturated solution were slowly added dropwise to the solution. The mixture was refluxed for 4 hours by gradually raising the temperature. After completing the reaction, the reaction product was cooled to room temperature, and washed with distilled water and methanol. After drying the solid, it was separated by a column under the condition of DCM:Hexane=1:1 to obtain 30.53 g (111 mmol) (82%) of Intermediate A-2.
30.5 g (111 mmol) of Intermediate A-2 was put into a 1 L round-bottom flask and dissolved in 300 mL of chloroform, and then 6.4 mL (117 mmol) of bromine was slowly added dropwise. Thereafter, after stirring the mixture at room temperature, when the reaction was completed, the reaction product was washed with methanol, and the solid was dried. After dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 31.4 g (80%) of Intermediate A-1. DCB refers to 1,2-dichlorobenzene (hereinafter referred to as DCB).
10.0 g (28.3 mmol) of Intermediate A-1, 10.8 g (42.5 mmol) of bis(pinacolato)diboron, 1.04 g (1.42 mmol) of Pd(dppf)Cl2, 5.55 g (56.6 mmol) of potassium acetate (hereinafter referred to as KOAc), and 100 mL of 1,4-dioxane were put into a 250 mL round-bottom flask, and refluxed at 130° C. for 3 hours. After sieving inorganic materials from a reaction product while it was hot, the reaction product was washed with DCM. The solution was dried with a rotary evaporator, and then separated by a column under the condition of DCM;Hexane=1:2 to obtain 10.1 g (25.2 mmol) (89%) of Intermediate A.
60.7 g (218 mmol) of 4-bromodibenzo[b,d]thiophen-3-ol, 30.0 g (218 mmol) of (2-hydroxyphenyl)boronic acid, 12.6 g (10.9 mmol of Pd(PPh3)4, 46.11 g (435 mmol) of Na2CO3, 300 mL of toluene, 50 mL of ethanol, and 50 mL of H2O were put into a 1 L round-bottom flask, and stirred at 130° C. for 14 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was extracted with distilled water, brine, and EtOAc.
Thereafter, the solution was dried over anhydrous MgSO4 and concentrated. The concentrated reaction product was purified by a column under the condition of MC to obtain 50.2 g (172 mmol) (79%) of Intermediate B-3.
50.2 g (172 mmol) of Intermediate B-3 was put into a 1 L round-bottom flask, dissolved in 28.6 mL (206 mmol) of p-toluenesulfonic acid and 500 mL of toluene under nitrogen condition, and then stirred at 100° C. for 14 hours. After completing the reaction, the reaction product was cooled to room temperature, and extracted with an aqueous NaHCO3 saturated solution, distilled water, and EtOAc. Thereafter, after drying the solution over anhydrous MgSO4, the reaction product was concentrated by a rotary evaporator. The concentrated reaction product was purified by a column under the condition of MC:Hex=1:1 to obtain 26.4 g (96.2 mmol) (56%) of Intermediate B-2.
26.4 g (96.2 mmol) of Intermediate B-2 was put into a 1 L round-bottom flask and dissolved in 260 mL of chloroform, and then 5.6 mL (101 mmol) of bromine was slowly added dropwise. After stirring the mixture at room temperature, when the reaction was completed, the reaction product was washed with methanol, and the solid was dried. After dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 29.2 g (82.8 mmol) (86%) of Intermediate B-1.
10.0 g (28.3 mmol) of Intermediate B-1, 10.8 g (42.5 mmol) of bis(pinacolato)diboron, 1.04 g (1.42 mmol) of Pd(dppf)Cl2, 5.56 g (56.6 mmol) of KOAc, and 100 mL of 1,4-dioxane were put into a 250 mL round-bottom flask, and refluxed at 130° C. for 2 hours. After sieving inorganic materials from a reaction product while it was hot, the reaction product was washed with DCM. The solution was dried with a rotary evaporator, and then separated by a column under the condition of DCM;Hexane=1:2 to obtain 10.1 g (25.2 mmol) (89%) of Intermediate B.
10.0 g (36.5 mmol) of Intermediate A-2 was put into a 250 mL round-bottom flask and dissolved in 100 mL of chloroform, and then 4.2 mL (76.5 mmol) of bromine was slowly added dropwise. After stirring the mixture at room temperature, when the reaction was completed, the reaction product was washed with methanol, and the solid was dried. After dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 9.61 g (61%) of Intermediate C.
10.0 g (25.0 mmol) of Intermediate A, 6.55 g (24.5 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine (Compound C1), 1.44 g (1.2 mmol) of Pd(PPh3)4, 6.91 g (50.0 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 3 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was washed with distilled water and methanol. After drying the solid and dissolving the dried solid in hot DCB, it separated by a column under the condition of DCB to obtain 10.1 g (20.0 mmol) (80%) of Compound 1.
10.0 g (25.0 mmol) of Intermediate A, 7.78 g (24.5 mmol) of 2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3,5-triazine (Compound C2), 1.44 g (1.2 mmol) of Pd(PPh3)4, 6.91 g (50.0 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 2 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was washed with distilled water and methanol. After drying the solid and dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 11.8 g (21.2 mmol) (85%) of Compound 2.
10.0 g (25.0 mmol) of Intermediate A, 8.76 g (24.5 mmol) of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (Compound C2), 1.44 g (1.2 mmol) of Pd(PPh3)4, 6.91 g (50.0 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 3 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was washed with distilled water and methanol. After drying the solid and dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 12.1 g (20.3 mmol) (81%) of Compound 4.
Compounds 5, 6, 9, 10, 12, 14, 202, 236, 310, 426, 433, 437, and 441 were prepared and synthesized in the same manner as in the preparation of Compound 1 above except that C of Table 1 below was used instead of Compound C1 in the preparation of Compound 1 above.
Compounds 36, 38, and 41 were prepared and synthesized in the same manner as in the preparation of Compound 1 above except that Intermediate B of Table 1 below was used instead of Intermediate A in the preparation of Compound 1 above, and C of Table 1 below was used instead of Compound C1.
20.0 (50.0 mmol) of Intermediate A, 7.40 g (24.5 mmol) of 2-([1,1′-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (Compound C249), 1.44 g (1.2 mmol) of Pd(PPh3)4, 6.91 g (50.0 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 5 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was washed with distilled water and methanol. After drying the solid and dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 16.4 g (21.1 mmol) (86%) of Compound 249.
10.0 g (28.3 mmol) of Intermediate A-1, 12.9 g (29.7 mmol) of 4,6-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (Compound C17), 1.64 g (1.4 mmol) of Pd(PPh3)4, 7.82 g (56.6 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 4 hours. After completing the reaction, the temperature was lowered to room temperature, and the reaction product was washed with distilled water and methanol. After drying the solid and dissolving the dried solid in hot DCB, it was separated by a column under the condition of DCB to obtain 14.3 g (24.6 mmol) (87%) of Compound 17.
Compounds 23, 26, 446, and 450 were prepared and synthesized in the same manner as in the preparation of Compound 17 above except that C of Table 2 below was used instead of Compound C17 in the preparation of Compound 17 above.
10.0 g (28.3 mmol) of Intermediate A-1, 10.01 g (31.1 mmol) of di([1,1′-biphenyl]-4-yl)amine (Compound C51), 1.30 g (1.4 mmol) of Pd2dba3, 1.35 g (2.8 mmol) of XPhos, 5.44 g (56.6 mmol) of sodium tert-butoxide (hereinafter referred to as NaOtBu), and 100 mL of xylene were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 2 hours. After completing the reaction, the temperature was lowered to room temperature, and filtration was performed with a Celite filter. After concentrating the reaction product, the concentrated reaction product was separated by a column under the condition of MC:Hexane=1:4 to obtain 15.6 g (26.3 mmol) (93%) of Compound 51.
Compounds 67, 68, 70, 72, 80, 84, 256, 258, 276, and 351 were prepared and synthesized in the same manner as in the preparation of Compound 51 above except that C of Table 3 below was used instead of Compound C51 in the preparation of Compound 51 above.
Compounds 151, 152, 153, and 386 were prepared and synthesized in the same manner as in the preparation of Compound 51 above except that Intermediate B-1 was used instead of Intermediate A-1 in the preparation of Compound 51 above, and C of Table 3 below was used instead of Compound C51.
10.0 g (28.3 mmol) of Intermediate A-1, 11.36 g (31.1 mmol) of (4-([1,1′-biphenyl]-4-yl(phenyl)amino)phenyl)boronic acid (Compound C95), 1.64 g (1.4 mmol) of Pd(PPh3)4, 7.82 g (56.6 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 4 hours. After completing the reaction, the temperature was lowered to room temperature, and filtration was performed with a Celite filter. After concentrating the reaction product, the concentrated reaction product was separated by a column under the condition of MC:Hexane=1:4 to obtain 14.5 g (24.3 mmol) (86%) of Compound 95.
Compounds 97, 106, 109, 118, 122, 126, 140, 141, 143, 201, 208, and 384 were prepared and synthesized in the same manner as in the preparation of Compound 95 above except that C of Table 4 below was used instead of Compound C95 in the preparation of Compound 95 above.
Compounds 172 and 173 were prepared and synthesized in the same manner as in the preparation of Compound 95 above except that Intermediate B-1 was used instead of Intermediate A-1 in the preparation of Compound 95 above, and C of Table 4 below was used instead of Compound C95.
10.0 g (23.6 mmol) of 6,9-dibromobenzo[b]benzo[4,5]thieno[2,3-g]benzofuran (Intermediate C), 8.78 g (23.6 mmol) of N-(4-(naphthalen-2-yl)phenyl)-[1,1′-biphenyl]-4-amine (Compound C147), 1.06 g (1.16 mmol) of Pd2dba3, 1.13 g (2.36 mmol) of XPhos, 4.54 g (47.2 mmol) of NaOtBu, and 100 mL of xylene were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 4 hours. After completing the reaction, the temperature was lowered to room temperature, and filtration was performed with a Celite filter. After concentrating the reaction product, the concentrated reaction product was separated by a column under the condition of MC:Hexane=1:4 to obtain 10.2 g (14.1 mmol) (61%) of N-([1,1′-biphenyl]-4-yl)-9-bromo-N-(4-(naphthalen-2-yl)phenyl)benzo[b]benzo[4,5]thieno[2,3-g]benzofuran-6-amine (Compound D147). 10.0 g (13.8 mmol) of D147, 2.53 g (20.8 mmol) of phenylboronic acid (Compound E1), 0.80 g (0.7 mmol) of Pd(PPh3)4, 3.81 g (27.6 mmol) of K2CO3, 30 mL of distilled water, and 100 mL of 1,4-dioxane were put into a 500 mL round-bottom flask, and refluxed at 130° C. for 4 hours. After completing the reaction, the temperature was lowered to room temperature, and filtration was performed with a Celite filter. After concentrating the reaction product, the concentrated reaction product was separated by a column under the condition of MC:Hexane=1:4 to obtain 9.36 g (13.0 mmol) (94%) of Compound 147.
Compounds 148 and 149 were prepared and synthesized in the same manner as in the preparation of Compound 147 above except that C and E of Table 5 below were used instead of Compound C147 and Compound E1 in the preparation of Compound 147 above.
The compounds described in the present specification were prepared in the same manner as in Preparation Examples above, and the synthesis confirmation results of the prepared compounds are shown in Tables 6 and 7 below. Table 6 below is the measurement values of 1H NMR (CDCl3, 400 Mz), and Table 7 below is the measurement values of the FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).
1H NMR (CDCl3, 400 Mz)
Glass substrates coated with a thin film of ITO to a thickness of 1,500 Å were washed with distilled water and ultrasonic waves. After washing the substrates with distilled water, ultrasonic cleaning was performed on the washed substrates with solvents such as acetone, methanol, isopropyl alcohol, etc., and the ultrasonic cleaned substrates were dried, and WOC-treated for 5 minutes using UV in a UV cleaner. Thereafter, after transferring the substrates to a plasma cleaner (PT), plasma treatment was performed in order to remove the ITO work function and residual film in a vacuum state, and then the substrates were transferred to thermal deposition equipment for organic deposition.
As common layers on the ITO transparent electrodes (anodes), a hole injection layer 2-TNATA (4,4′,4″-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine) were formed.
A light emitting layer was thermal vacuum deposited thereon as follows. The light emitting layer was deposited to a thickness of 500 Å by doping 3 wt % of (piq)2(Ir)(acac) on the host using the compounds shown in Table 8 below as a host and (piq)2(Ir)(acac) as a red phosphorescent dopant. Thereafter, BCP was deposited to a thickness of 60 Å as a hole blocking layer, and Alq3 was deposited to a thickness of 200 Å thereon as an electron transport layer. Finally, after depositing lithium fluoride (LiF) to a thickness of 10 Å on the electron transport layer to form an electron injection layer, organic light emitting devices were manufactured by depositing an aluminum (Al) cathode to a thickness of 1,200 Å on the electron injection layer to form cathodes.
Meanwhile, all organic compounds required for fabricating OLED devices were vacuum sublimated and purified under 10−6 to 10−8 torr for each material respectively, and used for OLED fabrication.
Electroluminescence (EL) characteristics were measured for the organic light emitting devices fabricated as described above with M7000 of McScience, and T90 values were measured with the measurement results when the reference luminance was 6,000 cd/m7 through the device lifespan measuring system (M6000) manufactured by McScience. The characteristics of the organic light emitting devices of the present disclosure are as shown in Table 8 below.
Glass substrates coated with a thin film of ITO to a thickness of 1,500 Å were washed with distilled water and ultrasonic waves. After washing the substrates with distilled water, ultrasonic cleaning was performed on the washed substrates with solvents such as acetone, methanol, isopropyl alcohol, etc., and the ultrasonic cleaned substrates were dried, and UVO-treated for 5 minutes using UV in a UV cleaner. Thereafter, after transferring the substrates to a plasma cleaner (PT), plasma treatment was performed in order to remove the ITO work function and residual film in a vacuum state, and then the substrates were transferred to thermal deposition equipment for organic deposition.
As common layers on the ITO transparent electrodes (anodes), a hole injection layer 2-TNATA (4,4,4′-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine) were formed.
A light emitting layer was thermal vacuum deposited thereon as follows. The light emitting layer was deposited to a thickness of 500 Å by doping 3 wt % of (piq)2(Ir)(acac) on the host using one of the compounds shown in Table 9 below as a host and (piq)2(Ir)(acac) as a red phosphorescent dopant. Thereafter, BCP was deposited to a thickness of 60 Å as a hole blocking layer, and Alq3 was deposited to a thickness of 200 Å thereon as an electron transport layer. Finally, after depositing lithium fluoride (LiF) to a thickness of 10 Å on the electron transport layer to form an electron injection layer, organic light emitting devices were manufactured by depositing an aluminum (Al) cathode to a thickness of 1,200 Å on the electron injection layer to form cathodes.
Meanwhile, all organic compounds required for fabricating OLED devices were vacuum sublimated and purified under 10−6 to 10−8 torr for each material respectively, and used for OLED fabrication.
Electroluminescence (EL) characteristics were measured for the organic light emitting devices fabricated as described above with M7000 of McScience, and T90 values were measured with the measurement results when the reference luminance was 6,000 cd/m2 through the device lifespan measuring system (M6000) manufactured by McScience. The characteristics of the organic light emitting devices according to an embodiment of the present disclosure are as shown in Table 9.
Compounds A to I used in Tables 8 and 9 above are as follows.
As can be seen from the results of Tables 8 and 9 above, in the case of the organic light emitting devices of Examples 1 to 94 in which the heterocyclic compound of Chemical Formula 1 above of the present application was used as a host for the organic material layer, particularly the light emitting layer, of the organic light emitting device, it could be confirmed that the driving voltage and efficiency could be improved compared to those of the organic light emitting devices of Comparative Examples 1 to 18.
That is, when compared with Compounds A to C used in Comparative Examples 1 to 3, it could be confirmed that the heterocyclic compound of Chemical Formula 1 above of the present application used in Examples 1 to 94 has a steric arrangement by fixing the position of an amine group or a heteroaryl group corresponding to the substituent Z of Chemical Formula 1 above to a specific position as in Chemical Formula 1 above, the heterocyclic compound is suitable as a red host since a strong charge transfer is possible by spatially separating Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO), and high efficiency may be expected when it is used as an organic material in an organic light emitting device.
Further, HOMO, LUMO, Eg, S1, T1, and dipole moment values were respectively calculated for the molecules of Compounds D to I used in Comparative Examples 4 to 18 above and Compounds 1, 6, 51, 95, and 100 included in the heterocyclic compounds of Chemical Formula 1 above of the present application, and the results are shown in Table 10 below.
Eg, T1, and S1 denote a bandgap, a triplet excited state (T1 level), and a singlet excited state (S1 level) respectively.
It can be confirmed from the molecular calculation results of Table 10 above that the band gap is smaller when Z in Chemical Formula 1 above of the present application is an amine group or a heteroaryl group than when it is an aryl group (Compounds D and E).
That is, the compounds (Compounds 1 and 6) in which Z of Chemical Formula 1 above is a heteroaryl group having N-type characteristics have a lower LUMO than the compounds (Compounds D and E) in which Z of Chemical Formula 1 above is an aryl group, thereby facilitating electron injection.
Further, the compounds (Compounds 51, 95, and 100) in which Z of Chemical Formula 1 above is an amine group having P-type characteristics has a higher HOMO than the compounds (Compounds D and E) in which Z of Chemical Formula 1 above is an aryl group, thereby facilitating hole injection.
The cause of such results is that an exciplex phenomenon, which is a phenomenon of emission by an energy difference between the LUMO level of the acceptor (N-type host) and the HOMO level of the donor (P-type host) due to electron exchange between two molecules, is more likely to occur in the heterocyclic compound represented by Chemical Formula 1 according to the present application when the heterocyclic compound represented by Chemical Formula 1 according to the present application is used in a device by having as substituents a heteroaryl group having an N-type characteristic rather than an aryl group that is the substituent Z of Chemical Formula 1 above, and an amine group having a P-type characteristic rather than the aryl group.
When a donor (P-type host) having a good hole transport ability and an acceptor (N-type host) having a good electron transport ability are used as a host of the light emitting layer by the exciplex phenomenon, since holes are injected into the P-type host and electrons are injected into the N-type host, the electrons and holes are easily combined in the light emitting layer.
That is, when the heterocyclic compound represented by Chemical Formula 1 above of the present application is used in a device, it can be confirmed that there is an effect of improving the driving voltage and efficiency compared to when Z of Chemical Formula 1 above is an aryl group.
Further, as can be seen from the results of Table 9 above, it can be confirmed that effects of improving the driving voltage and efficiency are excellent when X1 and X2 above are different compared to when X1 and X2 of Chemical Formula 1 above of the present application are the same (Compounds F to I).
It is judged that this is since, when looking at the molecular calculation results of Table 10 above, as the HOMO of the heteroskeleton composed of two or more atoms is formed lower than the HOMO of the heteroskeleton composed of one atom, energy may be transferred more efficiently without energy loss.
Further, as can be seen from the molecular calculation results of Table 10 above, it is judged that, as the dipole moment of the heteroskeleton composed of two or more atoms is formed higher than the dipole moment of the heteroskeleton composed of one atom, the recombination ratio of the electrons and holes is increased, and the driving voltage and lifespan characteristics of the device are excellent.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0180272 | Dec 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/017701 | 11/29/2021 | WO |
