Patent Application
20230165145
This application claims priority to and the benefits of Korean Patent Application No. 10-2020-0125761, filed with the Korean Intellectual Property Office on Sep. 28, 2020, the entire contents of which are incorporated herein by reference.
The present specification relates to a heterocyclic compound, an organic light emitting device comprising the same, and a composition for an organic material layer.
An organic 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.
U.S. Pat. No. 4,356,429
The present disclosure is directed to providing a heterocyclic compound, an organic light emitting device comprising the same, and a composition for an organic material layer.
One embodiment of the present application provides a heterocyclic compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
X is O; or S,
R1 to R5 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring,
X1 to X3 are N; or CRe, and at least one of X1 to X3 is N,
L1 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ar1 and Ar2 are the same as or different from each other, and each independently 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,
Lin is a substituted or unsubstituted C6 to C20 arylene group,
Chemical Formula 1 has a deuterium content of greater than or equal to 20% and less than or equal to 100%,
R, R′, R″ and Re are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group,
a and p are an integer of 0 to 3,
q is an integer of 1 to 5,
n is an integer of 0 to 2, and
when n is an integer of 2 or p, a and q are 2 or greater, substituents in the parentheses are the same as or different from each other.
In addition, one embodiment of the present application provides an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first 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 comprise the heterocyclic compound represented by Chemical Formula 1.
In addition, in the organic light emitting device provided in one embodiment of the present application, the organic material layer comprising the heterocyclic compound of Chemical Formula 1 further comprises a heterocyclic compound represented by the following Chemical Formula 2.
In Chemical Formula 2,
Rc and Rd are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring,
L2 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ra and Rb are the same as or different from each other, and each independently —CN; —SiRR′R″; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,
R, R′ and R″ are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group,
a is an integer of 0 to 4,
r and s are an integer of 0 to 7, and
when a, s and r are 2 or greater, substituents in the parentheses are the same as or different from each other.
In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, the composition comprising the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.
Lastly, one embodiment of the present application provides a method for manufacturing an organic light emitting device, the method comprising preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layers, wherein the foaming of organic material layers comprises forming one or more organic material layers using the composition for an organic material layer according to one embodiment of the present application.
A heterocyclic compound according to one embodiment of the present application can be used as a material of an organic material layer of an organic light emitting device. The heterocyclic compound can be used as a material of a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer, a charge generation layer or the like in an organic light emitting device.
Specifically, the heterocyclic compound of Chemical Formula 1 is particularly effective when used as a light emitting layer host since HOMO is localized on dibenzofuran and dibenzothiophene effectively stabilizing holes, and LUMO is localized on an azine-based substituent effectively stabilizing electrons.
In addition, the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 can be used as a material of a light emitting layer of an organic light emitting device at the same time. In addition, using the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 at the same time in an organic light emitting device is capable of reducing a driving voltage of the device, enhancing light efficiency, and enhancing lifetime properties of the device by thermal stability of the compound.
Particularly, the heterocyclic compound represented by Chemical Formula 1 has a phenylene linking group in the core structure of dibenzofuran or dibenzothiophene and has an azine-based substituent, which strengthens n-type properties, and, by comprising the heterocyclic compound represented by Chemical Formula 2 corresponding to biscarbazoles having a specific substituent, the driving voltage can be reduced, and efficiency and lifetime can be maximized.
100: Substrate
200: Anode
300: Organic Material Layer
301: Hole Injection Layer
302: Hole Transfer Layer
303: Light Emitting Layer
304: Hole Blocking Layer
305: Electron Transfer Layer
306: Electron Injection Layer
400: Cathode
Hereinafter, the present application will be described in detail.
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 is capable of substituting, 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 cyano group; a halogen 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% or a hydrogen content being 100%. In other words, an expression of “substituent X is hydrogen” does not exclude deuterium unlike a hydrogen content being 100% or a deuterium content being 0%, and therefore, may mean a state in which hydrogen and deuterium are mixed.
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/T1×100=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 comprise 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 comprises linear or branched having 1 to 60 carbon atoms, 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 comprise 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 4-methylhexyl group, a 5-methylhexyl group and the like, but are not limited thereto.
In the present specification, the alkenyl group comprises linear or branched having 2 to 60 carbon atoms, 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 comprise 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 comprises linear or branched having 2 to 60 carbon atoms, 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 alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably from 1 to 20. Specific examples thereof may comprise methoxy, ethoxy, n-propoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto. In the present specification, the cycloalkyl group comprises a monocyclic or polycyclic aryl group 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 groups 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 comprise 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 comprises O, S, Se, N or Si as a heteroatom, comprises 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 comprises 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 comprises 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. Specific examples of the aryl group may comprise 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 comprises S, O, Se, N or Si as a heteroatom, comprises 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 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. Specific examples of the heteroaryl group may comprise 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 triazolyl 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 triazinyl 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, a 5,10-dihydrobenzo[b,e][1,4]azasilinyl group, a pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group, a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, a 5,11-dihydroindeno[1,2-b]carbazolyl group and the like, but are not limited thereto.
In the present specification, 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 although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 30. Specific examples of the amine group may comprise 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 arylene group means the aryl group having two bonding sites, that is, a divalent group.
The descriptions on the aryl group provided above may be applied thereto except for those that are each a divalent group. In addition, the heteroarylene group means the heteroaryl group having two bonding sites, that is, a divalent group. The descriptions on the heteroaryl group provided above may be applied thereto except for those that are each a divalent group
In the present specification, the phosphine oxide group is represented by —P(═O)R101R102, and R101 and R102 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 heterocyclic group. Specifically, the phosphine oxide group may be substituted with an aryl group, and as the aryl group, the examples described above may be used. Examples of the phosphine oxide group may comprise a diphenylphosphine oxide group, a dinaphthylphosphine oxide group and the like, but are not limited thereto.
In the present specification, the silyl group is a substituent comprising Si, having the Si atom directly linked as a radical, and is represented by —SiR104R105R106. R104 to R106 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 heterocyclic group. Specific examples of the silyl group may comprise 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 “adjacent” group may mean a substituent substituting an atom directly linked to an atom substituted by the corresponding substituent, a substituent sterically most closely positioned to the corresponding substituent, or another substituent substituting an atom substituted by the corresponding substituent. For example, two substituents substituting ortho positions in a benzene ring, and two substituents substituting the same carbon in an aliphatic ring may be interpreted as groups “adjacent” to each other.
As the aliphatic or aromatic hydrocarbon ring or heteroring that adjacent groups may form, the structures illustrated as the cycloalkyl group, the cycloheteroalkyl group, the aryl group and the heteroaryl group described above may be used except for those that are not a monovalent group.
One embodiment of the present application provides a heterocyclic compound represented by Chemical Formula 1.
In one embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formula 3 to Chemical Formula 7.
In Chemical Formulae 3 to 7,
X, R1 to R5, a, X1 to X3, Ar1, Ar2, L1, q and p have the same definitions as in Chemical Formula 1,
R6 and R7 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring,
a1 and b1 are an integer of 0 to 4,
b2 is an integer of 0 to 5,
a2 is an integer of 0 to 3, and
when a1, b1, a2 and b2 are 2 or greater, substituents in the parentheses are the same as or different from each other.
In one embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formula 8 to Chemical Formula 11.
In Chemical Formulae 8 to 11,
each substituent has the same definition as in Chemical Formula 1.
In one embodiment of the present application, X may be O; or S.
In one embodiment of the present application, X may be O.
In one embodiment of the present application, X may be S.
In one embodiment of the present application, X1 to X3 are N; or CRe, and at least one of X1 to X3 may be N.
In one embodiment of the present application, X1 to X3 may be N.
In one embodiment of the present application, X1 and X2 are N, and X3 may be CRe.
In one embodiment of the present application, X1 and X3 are N, and X2 may be CRe.
In one embodiment of the present application, R1 to R5 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; 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 another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; or a substituted or unsubstituted C6 to C40 aryl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; or a C6 to C40 aryl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; or a C6 to C20 aryl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; a monocyclic C6 to C10 aryl group; or a polycyclic C10 to C20 aryl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted phenyl group; or a substituted or unsubstituted biphenyl group.
In another embodiment, R1 to R5 are the same as or different from each other, and may be each independently hydrogen; deuterium; a phenyl group; or a biphenyl group.
In one embodiment of the present application, R1 to R5 may be substituted with deuterium.
In one embodiment of the present application, Ar1 may be 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 another embodiment, Ar1 may be a substituted or unsubstituted C6 to C60 aryl group.
In another embodiment, Ar1 may be a substituted or unsubstituted C6 to C40 aryl group.
In another embodiment, Ar1 may be a C6 to C40 aryl group.
In another embodiment, Ar1 may be a monocyclic C6 to C10 aryl group; or a polycyclic C10 to C40 aryl group.
In another embodiment, Ar1 may be a monocyclic C6 to C10 aryl group; or a polycyclic C10 to C20 aryl group.
In another embodiment, Ar1 may be a substituted or unsubstituted phenyl group; or a substituted or unsubstituted biphenyl group.
In another embodiment, Ar1 may be a phenyl group; or a biphenyl group.
In one embodiment of the present application, when
of Chemical Formula 1 are expressed as an unsubstituted biphenyl group, the biphenyl group may be represented by any one of the following structural formulae.
In one embodiment of the present application, when Ar1 is a biphenyl group, Ar1 may be represented by any one of the following structural formulae.
In another embodiment, Ar1 may be 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,
means a position linked to Chemical Formula 1.
In one embodiment of the present application, L1 may be a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.
In another embodiment, L1 may be a direct bond; a substituted or unsubstituted C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 heteroarylene group.
In another embodiment, L1 may be a direct bond; or a substituted or unsubstituted C6 to C40 arylene group.
In another embodiment, L1 may be a direct bond; or a C6 to C40 arylene group.
In another embodiment, L1 may be a direct bond; or a C6 to C20 arylene group.
In another embodiment, L1 may be a direct bond; or a substituted or unsubstituted phenylene group.
In another embodiment, L1 may be a direct bond; or a phenylene group.
In one embodiment of the present application, Ar2 may be 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 another embodiment, Ar2 may be a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In another embodiment, Ar2 may be a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In another embodiment, Ar2 may be a C6 to C40 aryl group; or a C2 to C40 heteroaryl group.
In another embodiment, Ar2 may be a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted triphenylenyl group; a substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group.
In another embodiment, Ar2 may be a phenyl group; a biphenyl group; a terphenyl group; a triphenylenyl group; a dibenzofuran group; or a dibenzothiophene group.
In another embodiment, Ar2 may be represented by the following Chemical Formula 1-2-1 or 1-2-2.
In Chemical Formulae 1-2-1 and 1-2-2,
means a position linked to Chemical Formula 1,
X1 is O; or S,
R11 to R15 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring,
a11 is an integer of 0 to 3, and when a11 is 2 or greater, substituents in the parentheses are the same as or different from each other,
R, R′ and R″ have the same definitions as in Chemical Formula 1, and
Ar11 is a substituted or unsubstituted C6 to C60 aryl group.
In one embodiment of the present application, R11 to R15 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; deuterium; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; deuterium; a C6 to C20 aryl group; or a C2 to C20 heteroaryl group.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; deuterium; a C6 to C10 aryl group; or a C2 to C10 heteroaryl group.
In another embodiment, R11 to R15 are the same as or different from each other, and may be each independently hydrogen; or deuterium.
In one embodiment of the present application, Ar11 is a substituted or unsubstituted C6 to C60 aryl group.
In another embodiment, Ar11 is a substituted or unsubstituted C6 to C40 aryl group.
In another embodiment, Ar11 is a substituted or unsubstituted C6 to C20 aryl group.
In another embodiment, Ar11 is a C6 to C20 aryl group.
In another embodiment, Ar11 is a phenyl group; a biphenyl group; a terphenyl group; or a triphenylenyl group.
In one embodiment of the present application, Chemical Formula 1-2-2 may be represented by any one of the following Chemical Formulae 1-A to 1-D.
In Chemical Formulae 1-A to 1-D,
each substituent has the same definition as in Chemical Formula 1-2-2.
In one embodiment of the present application, R, R′ and R″ are the same as or different from each other, and may be each independently 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 another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a C1 to C60 alkyl group; or a C6 to C60 aryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a methyl group; or a phenyl group.
In another embodiment, R, R′ and R″ may be a substituted or unsubstituted methyl group.
In another embodiment, R, R′ and R″ may be a substituted or unsubstituted phenyl group.
In another embodiment, R, R′ and R″ may be a phenyl group.
In one embodiment of the present application, Re may be hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group.
In another embodiment, Re may be hydrogen.
In one embodiment of the present application, Lin may be a substituted or unsubstituted C6 to C20 arylene group.
In another embodiment, Lin may be a substituted or unsubstituted C6 to C15 arylene group.
In another embodiment, Lin may be a C6 to C15 arylene group.
In another embodiment, Lin may be a monocyclic C6 to C10 arylene group; or a polycyclic C10 to C15 arylene group.
In another embodiment, Lin may be a phenylene group; or a biphenylene group.
In one embodiment of the present application, n may be an integer of 0 or 1.
n being 0 means a substituent being linked without Lin bonding, that is, a direct bond.
In one embodiment of the present application, Lin may be represented by any one of the following structural formulae.
In the structural formulae,
means a position linked to the substituents of Chemical Formula 1.
In one embodiment of the present application, Lin may be substituted with deuterium.
In one embodiment of the present application, Chemical Formula 1 may be represented by a combination of the following Structural Formula A to the following Structural Formula C.
In Structural Formula A to Structural Formula C,
is a position to which Structural Formulae A to C each bond, and
Structural Formula A and Structural Formula B; or Structural Formula A has a deuterium content of 20% to 100%.
In one embodiment of the present application, Structural Formula A and Structural Formula B; or Structural Formula A has a deuterium content of 20% to 100%.
Molecules are thermally damaged by electron migration when driving an organic light emitting device. Particularly, structures comprising dibenzofuran and dibenzothiophene are highly likely to have defects in oxygen or sulfur, a most unstable site.
In the compound in which Structural Formula A and Structural Formula B; or Structural Formula A has a deuterium content of 20% to 100% as in the disclosure of the present application, the heterocyclic compound is substituted with deuterium having a larger molecular weight than hydrogen in order to prevent this phenomenon, and as a result, molecular energy is lowered by reducing changes in the vibrational frequency, which resultantly increases molecular stability. In addition, it is identified that, since single bond dissociation energy of carbon and deuterium is higher than single bond dissociation energy of carbon and hydrogen, thermal stability of the molecule increases, and a device lifetime is improved as a result.
A unipolar material that does not comprise carbazole such as the compound having triazine (Structural Formula C) bonding to a heteroring (Structural Formula A) has relatively faster electron migration compared to hole migration. A compound substituted with deuterium has higher packing density compared to a compound substituted with hydrogen. Accordingly, holes or electrons migrate faster when substituted with deuterium since the intermolecular distance is close. In the compound of the present disclosure, the HOMO region responsible for hole migration is mainly distributed in the heteroring (Structural Formula A) or the heteroring and the linker (Structural Formula B). Accordingly, when the compound is substituted deuterium, relatively slow hole migration becomes faster increasing probability of electrons and holes meeting in a light emitting layer, and as a result, light emission efficiency may increase.
In one embodiment of the present application, Structural Formula A has a deuterium content of 20% to 100%.
In another embodiment, Structural Formula A may have a deuterium content of 20% to 100%; 25% to 100%; or 30% to 100%.
In one embodiment of the present application, Structural Formula A may have a deuterium content of 100%.
In one embodiment of the present application, Structural Formula B has a deuterium content of 20% to 100%.
In another embodiment, Structural Formula B may have a deuterium content of 20% to 100%; 30% to 100%; or 60% to 100%.
In one embodiment of the present application, Structural Formula B may have a deuterium content of 100%.
In one embodiment of the present application, Structural Formula A has a deuterium content of 20% to 100%, and Structural Formula B and Structural Formula C may have a deuterium content of 0%.
In one embodiment of the present application, Structural Formula A and Structural Formula B have a deuterium content of 20% to 100%, and Structural Formula C may have a deuterium content of 0%.
In one embodiment of the present application, Structural Formula A and Structural Formula B have a deuterium content of 100%, and Structural Formula C may have a deuterium content of 0%.
In one embodiment of the present application, Structural Formula A has a deuterium content of 100%, and Structural Formula B and Structural Formula C may have a deuterium content of 0%.
In another embodiment, the deuterium content of each of Structural Formulae A, B and C may increase or decrease when additional substituents are further included depending on the deuterium substitution process.
In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 is represented by any one of the following compounds. In addition, in one embodiment of the present application, the following compounds are one example, and other compounds included in Chemical Formula 1 comprising additional substituents may be included without being limited to the following compounds.
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.
Meanwhile, the compound has a high glass transition temperature (Tg), and has excellent thermal stability. Such an increase in the thermal stability becomes an important factor providing driving stability to a device.
In addition, one embodiment of the present application provides an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first 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 comprise the heterocyclic compound represented by Chemical Formula 1.
In one embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.
In another embodiment, the first electrode may be a cathode, and the second electrode may be an anode.
In one 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 may be used as a material of the blue organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material of the green organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material of the red organic light emitting device.
In one 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 may be used as a light emitting layer material of the blue organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a light emitting layer material of the green organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a light emitting layer material of the red organic light emitting device.
Specific details on the heterocyclic compound represented by Chemical Formula 1 are the same as the descriptions provided above.
The organic light emitting device of the present disclosure 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 heterocyclic compound described above.
The heterocyclic compound may be formed into an organic material layer through 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 disclosure may be formed in a single layer structure, or may also be formed in a multilayer structure in which two or more organic material layers are laminated. For example, the organic light emitting device according to one embodiment of the present disclosure may have a structure comprising 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 comprise a smaller number of organic material layers.
In the organic light emitting device of the present disclosure, the organic material layer comprises a light emitting layer, and the light emitting layer may comprise the heterocyclic compound of Chemical Formula 1.
In the organic light emitting device of the present disclosure, the organic material layer comprises a light emitting layer, and the light emitting layer may comprise the heterocyclic compound of Chemical Formula 1 as a light emitting layer host.
In the organic light emitting device provided in one embodiment of the present application, the organic material layer comprising the heterocyclic compound represented by Chemical Formula 1 further comprises a heterocyclic compound represented by the following Chemical Formula 2.
In Chemical Formula 2,
Rc and Rd are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring,
L2 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ra and Rb are the same as or different from each other, and each independently —CN; —SiRR′R″; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,
R, R′ and R″ are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C6 to C60 aryl group,
a is an integer of 0 to 4,
r and s are an integer of 0 to 7, and
when a, s and r are 2 or greater, substituents in the parentheses are the same as or different from each other.
In one embodiment of the present application, L2 may be a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.
In another embodiment, L2 may be a direct bond; a substituted or unsubstituted C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 heteroarylene group.
In another embodiment, L2 may be a direct bond; a C6 to C40 arylene group; or a C2 to C40 heteroarylene group.
In another embodiment, L2 may be a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; or a substituted or unsubstituted divalent dibenzofuran group.
In another embodiment, L2 may be a direct bond; a phenylene group; a biphenylene group; or a divalent dibenzofuran group.
In one embodiment of the present application, L2 may be substituted with deuterium.
In one embodiment of the present application, Ra and Rb are the same as or different from each other, and may be each independently —CN; SiRR′R″; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, Ra may be —CN; SiRR′R″; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, Ra may be —CN; SiRR′R″; a C6 to C40 aryl group unsubstituted or substituted with a C1 to C40 alkyl group or a C6 to C40 aryl group; or a C2 to C60 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group.
In another embodiment, Ra may be —CN; SiRR′R″; a phenyl group; a biphenyl group; a terphenyl group; a dimethylfluorenyl group; a diphenylfluorenyl group; a spirobifluorenyl group; or a dibenzofuran group unsubstituted or substituted with a phenyl group.
In another embodiment, Rb may be a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, Rb may be a C6 to C60 aryl group unsubstituted or substituted with a C1 to C40 alkyl group, —CN, SiRR′R″ or a C6 to C40 aryl group.
In another embodiment, Rb may be a C6 to C40 aryl group unsubstituted or substituted with a C1 to C40 alkyl group, —CN, SiRR′R″ or a C6 to C40 aryl group.
In another embodiment, Rb may be a phenyl group unsubstituted or substituted with —CN or SiRR′R″; a biphenyl group unsubstituted or substituted with a phenyl group; a terphenyl group; or a dimethylfluorenyl group.
In one embodiment of the present application, Ra and Rb may be substituted with deuterium.
In one embodiment of the present application, -(L2)a-Ra and Rb of Chemical Formula 2 may be different from each other.
In one embodiment of the present application, -(L2)a-Ra and Rb of Chemical Formula 2 may be the same as each other.
In another embodiment, R, R′ and R″ may be a phenyl group.
In one embodiment of the present application, Chemical Formula 2 may have a deuterium content of greater than or equal to 0% and less than or equal to 100%.
In another embodiment, Chemical Formula 2 may have a deuterium content of greater than or equal to 10% and less than or equal to 100%.
In another embodiment, Chemical Formula 2 may have a deuterium content of 0%, 100%, or 10% to 80%.
In one embodiment of the present application, Rc and Rd are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroring.
In another embodiment, Rc and Rd are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; SiRR′R″; —P(═O)RR′; and —NRR′.
In another embodiment, Rc and Rd are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; SiRR′R″; —P(═O)RR′; and —NRR′.
In another embodiment, Rc and Rd are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a C1 to C40 alkyl group; a C6 to C40 aryl group; a C2 to C40 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′.
In another embodiment, Rc and Rd are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a C1 to C20 alkyl group; a C6 to C20 aryl group; a C2 to C20 heteroaryl group; —SiRR′R″; —P(═O)RR′; and —NRR′.
In another embodiment, Rc and Rd are the same as or different from each other, and may be each independently hydrogen; or deuterium.
In one embodiment of the present application, r is 7, and Rc may be hydrogen.
In one embodiment of the present application, r is 7, and Rc may be deuterium.
In one embodiment of the present application, r is 7, and Rc may be hydrogen; or deuterium.
In one embodiment of the present application, s is 7, and Rd may be hydrogen.
In one embodiment of the present application, s is 7, and Rd may be deuterium.
In one embodiment of the present application, s is 7, and Rd may be hydrogen; or deuterium.
Effects of more superior efficiency and lifetime are obtained when comprising the compound of Chemical Formula 1 and the compound of Chemical Formula 2 at the same time in the organic material layer of the organic light emitting device. Such results may lead to a forecast that an exciplex phenomenon occurs when comprising 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 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 one embodiment of the present application, the heterocyclic compound of Chemical Formula 2 may be represented by any one of the following compounds.
In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, the composition comprising the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.
Specific descriptions on the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are the same as the descriptions provided above.
In the composition, the heterocyclic compound represented by Chemical Formula 1:the heterocyclic compound represented by Chemical Formula 2 may have a weight ratio of 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1 or 1:2 to 2:1, however, the weight ratio is not limited thereto.
The composition may be used when forming an organic material of an organic light emitting device, and may be more preferably used when forming a host of a light emitting layer.
The composition has a form in which two or more compounds are simply mixed, and materials in a powder state may be mixed before forming the organic material layer of the organic light emitting device, or compounds in a liquid state may be mixed at a proper temperature or higher. The composition is in a solid state below the melting point of each material, and may be maintained in a liquid state when adjusting a temperature.
The composition may further comprise materials known in the art such as solvents and additives.
The organic light emitting device according to one embodiment of the present application 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 heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 described above.
The compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 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 disclosure may be formed in a single layer structure, or may also 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 comprising 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 comprise a smaller number of organic material layers.
In one 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 and the heterocyclic compound according to Chemical Formula 2 may be used as a material of the blue organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as a material of the green organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as a material of the red organic light emitting device.
The organic light emitting device of the present disclosure may further comprise 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.
In the organic light emitting device provided in one embodiment of the present application, the organic material layer comprises at least one of a hole blocking layer, an electron injection layer and an electron transfer layer, and the at least one of the hole blocking layer, the electron injection layer and the electron transfer layer comprises the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.
In the organic light emitting device provided in one embodiment of the present application, the organic material layer comprises a light emitting layer, and the light emitting layer comprises the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.
In the organic light emitting device provided in one embodiment of the present application, the organic material layer comprises a light emitting layer, the light emitting layer comprises a host material, and the host material comprises the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.
One embodiment of the present application provides a method for manufacturing an organic light emitting device, the method comprising preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the foaming of organic material layers comprises forming one or more organic material layers using the composition for an organic material layer according to one embodiment of the present application.
In the method for manufacturing an organic light emitting device provided in one embodiment of the present application, the forming of organic material layers is forming the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 using a thermal vacuum deposition method after pre-mixing.
The pre-mixing means first mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 in one source of supply before depositing on the organic material layer.
The pre-mixed material may be referred to as the composition for an organic material layer according to one embodiment of the present application.
In the organic light emitting device according to one embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 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 comprise 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 comprise 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-styrene-sulfonate) 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 pre-mixed 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 application may be a top-emission type, a bottom-emission type or a dual-emission type depending on the materials used.
The heterocyclic compound according to one embodiment of the present application may also be used in an organic electronic device comprising 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.
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) Preparation of Compound 3-P3
Compound 3-P4 (20 g, 80.94 mmol) and (4-chlorophenyl)boronic acid (12.66 g, 80.94 mmol) were dissolved in 1,4-dioxane (200 mL) and distilled water (40 mL), and after introducing Pd(PPh3)4 (4.67 g, 4.047 mmol) and K2CO3 (28 g, 202.35 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 3-P3 (15.8 g, yield 70%).
2) Preparation of Compound 3-P2
*Compounds and reaction conditions are as shown in the following Table 1 and Table 2.
Compound 3-P2 was synthesized under the reaction condition of Example 9 having the highest yield in Table 1 and Table 2.
Compound 3-P3 (15.8 g, 56.66 mmol) was dissolved in benzene-d6 (790 g) and CF3SO3H (214.9 g), and stirred for 1 hour at 50° C. After the reaction was completed, the result was quenched with Na2CO3 in D2O. After the quenching, ethyl acetate was introduced to the mixture solution for dissolution, and after the organic layer was separated and dried with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 3-P2 (11.2 g, yield 68%).
3) Preparation of Compound 3-P1
Compound 3-P2 (11.2 g, 38.64 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (14.72 g, 57.97 mmol) were dissolved in 1,4-dioxane (120 mL), and after introducing Pd2(dba)3 (1.77 g, 1.93 mmol), potassium acetate (11.36 g, 115.94 mmol) and Sphos (1.58 g, 3.86 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 3-P1 (11.8 g, yield=80%).
4) Preparation of Compound 3
Compound 3-P1 (11.8 g, 30.91 mmol) and 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (13.41 g, 30.91 mmol) were dissolved in 1,4-dioxane (125 mL) and distilled water (25 mL), and after introducing Pd(PPh3)4 (1.78 g, 1.54 mmol) and K2CO3 (10.68 g, 77.29 mmol) thereto, the mixture was stirred for 6 hours under reflux. After the reaction was completed, dichloromethane was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 3 (14.12 g, yield=70%).
Target compounds of the following Table 3 were synthesized in the same manner as in Preparation Example 1 except that Intermediate 1 of the following Table 3 was used instead of Compound 3-P4, Intermediate 2 of the following Table 3 was used instead of Compound A, and Intermediate 3 of the following Table 3 was used instead of Compound B.
1) Preparation of Compound 141-P5
Compound 141-P6 (22.79 g, 80.94 mmol) and phenylboronic acid (9.8 g, 80.94 mmol) were dissolved in 1,4-dioxane (250 mL) and distilled water (50 mL), and after introducing Pd(PPh3)4 (4.67 g, 4.047 mmol) and K2CO3 (28 g, 202.35 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141-P5 (16.9 g, yield 75%).
2) Preparation of Compound 141-P4
Compound 141-P5 (16.9 g, 60.70 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (23.12 g, 91.05 mmol) were dissolved in 1,4-dioxane (170 mL), and after introducing Pd2(dba)3 (2.78 g, 3.03 mmol), potassium acetate (14.87 g, 151.75 mmol) and S phos (2.50 g, 6.07 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141-P4 (17.98 g, yield=80%).
3) Preparation of Compound 141-P3
Compound 141-P4 (17.98 g, 48.56 mmol) and 1-bromo-4-iodobenzene (17.86 g, 63.13 mmol) were dissolved in 1,4-dioxane (220 mL) and distilled water (45 mL), and after introducing Pd(PPh3)4 (2.80 g, 2.43 mmol) and K2CO3 (16.78 g, 121.4 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141-P3 (13.57 g, yield 70%).
4) Preparation of Compound 141-P2
Compound 141-P3 (13.57 g, 33.99 mmol) was dissolved in benzene-d6 (678.5 g) and CF3SO3H (184.5 g), and stirred for 1 hour at 50° C. After the reaction was completed, the result was quenched with Na2CO3 in D2O. After the quenching, ethyl acetate was introduced to the mixture solution for dissolution, and after the organic layer was separated and dried with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141-P2 (9.58 g, yield 68%).
5) Preparation of Compound 141-P1
Compound 141-P2 (9.58 g, 23.11 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (8.80 g, 34.67 mmol) were dissolved in 1,4-dioxane (100 mL), and after introducing Pd(dppf)Cl2 (0.85 g, 1.16 mmol) and potassium acetate (6.8 g, 69.33 mmol) thereto, the mixture was stirred for 6 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141-P1 (8.53 g, yield=80%).
6) Preparation of Compound 141
Compound 141-P1 (8.3 g, 18.49 mmol) and 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (6.36 g, 18.49 mmol) were dissolved in 1,4-dioxane (100 mL) and distilled water (20 mL), and after introducing Pd(PPh3)4 (1.07 g, 0.93 mmol) and K2CO3 (6.39 g, 46.23 mmol) thereto, the mixture was stirred for 4 hours under reflux. After the reaction was completed, dichloromethane was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 141 (8.32 g, yield=70%).
Target compounds of the following Table 4 were synthesized in the same manner as in Preparation Example 2 except that Intermediate 1 of the following Table 4 was used instead of Compound 141-P6, and Intermediate 2 of the following Table 4 was used instead of Compound A.
1) Preparation of Compound 181-P3
Compound 181-P4 (22.79 g, 80.94 mmol) and phenylboronic acid (9.8 g, 80.94 mmol) were dissolved in 1,4-dioxane (250 mL) and distilled water (50 mL), and after introducing Pd(PPh3)4 (4.67 g, 4.047 mmol) and K2CO3 (28 g, 202.35 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 181-P3 (16.9 g, yield 75%).
2) Preparation of Compound 181-P2
Compound 3-P3 (16.9 g, 60.70 mmol) was dissolved in benzene-d6 (845 g) and CF3SO3H (230 g), and stirred for 1 hour at 50° C. After the reaction was completed, the result was quenched with Na2CO3 in D2O. After the quenching, ethyl acetate was introduced to the mixture solution for dissolution, and after the organic layer was separated and dried with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 181-P2 (11.96 g, yield 68%).
3) Preparation of Compound 181-P1
Compound 181-P2 (11.96 g, 41.28 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (15.72 g, 61.92 mmol) were dissolved in 1,4-dioxane (120 mL), and after introducing Pd2(dba)3 (1.89 g, 2.06 mmol), potassium acetate (12.14 g, 123.84 mmol) and S phos (1.69 g, 4.12 mmol) thereto, the mixture was stirred for 16 hours under reflux. After the reaction was completed, ethyl acetate was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 181-P1 (12.6 g, yield=80%).
4) Preparation of Compound 181
Compound 181-P1 (12.6 g, 33.02 mmol) and 2,4-di([1,1′-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (13.87 g, 30.91 mmol) were dissolved in 1,4-dioxane (125 mL) and distilled water (25 mL), and after introducing Pd(PPh3)4 (1.91 g, 1.65 mmol) and K2CO3 (11.41 g, 82.55 mmol) thereto, the mixture was stirred for 5 hours under reflux. After the reaction was completed, dichloromethane was introduced to the reaction solution for dissolution. The result was extracted with distilled water, and after drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain Compound 181 (14.76 g, yield=70%).
Target compounds of the following Table 5 were synthesized in the same manner as in Preparation Example 3 except that Intermediate 1 of the following Table 5 was used instead of Compound 181-P4, and Intermediate 2 of the following Table 5 was used instead of Compound A.
4-1) Preparation of Intermediate 2-79-1
In a one-neck round bottom flask, 9H,9′H-3,3′-bicarbazole (10 g, 0.030 mol), 4-bromo-1,1′-biphenyl [E] (7.26 g, 0.030 mol), CuI (0.57 g, 0.003 mol), trans-1,2-diaminocyclohexane (0.34 g, 0.003 mol) and K3PO4 (12.74 g, 0.06 mol) were dissolved in 1,4-dioxane (100 mL), and refluxed for 8 hours at 125° C. 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 Intermediate 2-79-1 (13.92 g, yield 94%).
4-2) Preparation of Compound 2-79
In a one-neck round bottom flask, Intermediate 2-2-1 (13.92 g, 0.028 mol), 3-bromo-1,1′-biphenyl [E′] (6.83 g, 0.028 mol), CuI (0.53 g, 0.0028 mol), trans-1,2-diaminocyclohexane (0.32 g, 0.0028 mol) and K3PO4 (11.89 g, 0.056 mol) were dissolved in 1,4-dioxane (140 mL), and refluxed for 8 hours at 125° C. 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 2-79 (16.14 g, yield 88%).
When Compound E and Compound E′ are the same, Compound E may be introduced in 2 equivalents in Preparation Example 4 to directly synthesize the target compound. In other words, when Compound E and Compound E′ are the same, Preparation Example 4-2 may be skipped.
The following target Compound G1 was synthesized in the same manner as in Preparation Example 4 except that Compounds E1 and E′1 of the following Table 6 were used instead of 4-bromo-1,1′-biphenyl [E] and 4-bromo-1,1′-biphenyl [E′].
1) Preparation of Compound 2-57
In a one-neck round bottom flask, a mixture of Intermediate 2-79 (12.17 g, 0.017 mol), triflic acid (51.5 g) and D6-benzene (608.5 mL) was stirred for 1 hour at 50° C. After the reaction was completed, the result was quenched with Na2CO3 in D2O. After the quenching, DCM was introduced to the mixture solution for dissolution, and after the organic layer was separated and dried with anhydrous MgSO4, the solvent was removed using a rotary evaporator. After that, the result was purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain target Compound 2-57 (8.01 g, yield 70%).
The following target Compound G2 was synthesized in the same manner as in Preparation Example 5 except that Compound E3 of the following Table 7 was used instead of Compound 2-79.
Compounds other than the compounds described in Preparation Examples 1 to 5 and Table 1 to Table 7 were also prepared in the same manner as in the methods described in the preparation examples described above, and the synthesis results are shown in the following Table 8 and Table 9. The following Table 8 shows measurement values of 1H NMR (CDCl3, 400 MHz), and the following Table 9 shows measurement values of FD-mass spectrometry (FD-Mass: field desorption mass spectrometry).
1H NMR (CDCl3, 300 MHz)
1) Manufacture of Organic Light Emitting Device
A glass substrate on which 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 WO treatment was conducted for 5 minutes using UV in a 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. The light emitting layer was deposited to 360 Å using the heterocyclic compound of Chemical Formula 1 as a host and Ir(ppy)3 (tris(2-phenylpyridine)iridium) as a green phosphorescent dopant, and doping Ir(ppy)3 to the host by 7%. After that, BCP 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.
In the following Table 10, a green host was used in the examples and the comparative examples except for the example separately indicated to use a red host. As a red phosphorescent dopant, Ir(piq)2(acac) was used.
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.
2) Driving Voltage and Light Emission Efficiency of Organic Electroluminescent Device
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 coordinate (CIE) and lifetime of the organic light emitting devices manufactured according to the present disclosure are as shown in the following Table 10.
From the results of Table 10, it is seen that the organic light emitting device comprising the heterocyclic compound of Chemical Formula 1 of the present disclosure is superior in all aspects of driving voltage, light emission efficiency and lifetime compared to the comparative examples.
Specifically, when examining Comparative Example 1 to Comparative Example 6, terminal phenyl is substituted with deuterium instead of hydrogen, and in the present disclosure, the heteroring is substituted with deuterium. Molecules are thermally damaged by electron migration when driving an organic light emitting device. Particularly, structures comprising dibenzofuran and dibenzothiophene are highly likely to have defects in oxygen or sulfur, a most unstable site.
In the compound of the present disclosure, the heterocyclic compound is substituted with deuterium having a larger molecular weight than hydrogen in order to prevent this phenomenon, and as a result, molecular energy is lowered by reducing changes in the vibrational frequency, which resultantly increases molecular stability. In addition, it may be identified that, since single bond dissociation energy of carbon and deuterium is higher than single bond dissociation energy of carbon and hydrogen, thermal stability of the molecule increases, and a device lifetime is improved as a result.
A host material needs to readily receive electrons and holes and readily transfer these to a dopant, and in Comparative Example 7 to Comparative Example 10, the triazine group is substituted with biphenyl bonding at an ortho position. In the ortho bonding, steric hindrance occurs between substituents, and electrons and holes are not stably received. Overall device performance is considered to decline due to structural instability caused by such steric hinderance.
Meanwhile, in the present disclosure, a biphenyl-based substituent bonds to the triazine group bonding at a para position. Since the biphenyl-based substituent is stretched lengthwise in para, steric hindrance does not occur in the molecule compared to when the biphenyl-based bonds at an ortho position, which is considered to more stably receive electrons and holes.
An OLED has excellent efficiency and lifetime as a recombination zone (RZ) locates at the center of a light emitting layer. A unipolar material that does not comprise carbazole such as a compound having triazine bonding to a heteroring has relatively faster electron migration compared to hole migration (refer to
Accordingly, when checking the RZ, the RZ is formed closer to a hole transfer layer than the center of EML (refer to
In other words, it was identified that driving voltage, light emission efficiency and lifetime were significantly superior when using the heterocyclic compound of Chemical Formula 1 of the present disclosure as a host of the light emitting layer.
The experiment of identifying the recombination zone (RZ) was prepared in the same manner as the method for manufacturing an organic light emitting device as in Experimental Example 1. The difference is a doping position of the green phosphorescent dopant in the light emitting layer.
#1 of
In Reference Compound K, RZ is positioned close to the hole transfer layer, and #2 was identified to have the best efficiency and lifetime. This also indicates the result of electron migration being relatively faster than hole migration in
With a compound having relatively faster electron migration as the compound of the present disclosure, higher efficiency is expected when using an electron blocking layer by preventing electrons from coming over from the light emitting layer.
Results of the experiments of identifying the recombination zone (RZ) for Reference Compounds K, L and M, and Compound 17, and results of the experiments on the hole only device (HOD) and the electron only device (EOD) may be identified in
1) Manufacture of Organic Light Emitting Device
A glass substrate on which 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 UVO treatment was conducted for 5 minutes using UV in a 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 the heterocyclic compound of Chemical Formula 1 and one type of the compound of Chemical Formula 2 were pre-mixed and then deposited to 360 Å in one source of supply as a host, and Ir(ppy)3, a green phosphorescent dopant, was doped and deposited by 7% of the deposited thickness of the light emitting layer. After that, BCP 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.
In the following Table 11, a green host was used in the examples and the comparative examples except for the example separately indicated to use a red host. As a red phosphorescent dopant, Ir(piq)2(acac) was used.
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 coordinate (CIE) and lifetime of the organic light emitting devices manufactured according to the present disclosure are as shown in the following Table 11.
A:2-78
B:2-76
G:2-79
H:2-77
C:2-74
When comparing the results of Table 10 with the results of Table 11, it may be identified that driving voltage, light emission efficiency and lifetime are all improved when using the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 at the same time as a host of the light emitting layer.
Effects of more superior efficiency and lifetime are obtained when comprising the compound of Chemical Formula 1 and the compound of Chemical Formula 2 at the same time. Such results may lead to a forecast that an exciplex phenomenon occurs when comprising 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 present disclosure, excellent device properties were obtained when using the compound of Chemical Formula 2 performing a donor role and the compound of Chemical Formula 1 performing an acceptor role donor as a host of the light emitting layer.
Particularly, it is identified that excellent lifetime properties are obtained when substituted with deuterium. This is a result obtained from deuterium substitution as described in the results of Table 10, and implies that compound properties may vary depending on deuterium substitution even when having a similar structure.
On the other hand, it is seen that performance in terms of driving voltage, light emission efficiency and lifetime declines when the compound not included in the scope of the present disclosure (Comparative Examples 11 to 28) is used in combination with the compound of Chemical Formula 2.
In other words, it is identified that driving voltage, light emission efficiency and lifetime are significantly superior when using the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 of the present disclosure at the same time as a host of the light emitting layer.
Particularly, it is identified that excellent lifetime properties are obtained when substituted with deuterium. This is a result obtained from deuterium substitution as described in the results of Table 10, and implies that compound properties may vary depending on deuterium substitution even when having a similar structure.
On the other hand, it is seen that performance in terms of driving voltage, light emission efficiency and lifetime declines when the compound not included in the scope of the present disclosure (Comparative Examples 14 to 31) is used in combination with the compound of Chemical Formula 2.
In other words, it is identified that driving voltage, light emission efficiency and lifetime are significantly superior when using the heterocyclic compound of Chemical Formula 1 and the compound of Chemical Formula 2 of the present disclosure at the same time as a host of the light emitting layer.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0125761 | Sep 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/012272 | 9/9/2021 | WO |
