Patent Application
20230337526
The present specification relates to a compound, and an organic light emitting device including the same.
This application claims priority to and the benefits of Korean Patent Application No. 10-2020-0078447, filed with the Korean Intellectual Property Office on Jun. 26, 2020, the entire contents of which are incorporated herein by reference.
An electroluminescent device is one type of self-emissive display devices, and has an advantage of having a wide viewing angle, and a high response speed as well as having an excellent contrast.
An organic light emitting device has a structure disposing an organic thin film between two electrodes. When a voltage is applied to an organic light emitting device having such a structure, electrons and holes injected from the two electrodes bind and pair in the organic thin film, and light emits as these annihilate. The organic thin film may be formed in a single layer or a multilayer as necessary.
A material of the organic thin film may have a light emitting function as necessary. For example, as a material of the organic thin film, compounds capable of forming a light emitting layer themselves alone may be used, or compounds capable of performing a role of a host or a dopant of a host-dopant-based light emitting layer may also be used. In addition thereto, compounds capable of performing roles of hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection and the like may also be used as a material of the organic thin film.
Development of an organic thin film material has been continuously required for enhancing performance, lifetime or efficiency of an organic light emitting device.
The present specification is directed to providing a compound, and an organic light emitting device including the same.
One embodiment of the present specification provides a compound of the following Chemical Formula 1.
In Chemical Formula 1,
Another embodiment provides an organic light emitting device including a first electrode; a second electrode provided opposite to the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes one or more types of the compound of Chemical Formula 1.
Another embodiment provides a composition for forming an organic material layer, the composition including the compound of Chemical Formula 1; and a compound of the following Chemical Formula 2 or 3.
In Chemical Formula 2,
A compound described in the present specification can be used as a material of an organic material layer of an organic light emitting device. The compound is capable of performing a role of a hole injection material, a hole transfer material, a light emitting material, an electron transfer material, an electron injection material, a charge generation material and the like in an organic light emitting device. Particularly, the compound can be used as a material of a light emitting layer of an organic light emitting device.
Chemical Formula 1 has two substituents at specific positions of triphenylene, and by necessarily including a heteroaryl group including N, superior light emission efficiency and lifetime can be provided when used in a device by enhancing electron stability and mobility.
In addition, the triphenylene and all substituents substituting the triphenylene may be substituted with deuterium in Chemical Formula 1, and by the compound of Chemical Formula 1 being substituted with one or more deuterium, BDE (bond-dissociation energy) of the C-D bond of the molecule substituted with deuterium is enhanced, and a superior lifetime can be provided when used in a device.
When using the compound of Chemical Formula 1 and a compound of Chemical Formula 2 or 3 together as a material of a light emitting layer of an organic light emitting device, a driving voltage can be lowered, light emission efficiency can be enhanced, and lifetime properties can be enhanced in the device.
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Hereinafter, the present specification will be described in more detail.
In the present specification, a description of a certain part “including” certain constituents means capable of further including other constituents, and does not exclude other constituents unless particularly stated on the contrary.
A term “substitution” means a hydrogen atom bonding to a carbon atom of a compound being changed to another substituent, and the position of substitution is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which a substituent can substitute, and when two or more substituents substitute, the two or more substituents may be the same as or different from each other.
In the present specification, “substituted or unsubstituted” means being 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 being unsubstituted, or being substituted with a substituent linking two or more substituents selected from among the substituents illustrated above, or being unsubstituted.
In the present specification, a “case of a substituent being not indicated in a chemical formula or compound structure” means that a hydrogen atom bonds to a carbon atom. However, since deuterium (2H) is an isotope of hydrogen, some hydrogen atoms may be deuterium.
In one embodiment of the present application, a “case of a substituent being not indicated in a chemical formula or compound structure” may mean that positions that may come as a substituent may all be hydrogen or deuterium. In other words, since deuterium is an isotope of hydrogen, some hydrogen atoms may be deuterium that is an isotope, and herein, a content of the deuterium may be from 0% to 100%.
In one embodiment of the present application, in a “case of a substituent being not indicated in a chemical formula or compound structure”, hydrogen and deuterium may be mixed in compounds when deuterium is not explicitly excluded such as a deuterium content being 0%, a hydrogen content being 100% or substituents being all hydrogen.
In one embodiment of the present application, deuterium is one of isotopes of hydrogen, is an element having deuteron formed with one proton and one neutron as a nucleus, and may be expressed as hydrogen-2, and the elemental symbol may also be written as D or 2H.
In one embodiment of the present application, an isotope means an atom with the same atomic number (Z) but with a different mass number (A), and may also be interpreted as an element with the same number of protons but with a different number of neutrons.
In one embodiment of the present application, a meaning of a content T% of a specific substituent may be defined as T2/T1x100=T% when the total number of substituents that a basic compound may have is defined as T1, and the number of specific substituents among these is defined as T2.
In other words, in one example, having a deuterium content of 20% in a phenyl group represented by
means that the total number of substituents that the phenyl group may have is 5 (T1 in the formula), and the number of deuterium among these is 1 (T2 in the formula). In other words, having a deuterium content of 20% in a phenyl group may be represented by the following structural formulae.
In addition, in one embodiment of the present application, “a phenyl group having a deuterium content of 0%” may mean a phenyl group that does not include a deuterium atom, that is, a phenyl group that has 5 hydrogen atoms.
In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group includes linear or branched, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be from 1 to 60, specifically from 1 to 40 and more specifically from 1 to 20. Specific examples thereof 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, 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 linear or branched, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20. Specific examples thereof may 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, 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, a stilbenyl group, a styrenyl group and the like, but are not limited thereto.
In the present specification, the alkynyl group includes linear or branched, and may be further substituted with other substituents. The number of carbon atoms of the alkynyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20.
In the present specification, the cycloalkyl group includes monocyclic or polycyclic having 3 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the polycyclic means a group in which the cycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a cycloalkyl group, but may also be different types of cyclic groups such as a heterocycloalkyl group, an aryl group and a heteroaryl group. The number of carbon atoms of the cycloalkyl group may be from 3 to 60, specifically from 3 to 40 and more specifically from 5 to 20. Specific examples thereof 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 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 monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the polycyclic means a group in which the heterocycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heterocycloalkyl group, but may also be different types of cyclic groups such as a cycloalkyl group, an aryl group and a heteroaryl group. The number of carbon atoms of the heterocycloalkyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 20.
In the present specification, the aryl group includes monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the polycyclic means a group in which the aryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be an aryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and a heteroaryl group. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be from 6 to 60, specifically from 6 to 40 and more specifically from 6 to 25. When the aryl group is dicyclic or higher, the number of carbon atoms may be from 8 to 60, 8 to 40, or 8 to 30. Specific examples of the aryl group may include a phenyl group, a biphenyl group, a triphenyl 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 ring group thereof, and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.
When the fluorenyl group is substituted,
and the like may be included, however, the structure is not limited thereto.
In the present specification, the heteroaryl group includes O, S, SO2, Se, N or Si as a heteroatom, includes monocyclic or polycyclic, and may be further substituted with other substituents. Herein, the polycyclic means a group in which the heteroaryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heteroaryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and an aryl group. The number of carbon atoms of the heteroaryl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 25. When the heteroaryl group is dicyclic or higher, the number of carbon atoms may be from 4 to 60, 4 to 40, or 4 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 dioxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a qninozolinyl 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 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, 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 phenothiathiazinyl group, a phthalazinyl group, a naphthylidinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrobenzo[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 benzofuro[2,3-d]pyrimidyl group; a benzothieno[2,3-d]pyrimidyl group; a benzofuro[2,3-a]carbazolyl group, a benzothieno[2,3-a]carbazolyl group, a 1,3-dihydroindolo[2,3-a]carbazolyl group, a benzofuro[3,2-a]carbazolyl group, a benzothieno[3,2-a]carbazolyl group, a 1,3-dihydroindolo[3,2-a]carbazolyl group, a benzofuro[2,3-b]carbazolyl group, a benzothieno[2,3-b]carbazolyl group, a 1,3-dihydroindolo[2,3-b]carbazolyl group, a benzofuro[3,2-b]carbazolyl group, a benzothieno[3,2-b]carbazolyl group, a 1,3-dihydroindolo[3,2-b]carbazolyl group, a benzofuro[2,3-c]carbazolyl group, a benzothieno[2,3-c]carbazolyl group, a 1,3-dihydroindolo[2,3-c]carbazolyl group, a benzofuro[3,2-c]carbazolyl group, a benzothieno[3,2-c]carbazolyl group, a 1,3-dihydroindolo[3,2-c]carbazolyl group, a 1,3-dihydroindeno[2,1-b]carbazolyl group, a 5,11-dihydroindeno[1,2-b]carbazolyl group, a 5,12-dihydroindeno[1,2-c]carbazolyl group, a 5,8-dihydroindeno[2,1-c]carbazolyl group, a 7,12-dihydroindeno[1,2-a]carbazolyl group, a 11,12-dihydroindeno[2,1-a]carbazolyl group and the like, but are not limited thereto.
In the present specification, the silyl group is a substituent including Si, having the Si atom directly linked as a radical, and is represented by -Si(R101)(R102)(R103). R101 to R103 are the same as or different from each other, and may be each independently a substituent formed with at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heteroaryl 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 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 formed with at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl 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 as the alkyl group or the aryl group, the examples described above may be applied. Examples of the phosphine oxide group may include a 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 formed with at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl 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 although not particularly limited thereto, the number of carbon atoms is preferably from 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 and the like, but are not limited thereto.
In the present specification, the examples of the aryl group described above may be applied to the arylene group except that the arylene group is a divalent group.
In the present specification, the examples of the heteroaryl group described above may be applied to the heteroarylene group except that the heteroarylene group is a divalent group.
One embodiment of the present specification provides a compound represented by Chemical Formula 1.
In one embodiment of the present specification, d1 and d2 are each an integer of 0 to 3, and d3 is an integer of 0 to 4.
In one embodiment of the present specification, d1, d2 and d3 are 0.
In one embodiment of the present specification, d1 and d2 are 3, and d3 is 4.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C6 to C30 arylene group; or a substituted or unsubstituted C2 to C30 heteroarylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C6 to C20 arylene group; or a substituted or unsubstituted C2 to C20 heteroarylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted phenylene group.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or any one selected from among the following structures.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or a phenylene group. When L1 and L2 are a phenylene group, triphenylene and Z1, or triphenylene and Z2 may bond at a para or meta position, which is effective in increasing molecular stability by reducing steric hindrance between the molecules.
In one embodiment of the present specification, L1 and L2 may be a direct bond.
In one embodiment of the present specification, any one of L1 and L2 is a direct bond, and the other one may be a substituted or unsubstituted C6 to C20 arylene group.
In one embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted silyl group; a substituted or unsubstituted fluorenyl group; or a heteroaryl group represented by any one of the following Chemical Formulae 1-1 to 1-4, and at least one of Z1 and Z2 is a heteroaryl group represented by any one of the following Chemical Formulae 1-1 to 1-3.
In Chemical Formulae 1-1 to 1-4,
In one embodiment of the present specification, X1 to X3 of Chemical Formula 1-1 are each N or CR, and at least one of X1 to X3 is N.
In one embodiment of the present specification, X1 to X3 of Chemical Formula 1-1 may be N.
In one embodiment of the present specification, X1 and X2 of Chemical Formula 1-1 are N, X3 is CR, and R may be hydrogen.
In one embodiment of the present specification, X1 and X3 of Chemical Formula 1-1 are N, X2 is CR, and R may be hydrogen.
In one embodiment of the present specification, X1 of Chemical Formula 1-1 is N, X2 and X3 are CR, and R may be hydrogen.
In one embodiment of the present specification, X2 of Chemical Formula 1-1 is N, X1 and X3 are CR, and R may be hydrogen.
In one embodiment of the present specification, X3 of Chemical Formula 1-1 is N, X1 and X2 are CR, and R may be hydrogen.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted fluorenyl group; a substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted dibenzothiophene group; or a substituted or unsubstituted carbazole group.
In one embodiment of the present specification, Ar1 and Ar2 of Chemical Formula 1-1 are each independently a phenyl group unsubstituted or substituted with deuterium; a biphenyl group; a fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; 9,9′-spirobi[fluorene]; a substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted dibenzothiophene group; or a substituted or unsubstituted carbazole group.
When Ar1 or Ar2 of Chemical Formula 1-1 is a substituted or unsubstituted carbazole group, the bonding position is either nitrogen of the pyridine ring or carbon of the benzene ring.
In one embodiment of the present specification, X4 and X5 of Chemical Formula 1-2 are each N or CR, and at least one of X4 and X5 is N.
In one embodiment of the present specification, X4 and X5 of Chemical Formula 1-2 are N.
In one embodiment of the present specification, A of Chemical Formula 1-2 is a substituted or unsubstituted monocyclic or polycyclic aryl ring; or a monocyclic or polycyclic heteroring substituted or unsubstituted and including O or S.
In one embodiment of the present specification, A of Chemical Formula 1-2 is a substituted or unsubstituted monocyclic aryl ring; or a polycyclic heteroring substituted or unsubstituted and including O or S.
In one embodiment of the present specification, A of Chemical Formula 1-2 is a substituted or unsubstituted benzene ring; a substituted or unsubstituted benzofuran ring; or a substituted or unsubstituted benzothiophene ring.
In one embodiment of the present specification, A of Chemical Formula 1-2 is a benzene ring; a benzofuran ring; or a benzothiophene ring.
In one embodiment of the present specification, Ar3 of Chemical Formula 1-2 is a substituted or unsubstituted C6 to C60 aryl group.
In one embodiment of the present specification, Ar3 of Chemical Formula 1-2 is a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, Ar3 of Chemical Formula 1-2 is a substituted or unsubstituted phenyl group.
In one embodiment of the present specification, Ar3 of Chemical Formula 1-2 is a phenyl group.
In one embodiment of the present specification, X6 of Chemical Formula 1-3 is N.
In one embodiment of the present specification, B of Chemical Formula 1-3 is a substituted or unsubstituted monocyclic or polycyclic aryl ring.
In one embodiment of the present specification, B of Chemical Formula 1-3 is a substituted or unsubstituted monocyclic aryl ring.
In one embodiment of the present specification, B of Chemical Formula 1-3 is a substituted or unsubstituted benzene ring.
In one embodiment of the present specification, B of Chemical Formula 1-3 is a benzene ring.
In one embodiment of the present specification, Ar4 of Chemical Formula 1-3 is a substituted or unsubstituted C6 to C60 aryl group.
In one embodiment of the present specification, Ar4 of Chemical Formula 1-3 is a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, Ar4 of Chemical Formula 1-3 is a substituted or unsubstituted phenyl group.
In one embodiment of the present specification, Ar4 of Chemical Formula 1-3 is a phenyl group.
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 is O; S or NR’ .
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 may be O.
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 may be S.
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 is NR’, and R’ may be a substituted or unsubstituted C6 to C60 aryl group.
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 is NR’,and R′ may be a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, Y1 of Chemical Formula 1-4 is NR’, and R′ may be a substituted or unsubstituted phenyl group.
In one embodiment of the present specification, d4 of Chemical Formula 1-4 is an integer of 0 to 7.
In one embodiment of the present specification, d4 of Chemical Formula 1-4 is 0 or 7.
In one embodiment of the present specification, at least one of Z1 and Z2 may be the heteroaryl group represented by Chemical Formula 1-1.
In one embodiment of the present specification, at least one of Z1 and Z2 may be the heteroaryl group represented by Chemical Formula 1-2.
In one embodiment of the present specification, at least one of Z1 and Z2 may be the heteroaryl group represented by Chemical Formula 1-3.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is a substituted or unsubstituted silyl group; a substituted or unsubstituted fluorenyl group; or the tricyclic or higher heteroaryl group represented by any one of Chemical Formulae 1-2 to 1-4.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is a substituted or unsubstituted silyl group; a substituted or unsubstituted fluorenyl group; or the heteroaryl group represented by Chemical Formula 1-4.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 may be a substituted or unsubstituted silyl group; or a substituted or unsubstituted fluorenyl group.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 may be a silyl group unsubstituted or substituted with an aryl group; a fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; or 9,9′-spirobi[fluorene].
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is the heteroaryl group represented by Chemical Formula 1-2, and herein, A of Chemical Formula 1-2 may be a substituted or unsubstituted polycyclic aryl ring; or a polycyclic heteroring substituted or unsubstituted and including O or S.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is the heteroaryl group represented by Chemical Formula 1-2, and herein, A of Chemical Formula 1-2 may be a substituted or unsubstituted dicyclic aryl ring; or a dicyclic heteroring substituted or unsubstituted and including O or S.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is the heteroaryl group represented by Chemical Formula 1-2, and herein, A of Chemical Formula 1-2 may be a dicyclic heteroring substituted or unsubstituted and including O or S.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is the heteroaryl group represented by Chemical Formula 1-2, and herein, A of Chemical Formula 1-2 may be a benzofuran ring; or a benzothiophene ring.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 may be the heteroaryl group represented by Chemical Formula 1-4.
In one embodiment of the present specification, when L1 is a direct bond and Z1 is the heteroaryl group represented by Chemical Formula 1-1, Z2 is a substituted or unsubstituted silyl group; a substituted or unsubstituted fluorenyl group; or a heteroaryl group represented by any one of the following Chemical Formulae 1-1-1 to 1-1-3.
In Chemical Formulae 1-1-1 to 1-1-3,
In one embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds, but is not limited thereto.
In addition, by introducing various substituents to the structure of Chemical Formula 1, compounds having unique properties of the introduced substituents may be synthesized. For example, by introducing substituents normally used as hole injection layer materials, hole transfer layer materials, light emitting layer materials, electron transfer layer materials and charge generation layer materials used for manufacturing an organic light emitting device to the core structure, materials satisfying conditions required for each organic material layer may be synthesized.
In addition, by introducing various substituents to the structure of Chemical Formula 1, the energy band gap may be finely controlled, and meanwhile, properties at interfaces between organic materials are enhanced, and material applications may become diverse.
One embodiment of the present specification provides an organic light emitting device including a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include one or more types of the compound of Chemical Formula 1.
In one embodiment of the present specification, one or more layers of the organic material layers include one type of the compound of Chemical Formula 1.
In one embodiment of the present specification, the first electrode may be an anode, and the second electrode may be a cathode.
In another embodiment of the present specification, the first electrode may be a cathode, and the second electrode may be an anode.
In one embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the compound of Chemical Formula 1 may be used as a material of the blue organic light emitting device. For example, the compound of Chemical Formula 1 may be included in a light emitting layer of the blue organic light emitting device.
In one embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the compound of Chemical Formula 1 may be used as a material of the green organic light emitting device. For example, the compound of Chemical Formula 1 may be included in a light emitting layer of the green organic light emitting device.
In one embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the compound of Chemical Formula 1 may be used as a material of the red organic light emitting device. For example, the compound of Chemical Formula 1 may be included in a light emitting layer of the red organic light emitting device.
The organic light emitting device of the present specification may be manufactured using common organic light emitting device manufacturing methods and materials except that one or more organic material layers are formed using the compound described above.
The compound may be formed into an organic material layer using a solution coating method as well as a vacuum deposition method when manufacturing the organic light emitting device. 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.
The organic material layer of the organic light emitting device of the present specification may be formed in a single layer structure, but may be formed in a multilayer structure in which two or more organic material layers are laminated. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer and the like as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers.
In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include the compound of Chemical Formula 1.
In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host may include the compound of Chemical Formula 1.
In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may further include, in addition to the compound of Chemical Formula 1, a compound of the following Chemical Formula 2 or 3.
In Chemical Formula 2,
In one embodiment of the present specification, R21 to R24 of Chemical Formula 2 are each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In one embodiment of the present specification, R21 to R24 of Chemical Formula 2 are each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
In one embodiment of the present specification, R21 to R24 of Chemical Formula 2 are each independently hydrogen; deuterium; or a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, R21 to R24 of Chemical Formula 2 are hydrogen; or deuterium.
In one embodiment of the present specification, R21 to R24 of Chemical Formula 2 are hydrogen.
In one embodiment of the present specification, L21 of Chemical Formula 2 is a direct bond; a substituted or unsubstituted C6 to C30 arylene group; or a substituted or unsubstituted C2 to C30 heteroarylene group.
In one embodiment of the present specification, L21 of Chemical Formula 2 is a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.
In one embodiment of the present specification, L21 of Chemical Formula 2 is a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.
In one embodiment of the present specification, L21 of Chemical Formula 2 is a direct bond; or a substituted or unsubstituted phenylene group.
In one embodiment of the present specification, L21 of Chemical Formula 2 is a direct bond; or a phenylene group.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a substituted or unsubstituted C6 to C30 aryl group; or a C2 to C30 heteroaryl group substituted or unsubstituted and including O or S.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluorenyl group; a substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a phenyl group; a biphenyl group; a naphthyl group; a fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; a dibenzofuran group; or a dibenzothiophene group.
In one embodiment of the present specification, Ar21 and Ar22 of Chemical Formula 2 are each independently a phenyl group; a biphenyl group; a naphthyl group; a fluorenyl group unsubstituted or substituted with an alkyl group; a dibenzofuran group; or a dibenzothiophene group.
In one embodiment of the present specification, Ar21 of Chemical Formula 2 is a phenyl group; a biphenyl group; a naphthyl group; a fluorenyl group unsubstituted or substituted with an alkyl group; a dibenzofuran group; or a dibenzothiophene group.
In one embodiment of the present specification, Ar22 of Chemical Formula 2 is a phenyl group.
In one embodiment of the present specification, Chemical Formula 2 may be represented by any one of the following Chemical Formulae 2-1 to 2-3.
In Chemical Formulae 2-1 to 2-3,
each substituent has the same definition as in Chemical Formula 2.
In one embodiment of the present specification, Chemical Formula 2 may be represented by any one of the following compounds, but is not limited thereto.
In one embodiment of the present specification, R31 and R32 of Chemical Formula 3 are each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In one embodiment of the present specification, R31 and R32 of Chemical Formula 3 are each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
In one embodiment of the present specification, R31 and R32 of Chemical Formula 3 are each independently hydrogen; deuterium; or a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, R31 and R32 of Chemical Formula 3 are hydrogen; or deuterium.
In one embodiment of the present specification, R31 and R32 of Chemical Formula 3 are hydrogen.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a substituted or unsubstituted C6 to C40 aryl group; or a C2 to C40 heteroaryl group substituted or unsubstituted and including O or N.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a substituted or unsubstituted C6 to C40 aryl group.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted triphenylene group.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a phenyl group unsubstituted or substituted with a cyano group, a silyl group or an aryl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; 9,9′-spirobi[fluorene]; or a triphenylene group.
In one embodiment of the present specification, Ar31 and Ar32 of Chemical Formula 3 are each independently a phenyl group unsubstituted or substituted with a cyano group, a triphenylsilyl group or an aryl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; 9,9′-spirobi[fluorene]; or a triphenylene group.
In one embodiment of the present specification, Chemical Formula 3 may be represented by any one of the following compounds, but is not limited thereto.
In one embodiment of the present specification, the organic material layer includes the compound of Chemical Formula 1 and the compound of Chemical Formula 2 or 3 in a weight ratio of 1:10 to 10:1, a weight ratio of 1:8 to 8:1, a weight ratio of 1:5 to 5:1, and a weight ratio of 1:2 to 2:1.
When the compound of Chemical Formula 1 and the compound of Chemical Formula 2 or 3 are included in the above-described weight ratio ranges, an organic light emitting device having a low driving voltage, and superior light emission efficiency and lifetime may be provided. Particularly, when these compounds are included in a weight ratio of 1:2 to 2:1, an organic light emitting device having high light emission efficiency and lifetime is obtained.
The organic light emitting device of the present disclosure may further include one, two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer and a hole blocking layer.
The organic material layer including the compound of Chemical Formula 1 may further include other materials as necessary.
In the organic light emitting device according to one embodiment of the present specification, materials other than the compound of Chemical Formula 1 are illustrated below, however, these are for illustrative purposes only and not for limiting the scope of the present application, and may be replaced by materials known in the art.
As the anode material, materials having relatively large work function may be used, and transparent conductive oxides, metals, conductive polymers or the like may be used. Specific examples of the anode material 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 and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
As the cathode material, materials having relatively small work function may be used, and metals, metal oxides, conductive polymers or the like may be used. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; multilayer structure materials such as LiF/Al or LiO2/Al, and the like, but are not limited thereto.
As the hole injection material, known hole injection materials may be used, and for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429, or starburst-type amine derivatives such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4’,4″-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA) or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) described in the literature [Advanced Material, 6, p.677 (1994)], polyaniline/dodecylbenzene sulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/camphor sulfonic acid or polyaniline/poly(4-styrenesulfonate) that are conductive polymers having solubility, and the like, may be used.
As the hole transfer material, pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives and the like may be used, and low molecular or high molecular materials may also be used.
As the electron transfer material, metal complexes of oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, and the like, may be used, and high molecular materials may also be used as well as low molecular materials.
As examples of the electron injection material, LiF is typically used in the art, however, the present application is not limited thereto.
As the light emitting material, red, green or blue light emitting materials may be used, and as necessary, two or more light emitting materials may be mixed and used. Herein, two or more light emitting materials may be used by being deposited as individual sources of supply or by being premixed and deposited as one source of supply. In addition, fluorescent materials may also be used as the light emitting material, however, phosphorescent materials may also be used. As the light emitting material, materials emitting light by bonding electrons and holes injected from an anode and a cathode, respectively, may be used alone, however, materials having a host material and a dopant material involving in light emission together may also be used.
When mixing light emitting material hosts, same series hosts may be mixed, or different series hosts may be mixed. For example, any two or more types of materials among n-type host materials or p-type host materials may be selected and used as a host material of a light emitting layer.
The organic light emitting device according to one embodiment of the present specification may be a top-emission type, a bottom-emission type or a dual-emission type depending on the materials used.
The compound according to one embodiment of the present specification may also be used in an organic electronic device including an organic solar cell, an organic photo conductor, an organic transistor and the like under a similar principle used in the organic light emitting device.
One embodiment of the present specification provides a composition for forming an organic material layer, the composition including the compound of Chemical Formula 1; and the compound of Chemical Formula 2 or 3.
The composition for forming an organic material layer according to one embodiment of the present specification includes the compound of Chemical Formula 1 and the compound of Chemical Formula 2 or 3 in a weight ratio of 1:10 to 10:1, a weight ratio of 1:8 to 8:1, a weight ratio of 1:5 to 5:1, and a weight ratio of 1:2 to 2:1.
When the compound of Chemical Formula 1 and the compound of Chemical Formula 2 or 3 are included in the above-described weight ratio ranges, an organic light emitting device having a low driving voltage, and superior light emission efficiency and lifetime may be provided. Particularly, when these compounds are included in a weight ratio of 1:2 to 2:1, an organic light emitting device having high light emission efficiency and lifetime is obtained.
The composition for forming an organic material layer according to one embodiment of the present specification may be used as a material of a light emitting layer of an organic light emitting device.
Hereinafter, the present specification will be described in more detail with reference to examples, however, these are for illustrative purposes only, and the scope of the present application is not limited thereto.
1-Bromochloro-4-iodobenzene (20.0 g, 63.0 mM), dibenzo[b,d]furan-2-ylboronic acid (11.1 g, 52.5 mM), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium(0)) (3.0 g, 2.6 mM) and K2CO3 (14.5 g, 105.0 mM) were dissolved in 1,4-dioxane/H2O (400 mL/80 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and dichloromethane (DCM) thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:10) to obtain Compound 1-3-6 (14.4 g, 80%).
Compound 1-3-6 (13.4 g, 37.4 mM), phenylboronic acid (5.5 g, 44.9 mM), Pd(PPh3)4 (2.2 g, 1.9 mM) and K2CO3 (10.3 g, 74.8 mM) were dissolved in 1,4-dioxane/H2O (200 mL/40 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:Hex=1:10) to obtain Compound 1-3-5 (10.8 g, 85%).
Compound 1-3-5 (6.8 g, 19.2 mM), bis(pinacolato)diboron (7.3 g, 28.8 mM), Pd(dppf)Cl2 ([1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)) (702 mg, 1.0 mM), tricyclohexylphosphine (PCy3) (533 mg, 1.9 mM) and potassium acetate (KOAc) (5.6 g, 57.3 mM) were dissolved in DMF (100 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:3), and recrystallized with methanol to obtain Compound 1-3-4 (7.1 g, 85%).
Compound 1-3-4 (16.7 g, 37.4 mM), 2-bromo-4-chloro-1-iodobenzene (14.2 g, 44.9 mM), Pd(PPh3)4 (2.2 g, 1.9 mM) and NaOH (3.0 g, 74.8 mM) were dissolved in 1,4-dioxane/H2O (200 mL/40 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:10) to obtain Compound 1-3-3 (15.8 g, 85%).
Compound 1-3-3 (14.1 g, 27.7 mM), Pd(OAc)2 (palladium(II) acetate) (622 mg, 2.8 mM), PCy3·HBF4 (tricyclohexylphosphine tetrafluoroborate) (2.0 g, 5.5 mM) and K2CO3 (7.7 g, 55.4 mM) were dissolved in dimethylacetamide (DMA) (100 mL), and then refluxed for 12 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:10) to obtain Compound 1-3-2 (8.0 g, 70%).
Compound 1-3-2 (8.2 g, 19.2 mM), bis(pinacolato)diboron (7.3 g, 28.8 mM), Pd2(dba)3 (879 mg, 1.0 mM), Xphos (2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl) (915 mg, 1.9 mM) and KOAc (5.6 g, 57.3 mM) were dissolved in 1,4-dioxane (100 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:3), and recrystallized with methanol to obtain Compound 1-3-1 (8.3 g, 85%).
Compound 1-3-1 (8.4 g, 16.1 mM), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.7 g, 17.7 mM), Pd(PPh3)4 (0.9 g, 0.8 mM) and K2CO3 (4.5 g, 32.3 mM) were dissolved in 1,4-dioxane/H2O (200 mL/40 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:hexane=1:3), and recrystallized with methanol to obtain target Compound 1-3 (8.1 g, 82%).
Target compounds were synthesized in the same manner as in Preparation Example 1 except that Intermediate A of the following Table 1 was used instead of 1-bromo-2-chloro-4-iodobenzene, Intermediate B of the following Table 1 was used instead of dibenzo[b,d]furan-2-ylboronic acid, Intermediate C of the following Table 1 was used instead of 2-bromo-4-chloro-1-iodobenzene, and Intermediate D of the following Table 1 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine.
2-Bromodibenzo[b,d]thiophene (4.2 g, 15.8 mM), 9-phenyl-9H,9′H-3,3′-bicarbazole (6.5 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and K3PO4 (3.3 g, 31.6 mM) were dissolved in 1,4-dioxane (100 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain Compound 2-2-2 (7.9 g, 85%).
To a mixture solution obtained by introducing Compound 2-2-2 (8.4 g, 14.3 mmol) and tetrahydrofuran (THF) (100 mL), 2.5 M n-butyllithium (n-BuLi) (7.4 mL, 18.6 mmol) was added dropwise at -78° C., and the result was stirred for 1 hour at room temperature. Trimethyl borate (4.8 mL, 42.9 mmol) was added dropwise to the reaction mixture, and the result was stirred for 2 hours at room temperature. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:methanol (MeOH)=100:3), and recrystallized with DCM to obtain Compound 2-2-1 (3.9 g, 70%).
Compound 2-2-1 (6.7 g, 10.5 mM), iodobenzene (2.1 g, 10.5 mM), Pd(PPh3)4 (606 mg, 0.52 mM) and K2CO3 (2.9 g, 21.0 mM) were dissolved in toluene/ethanol (EtOH)/H2O (100 mL/20 mL/20 mL), and then refluxed for 12 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain target compound 2-2 (4.9 g, 70%).
Target Compound 2-3 (83%) was obtained in the same manner as in Preparation of Compound 2-2 of Preparation Example 2 except that 4-iodo-1,1′-biphenyl was used instead of iodobenzene.
Target Compound 2-12 (80%) was obtained in the same manner as in Preparation of Compound 2-2 of Preparation Example 2 except that 4-iododibenzo[b,d]furan was used instead of iodobenzene.
3-Bromo-1,1′-biphenyl (3.7 g, 15.8 mM), 9-phenyl-9H,9′H-3,3′-bicarbazole (6.5 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and K3PO4 (3.3 g, 31.6 mM) were dissolved in 1,4-dioxane (100 mL), and then refluxed for 24 hours. After the reaction was completed, the result was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified by column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain target Compound 3-3 (7.5 g, 85%).
Target compounds were synthesized in the same manner as in Preparation Example 3 except that Intermediate A of the following Table 2 was used instead of 3-bromo-1,1′-biphenyl, and Intermediate B of Table 2 was used instead of 9-phenyl-9H,9′H-3,3′-bicarbazole.
Compounds other than the compounds described in Preparation Examples 1 to 3 and Tables 1 and 2 were also prepared in the same manner as in the preparation examples described above, and the synthesis results are shown in the following Table 3 and Table 4.
1H NMR (CDCl3, 200 Mz)
A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1,500 Å was cleaned with distilled water ultrasonic waves. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents such as acetone, methanol and isopropyl alcohol, then dried, and ultraviolet ozone (UVO) treatment was conducted for 5 minutes using UV in an ultraviolet (UV) cleaner. After that, the substrate was transferred to a plasma cleaner (PT), and after conducting plasma treatment under vacuum for ITO work function and residual film removal, the substrate was transferred to a thermal deposition apparatus for organic deposition.
On the transparent ITO electrode (anode), a hole injection layer 2-TNATA (4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transfer layer NPB (N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine), which are common layers, were formed.
A light emitting layer was thermal vacuum deposited thereon as follows. As the light emitting layer, a compound of Chemical Formula 1 described in the following Table 5 was deposited to 400 Å as a host, and a green phosphorescent dopant [Ir(ppy)3] was doped by 7% of the deposited thickness of the light emitting layer and deposited. After that, BCP (bathocuproine) was deposited to 60 Å as a hole blocking layer, and Alq3 was deposited to 200 Å thereon as an electron transfer layer. Lastly, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 Å, and then a cathode was formed on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1.200 Å, and as a result, an organic electroluminescent device was manufactured.
Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10-8 torr to 10-6 torr for each material to be used in the OLED manufacture.
For each of the organic electroluminescent devices manufactured as above, electroluminescent (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, T90 was measured when standard luminance was 6,000 cd/m2 through a lifetime measurement system (M6000) manufactured by McScience Inc..
Results of measuring driving voltage, light emission efficiency, color (EL color) and lifetime of the organic light emitting devices manufactured according to the present disclosure are as shown in the following Table 5.
As seen from the results of Table 5, the organic electroluminescent device using the light emitting layer material of the organic electroluminescent device of the present disclosure had lower driving voltage, enhanced light emission efficiency, and significantly improved lifetime compared to Comparative Examples 1 to 9.
Specifically, in the following Table 6, the LUMO orbital of Compound Ref. 1 is widely delocalized across phenanthroline-triazine-triphenylene-triazine-phenanthroline, and the LUMO level is -2.38. It may be identified that such a result inhibits a charge balance by creating excessive electron mobility, and efficiency is measured to be low by the LUMO level lower than the dopant inhibiting energy transfer. In addition, it may be identified that having three substituents based on triazine (Compound 1-11) has superior stability and enhanced lifetime compared to having two substituents (Ref. 1).
-6.24
-2.38
-5.26
-1.88
In addition, in the following Table 7, the HOMO orbital of Compound Ref. 2 is localized to carbazole, whereas the HOMO orbital of Compound 1-11 is widely delocalized to carbazole and triphenylene. It may be identified that this enhances efficiency and lifetime of the device by enhancing hole stability and mobility.
-5.37
-2.08
Compounds Ref. 2, 3 and 4 are different from Chemical Formula 1 of the present disclosure in the position of substitution. In the structures of Compounds Ref. 2, 3 and 4, the HOMO core, the linker and the LUMO core are linearly connected facilitating charge transfer in the molecules and lowering a band gap. It may be identified that the low band gap inhibits hole and electron injections from the auxiliary layer to the host, which reduces efficiency and lifetime of the device.
Likewise, Compounds Ref. 5, 6 and 9 are also different from Chemical Formula 1 of the present disclosure in the position of substitution. Materials having a molecular steric hindrance as in the structures of Compounds Ref. 5, 6 and 9 may have problems in the molecular stability causing a problem of reducing a device lifetime.
In the following Table 8, Compounds Ref. 7 and 8 have the same position of substitution as Chemical Formula 1 of the present disclosure, but have different substituents. Specifically, when a monocyclic heteroaryl group directly substitutes as Z1 (or Z2) on the triphenylene in the present disclosure, the other substituent Z2 (or Z1) is a silyl group, a fluorenyl group or a tricyclic or higher heteroaryl group, whereas Compounds Ref. 7 and 8 are substituted with a dicyclic heteroaryl group and an aryl group (biphenyl group).
-5.63
-1.94
In Compound Ref. 7, the HOMO orbital is widely delocalized to imidazole and triphenylene. The HOMO core needs to stabilize holes, however, imidazole is not suited for stabilizing holes compared to carbazole of Compound 1-11, and reduces a lifetime of the device.
In addition, the HOMO orbital of Compound Ref. 8 is delocalized to phenyl and triphenylene. The HOMO core of Compound Ref. 8 is capable of stabilizing holes compared to imidazole, however, it may be identified that, compared to carbazole, low hole stability and short lifetime are obtained.
In an organic electroluminescent device, a result of a host in a light emitting layer may change depending on the degree of balance between holes and electrons transferred to the light emitting layer.
A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1,500 Å was cleaned with distilled water ultrasonic waves. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents such as acetone, methanol and isopropyl alcohol, then dried, and ultraviolet ozone (UVO) treatment was conducted for 5 minutes using UV in an ultraviolet (UV) cleaner. After that, the substrate was transferred to a plasma cleaner (PT), and after conducting plasma treatment under vacuum for ITO work function and residual film removal, the substrate was transferred to a thermal deposition apparatus for organic deposition.
On the transparent ITO electrode (anode), a hole injection layer 2-TNATA (4,4’,4”-tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transfer layer NPB (N,N′-di(1-naphthyl)-N,N’-diphenyl-(1,1’-biphenyl)-4,4’-diamine), which are common layers, were formed.
A light emitting layer was thermal vacuum deposited thereon as follows. As the light emitting layer, one type of a compound of Chemical Formula 1 and one type of a compound of Chemical Formula 2 or Chemical Formula 3 were pre-mixed as described in the following Table 9 and deposited to 400 Å in one source of supply as a host, and a green phosphorescent dopant [Ir(ppy)3] was doped by an amount of 7% of the deposited thickness of the light emitting layer and deposited. After that, BCP (bathocuproine) was deposited to 60 Å as a hole blocking layer, and Alq3 was deposited to 200 Å thereon as an electron transfer layer. Lastly, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 Å, and then a cathode was formed on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1,200 Å, and as a result, an organic electroluminescent device was manufactured.
Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10-8 torr to 10-6 torr for each material to be used in the OLED manufacture.
For each of the organic electroluminescent devices manufactured as above, electroluminescent (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, T90 was measured when standard luminance was 6,000 cd/m2 through a lifetime measurement system (M6000) manufactured by McScience Inc..
Results of measuring driving voltage, light emission efficiency, color (EL color) and lifetime of the organic light emitting devices manufactured according to the present disclosure are as shown in the following Table 9.
From the results of Table 9, it may be identified that effects of more superior efficiency and lifetime are obtained when including the compound of Chemical Formula 1 (N-type) and the compound of Chemical Formula 2 or 3 (P-type) at the same time. Such results may lead to a forecast that an exciplex phenomenon occurs when including the two compounds at the same time.
The exciplex phenomenon is a phenomenon of releasing energy having sizes of a donor (p-host) HOMO level and an acceptor (n-host) LUMO level due to electron exchanges between two molecules. When the exciplex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, and as a result, internal quantum efficiency of fluorescence may increase up to 100%. When a donor (p-host) having a favorable hole transfer ability and an acceptor (n-host) having a favorable electron transfer ability are used as a host of a light emitting layer, holes are injected to the p-host and electrons are injected to the n-host, and therefore, a driving voltage may be lowered, which resultantly helps with enhancement in the lifetime. In the disclosure of the present application, the compound of Chemical Formula 2 or 3 performed the donor role, and the compound of Chemical Formula 1 performed the acceptor role, and when used together as the light emitting layer host, excellent device properties were obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0078447 | Jun 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/007680 | 6/18/2021 | WO |
