Patent Grant
12150379
This application is the U.S. National Stage of International Application No. PCT/CN2022/134759, filed on Nov. 28, 2022, which claims the benefit of Chinese patent application No. 202210794941.1 filed on Jul. 7, 2022, the contents of each of which are incorporated herein by reference in their entirety as a part of this application.
The present disclosure relates to the technical field of organic electroluminescent materials, and in particular to an arylamine compound, an organic electroluminescent device comprising the arylamine compound, and an electronic apparatus.
With the development of electronic technology and the advancement of material science, electronic devices for achieving electroluminescence or photoelectric conversion have found an increasingly wide range of applications. An organic electroluminescent device typically includes a cathode and an anode that are disposed opposite to each other, and a functional layer disposed between the cathode and the anode. The functional layer consists of a plurality of organic or inorganic film layers, and generally comprises an organic light-emitting layer, a hole transport layer, an electron transport layer, etc. When a voltage is applied to the cathode and the anode, an electric field is formed between the two electrodes. Under the influence of the electric field, electrons on the cathode side migrate to the electroluminescent light-emitting layer, and holes on the anode side also migrate to the electroluminescent light-emitting layer. The electrons and the holes recombine in the electroluminescent light-emitting layer, forming excitons. The excitons in excited states release energy, causing the electroluminescent light-emitting layer to emit light to the outside.
Main problems with existing organic electroluminescent devices lie in their service life and efficiency. As display screens become larger and larger, driving voltages are increased accordingly, which necessitates improvement in luminous efficiency and current efficiency. It is therefore necessary to continue to develop new materials to further improve the performance of organic electroluminescent devices.
Directed against the above problems with the existing technology, the present disclosure aims at providing an arylamine compound, an organic electroluminescent device comprising the arylamine compound, and an electronic apparatus. The arylamine compound, when used in an organic electroluminescent device, can improve the performance of the device.
According to a first aspect of the present disclosure, there is provided an arylamine compound. The arylamine compound has a structure shown in Formula 1:
According to a second aspect of the present disclosure, there is provided an organic electroluminescent device comprising an anode and a cathode that are disposed opposite to each other, and a functional layer disposed between the anode and the cathode. The functional layer comprises the arylamine compound described above.
According to a third aspect of the present disclosure, there is provided an electronic apparatus comprising the organic electroluminescent device described in the second aspect.
The structure of the arylamine compound of the present disclosure includes benzocarbazolyl and benzoxazolyl or benzothiazolyl groups. The benzocarbazolyl group has an excellent hole transport property, and the benzoxazolyl or benzothiazolylgroup has a relatively large conjugation plane, which is conducive to intermolecular accumulation and can further improve hole mobility in the compound of the present disclosure. A triarylamine compound, when used as a hole transport-type host material, can be oxidized to form free radical cations. The benzoxazolyl or benzothiazolyl group linked, directly or indirectly via a benzene ring, to the nitrogen atoms of the arylamine can stabilize theses free radical cations and improve the electrochemical stability of the compound. Therefore, the compound of the present disclosure, when used as a hole transport-type host material in a mixed-type host material of an organic electroluminescent device, can significantly improve the efficiency of the device and significantly prolong service life thereof.
The accompanying drawings are intended to provide a further understanding of the present disclosure and form a part of the specification. The accompanying drawings, together with the following specific embodiments, are used to illustrate the present disclosure, but do not constitute any limitation on the present disclosure.
Exemplary embodiments will now be described more comprehensively with reference to the accompanying drawings. The exemplary embodiments, however, can be implemented in a variety of forms and should not be interpreted as being limited to the examples set forth herein. On the contrary, these embodiments are provided to make the present disclosure more comprehensive and complete, and to communicate the concepts of these exemplary embodiments fully to those skilled in the art. Features, structures, or characteristics described can be combined in one or more embodiments in any suitable manner. In the following description, many specific details are provided to give a full understanding of the embodiments of the present disclosure.
The present disclosure, in a first aspect, provides an arylamine compound. The arylamine compound has a structure shown in Formula 1;
In the present disclosure, the term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur. As an example, the expression “optionally, any two adjacent substituents form a saturated or unsaturated 3 to 15-membered ring” involve instances where any two adjacent substituents form a ring, and instances where any two adjacent substituents exist independently and do not form a ring. The expression “any two adjacent” may involve instances where there are two substituents on a same atom and also involve instances where there is one substituent on each of two adjacent atoms. When there are two substituents on a same atom, the two substituents, together with the atom to which they are attached, may form a saturated or unsaturated spiro ring; and when there is one substituent on each of two adjacent atoms, the two substituents may be fused into a ring.
In the present disclosure, the expression “each . . . independently” may be used interchangeably with the expressions “ . . . independently”, and “ . . . each independently”, and all these expressions should be interpreted in a broad sense. They can not only mean that, for same symbols in a same group, the selection of a specific option for one of the symbols and the selection of a specific option for another one of the symbols do not affect each other, but also mean that for same symbols in different groups, the selection of a specific option for one of the symbols and the selection of a specific option for another one of the symbols do not affect each other. Taking
as an example, each q is independently selected from 0, 1, 2, or 3, and each R″ is independently selected from hydrogen, deuterium, fluorine, and chlorine, which means: in Formula Q-1, there are q substituents R″ on the benzene ring, wherein each of the substituent R″ may be identical or different, with the selection of an option for one of the substituents R″ and the selection of an option for another one of the substituents R″ not affecting each other; and in Formula Q-2, there are q substituents R″ on each of the two benzene rings of biphenyl, wherein the number q of the substituent R″ on one benzene ring and the number q of the substituent R″ on the other benzene ring may be identical or different, and each substituent R″ may be identical or different, with the selection of an option for one of the substituents R″ and the selection of an option for another one of the substituents R″ not affecting each other.
In the present disclosure, the term “substituted or unsubstituted” means that the functional group defined by the term may or may not have a substituent (hereinafter referred to as Rc for ease of description). For example, “substituted or unsubstituted aryl” refers to aryl having a substituent Rc or aryl having no substituent. The foregoing substituent, namely Rc, may be, for example, deuterium, halogen, cyano, heteroaryl, aryl, trialkylsilyl, alkyl, haloalkyl, cycloalkyl, etc. The number of the substitutes may be one or more.
In the present disclosure, “more” means more than 2, such as 2, 3, 4, 5, 6, etc.
In the present disclosure, the number of carbon atoms of a substituted or unsubstituted functional group is the number of all carbon atoms.
Hydrogen atoms in the structure of the compound of the present disclosure include various isotopic atoms of hydrogen element, such as hydrogen (H), deuterium (D), or tritium (T).
“D” in a structural formula of a compound of the present disclosure represents “deuterated”.
In the present disclosure, “aryl” refers to any functional group or substituent group derived from an aromatic carbon ring. An aryl group may be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group. In other words, an aryl group may be a monocyclic aryl group, a fused aryl group, two or more monocyclic aryl groups linked by carbon-carbon bond conjugation, a monocyclic aryl group and a fused aryl group linked by carbon-carbon bond conjugation, or two or more fused aryl groups linked by carbon-carbon bond conjugation. That is, unless otherwise specified, two or more aromatic groups linked by carbon-carbon bond conjugation may also be regarded as an aryl group in the present disclosure. Among them, fused aryl groups may include, for example, bicyclic fused aryl groups (e.g., naphthyl), tricyclic fused aryl groups (e.g., phenanthryl, fluorenyl, anthryl) and the like. An aryl group does not contain heteroatoms such as B, N, O, S, P, Se, Si, etc. Examples of aryl may include, but are not limited to, phenyl, naphthyl, fluorenyl, spirodifluorenyl, anthryl, phenanthryl, biphenyl, terphenyl, triphenylene
perylenyl, benzo[9,10]phenanthryl, pyrenyl, benzofluoranthenyl, chrysenyl, etc.
In the present disclosure, “arylene” refers to a divalent group formed by further removing one or more hydrogen atoms from an aryl group.
In the present disclosure, “terphenyl” includes
and
In the present disclosure, the number of carbon atoms of substituted or unsubstituted aryl (arylene) may be 6, 8, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 30. In some embodiments, substituted or unsubstituted aryl is substituted or unsubstituted aryl having 6 to 30 carbon atoms. In other embodiments, substituted or unsubstituted aryl is substituted or unsubstituted aryl having 6 to 25 carbon atoms. In other embodiments, substituted or unsubstituted aryl is substituted or unsubstituted aryl having 6 to 18 carbon atoms. In other embodiments, substituted or unsubstituted aryl is substituted or unsubstituted aryl having 6 to 15 carbon atoms.
In the present disclosure, fluorenyl may be substituted by one or more substituents. In the case where the above fluorenyl is substituted, the substituted fluorenyl may be, but is not limited to,
etc.
In the present disclosure, aryl, as a substituent of L, L1, L2, Ar1, Ar3, and Ar4, may be, but is not limited to, phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, dimethylfluorenyl, etc.
In the present disclosure, “heteroaryl” refers to a monovalent aromatic ring containing 1, 2, 3, 4, 5, or 6 heteroatoms or a derivative thereof. The heteroatoms may be one or more selected from B, O, N, P, Si, Se, and S. A heteroaryl group may be a monocyclic heteroaryl group or polycyclic heteroaryl group. In other words, a heteroaryl group may be a single aromatic ring system, or a plurality of aromatic ring systems linked by carbon-carbon bond conjugation, with any of the aromatic ring systems being an aromatic monocyclic ring or a fused aromatic ring. For example, heteroaryl groups may include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridinyl, bipyridinyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, silylfluorenyl, dibenzofuranyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, etc.
In the present disclosure, “heteroarylene” is a divalent or polyvalent group formed by further removing one or more hydrogen atoms from a heteroaryl group.
In the present disclosure, the number of carbon atoms of substituted or unsubstituted heteroaryl (heteroarylene) may be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some embodiments, substituted or unsubstituted heteroaryl is substituted or unsubstituted heteroaryl having 12 to 18 carbon atoms. In other embodiments, substituted or unsubstituted heteroaryl is substituted or unsubstituted heteroaryl having 5 to 12 carbon atoms.
In the present disclosure, heteroaryl, as a substituent of L, L1, L2, Ar1, Ar3, and Ar4, may be, but is not limited to, for example, pyridyl, carbazolyl, dibenzothienyl, dibenzofuranyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl.
In the present disclosure, substituted heteroaryl may mean that one or more than two hydrogen atoms in the heteroaryl group are substituted by a group such as a deuterium atom, halogen, cyano, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, haloalkyl, etc.
In the present disclosure, alkyl having 1 to 10 carbon atoms may include linear alkyl having 1 to 10 carbon atoms and branched alkyl having 3 to 10 carbon atoms. For example, the number of carbon atoms of alkyl may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specific examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc.
In the present disclosure, halogen may be, for example, fluorine, chlorine, bromine, or iodine.
In the present disclosure, specific examples of trialkylsilyl include, but are not limited to, trimethylsilyl, triethylsilyl, etc.
In the present disclosure, specific examples of haloalkyl include, but are not limited to, trifluoromethyl.
In the present disclosure, the number of cycloalkyl having 3 to 10 carbon atoms may be, for example, 3, 4, 5, 6, 7, 8, or 10. Specific examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, adamantly, etc.
In the present disclosure, the number of carbon atoms of deuterated alkyl having carbon atoms 1 to 10 is, for example, 1, 2, 3, 4, 5, 6, 7, 8 or 10. Specific examples of deuterated alkyl include, but are not limited to, trideuteromethyl.
In the present disclosure, the number of carbon atoms of haloalkyl having 1 to 10 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8 or 10. Specific examples of haloalkyl include, but are not limited to, trifluoromethyl.
In the present disclosure, a ring system formed by n atoms is an n-membered ring. For example, phenyl is a 6-membered ring. A 3 to 15-membered ring refers to a cyclic group having 3 to 15 ring atoms. A 3 to 15-membered ring may be, for example, cyclopentane, cyclohexane, a fluorene ring, a benzene ring, etc.
In the present disclosure,
refers to a chemical bond linked with other groups.
In the present disclosure, a non-positional bond is single bond
extending from a ring system, and it indicates that the linkage bond can be linked at one end thereof to any position in the ring system through which the bond passes, and linked at the other end thereof to the rest of the compound molecule. For example, as shown in Formula (f) below, the naphthalyl group represented by Formula (f) is linked to other positions of the molecule via two non-positional bonds passing through the two rings, which indicates any of possible linkages shown in Formulae (f-1) to (f-10):
As another example, as shown in Formula (X′) below, the dibenzofuranyl group represented by Formula (X′) is linked to other positions of the molecule via a non-positional bond extending from the center of a side benzene ring, which indicates any of possible linkages shown in Formulae (X′-1) to (X′-4):
A non-positional substituent in the present disclosure refers to a substituent linked via single bond extending from the center of a ring system, and it means that the substituent may be linked to any possible position in the ring system. For example, as shown in Formula (Y) below, the substituent R′ represented by Formula (Y) is linked to a quinoline ring via a non-positional bond, which indicates any of possible linkages shown in Formulae (Y-1) to (Y-7):
In some embodiments, Formula 1 is specifically selected from structures shown in Formulae 1-1 to 1-3;
In the above Formulae 1-1 to 1-3, each symbol has a definition as it has in Formula 1.
A compound having the structure shown in Formula 1-2 or 1-3 requires a lower operating voltage.
In some embodiments, the compound shown in Formula 1 has a structure shown in the following Formulae 1-4 to 1-31;
In the above Formulae 1-4 to 1-31, each symbol has a definition as it has in Formula 1.
In some embodiments, L, L1, and L2 are each independently selected from the group consisting of single bond, substituted or unsubstituted arylene having 6 to 15 carbon atoms, and substituted or unsubstituted heteroarylene having 12 to 18 carbon atoms.
In some embodiments, L, L1, and L2 are each independently selected from the group consisting of single bond, substituted or unsubstituted arylene having 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms, and substituted or unsubstituted heteroarylene having 12, 13, 14, 15, 16, 17, or 18 carbon atoms.
Optionally, the substituents in L, L1, and L2 are identical or different, and are each independently selected from the group consisting of deuterium, halogen, cyano, alkyl having 1 to 5 carbon atoms, haloalkyl having 1 to 5 carbon atoms, deuterated alkyl having 1 to 5 carbon atoms, trialkylsilyl having 3 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, or heteroaryl having 5 to 12 carbon atoms.
In some embodiments, L, L1, and L2 are each independently selected from the group consisting of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorenylidene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzothienylene, and substituted or unsubstituted dibenzofuranylene.
Optionally, the substituents in L, L1, and L2 are each independently selected from the group consisting of deuterium, fluorine, cyano, trimethylsilyl, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, or naphthyl.
In some embodiments, L and L1 are each independently selected from the group consisting of single bond, phenylene, deuterated phenylene, or naphthylene.
In some embodiments, L and L1 are each independently selected from the group consisting of single bond and the following groups:
In some embodiments, L2 is selected from the group consisting of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted dibenzofuranylene.
Optionally, the substituents in L2 are each independently selected from the group consisting of deuterium, fluorine, cyano, trimethylsilyl, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, or phenyl.
In some embodiments, L2 is selected from the group consisting of single bond and the following groups:
In some embodiments, Ar1, Ar3, and Ar4 are each independently selected from the group consisting of substituted or unsubstituted aryl having 6 to 25 carbon atoms, and substituted or unsubstituted heteroaryl having 7 to 20 carbon atoms.
In some embodiments, Ar1, Ar3, and Ar4 are each independently selected from the group consisting of substituted or unsubstituted aryl having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 carbon atoms, and substituted or unsubstituted heteroaryl having 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
In some embodiments, the substituents in Ar1, Ar3, and Ar4 are each independently selected from the group consisting of deuterium, halogen, cyano, haloalkyl having 1 to 4 carbon atoms, deuterated alkyl having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 5 to 12 carbon atoms, and trialkylsilyl having 3 to 8 carbon atoms; optionally, any two adjacent substituents form a benzene ring or a fluorene ring.
In some embodiments, Ar1 and Ar3 are each independently selected from substituted or unsubstituted group W, the unsubstituted group W is selected from the group consisting of the following groups:
In some embodiments, Ar1 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, and substituted or unsubstituted carbazolyl.
Optionally, the substituents in Ar1 are each independently selected from the group consisting of deuterium, fluorine, cyano, trimethylsilyl, triphenylsilyl, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl, or carbazolyl.
In some embodiments, Ar1 is selected from the following groups:
In some embodiments, Ar1 and Ar3 are each independently selected from the following groups:
In some embodiments, Ar4 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, and substituted or unsubstituted carbazolyl.
Optionally, the substituents in Ar4 are each independently selected from the group consisting of deuterium, fluorine, cyano, trimethylsilyl, triphenylsilyl, trideuteromethyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, or carbazolyl.
In some embodiments, Ar4 is selected from the following groups:
In some embodiments, Ar2 is selected from the following groups:
In some embodiments. Ar2 is selected from the following groups:
In some embodiments,
is selected from the following groups:
In some embodiments, each R1, each R2, each R3 is identical or different, and is independently selected from the group consisting of deuterium, cyano, fluorine, trideuteromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, or naphthyl; optionally, any two adjacent R3 form a benzene ring.
In some embodiments,
is selected from the following groups:
In some embodiments, the arylamine compound is selected from the group consisting of the following compounds:
The present disclosure, in a second aspect, provides an organic electroluminescent device comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode. The functional layer comprises the arylamine compound described in the first aspect of the present disclosure.
The arylamine compound provided in the present disclosure may be used to form at least one organic film layer in the functional layer so as to improve properties of the organic electroluminescent device such as luminous efficiency and service life.
Optionally, the functional layer comprises an organic light-emitting layer. The organic light-emitting layer comprises the arylamine compound. The organic light-emitting layer may be composed of the arylamine compound provided in the present disclosure, or may be composed of the arylamine compound provided in the present disclosure together with other materials.
Optionally, the functional layer further comprises a hole transport layer (also known as first hole transport layer) and a hole adjustment layer (also known as second hole transport layer). The hole transport layer is located between the anode and the organic light-emitting layer, and the hole adjustment layer is located between the hole transport layer and the organic light-emitting layer. In some embodiments, the hole adjustment layer is composed of the arylamine compound provided in the present disclosure, or composed of the arylamine compound provided in the present disclosure together with other materials.
According to a specific embodiment, the organic electroluminescent device is as shown in
In the present disclosure, the anode 100 comprises an anode material, which is preferably a high-work function material contributing to injection of holes into the functional layer. Specific examples of the anode material include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc, gold, and 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; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline. Preferably, a transparent electrode comprising indium tin oxide (ITO) is included as the anode.
In the present disclosure, the hole transport layer and the hole adjustment layer each may comprise one or more hole transport materials. The hole transport material may be selected from carbazole polymer, carbazole-linked triarylamine compounds, or other types of compounds, which may be selected from the following compounds or any combination thereof:
In an embodiment, the hole transport layer 321 is composed of α-NPD.
In an embodiment, the hole adjustment layer 322 is composed of HT-1.
Optionally, a hole injection layer 310 is further provided between the anode 100 and the hole transport layer 321 so as to enhance the ability to inject holes into the hole transport layer 321. The hole injection layer 310 may be composed of a material selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, and other materials, and the present disclosure is not particularly restricted in this respect. The material of the hole injection layer 310 is, for example, selected from the following compounds or any combinations thereof:
In an embodiment of the present disclosure, the hole injection layer 310 is composed of PD.
Optionally, the organic light-emitting layer 330 may be composed of a single luminescent material, or may comprise a host material and a dopant material. Optionally, the organic light-emitting layer 330 is composed of a host material and a dopant material. Holes injected into the organic light-emitting layer 330 and electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons. The excitons transmit energy to the host material, and the host material transmits the energy to the dopant material, thereby enabling the dopant material to emit light.
The host material of the organic light-emitting layer 330 may include metal chelating compounds, stilbene derivatives, aromatic amine derivatives, dibenzofuran derivatives, or other types of materials. The host material of the organic light-emitting layer 330 may be one compound, or a combination of two or more compounds. Optionally, the host material comprises the arylamine compound of the present disclosure.
The dopant material of the organic light-emitting layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, and the present disclosure is not particularly restricted in this respect. The dopant material is also known as a doping material or a dopant, which can be categorized, according to its type of luminescence, as a fluorescent dopant or a phosphorescent dopant. Specific examples of the phosphorescent dopant include, but are not limited to:
In an embodiment of the present disclosure, the organic electroluminescent device is a red light-emitting organic electroluminescent device. In a more specific embodiment, the host material of the organic light-emitting layer 330 comprises the arylamine compound of the present disclosure. The dopant material may be, for example, RD-1.
The electron transport layer 340 may be a single-layer structure or a multi-layer structure, and may comprise one or more electron transport materials. The electron transport materials may be selected from, but are not limited to, LiQ, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which are not particularly limited in the present disclosure. The material of the electron transport layer 340 includes, but is not limited to, the following compounds:
In an embodiment of the present disclosure, the electron transport layer 340 is composed of ET-1 and LiQ.
In the present disclosure, the cathode 200 comprises a cathode material, which is a low-work function material contributing to injection of electrons into the functional layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, and alloys thereof; or multilayer materials such as LiF/Al, Liq/Al, LiO2/Al, LiF/Ca, LiF/Al, and BaF2/Ca. Optionally, a metal electrode comprising magnesium and silver is included as the cathode.
Optionally, an electron injection layer 350 is further provided between the cathode 200 and the electron transport layer 340 so as to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may comprise an inorganic material such as an alkali metal sulfide, an alkali metal halide, and the like, or may comprise a complex of an alkali metal and an organic compound. In an embodiment of the present disclosure, the electron injection layer 350 comprises ytterbium (Yb).
The present disclosure, in a third aspect, provides an electronic apparatus including the organic electroluminescent device described in the second aspect of the present disclosure.
According to an embodiment, as shown in
A synthesis method of the arylamine compound of the present disclosure is described in detail below in conjunction with Synthesis Examples, but the present disclosure is not limited thereto in any way.
Those skilled in the art should appreciate that chemical reactions described in the present disclosure may be used properly to prepare many arylamine compounds of the present disclosure, and other methods that can be used to prepare the compounds of the present disclosure are all considered to be within the scope of the present disclosure.
For example, the synthesis of those non-exemplary compounds of the present disclosure may be successfully accomplished by those skilled in the art by modifying the method, for example, by properly protecting an interfering group, by utilizing other known reagents other than those described in the present disclosure, or by making some conventional modifications to reaction conditions. Compounds for which a synthesis method is not mentioned in the present disclosure are raw material products obtained commercially.
7-bromo-2-phenylbenzooxazole (13.71 g, 50 mmol), 3-chlorophenylboronic acid (8.60 g, 55 mmol), tetrakis(triphenylphosphine)palladium (0.58 g, 0.5 mmol), tetrabutylammonium bromide (1.61 g, 5 mmol), anhydrous potassium carbonate (13.82 g, 100 mmol), toluene (140 mL), absolute ethanol (35 mL), and deionized water (35 mL) were sequentially added under a nitrogen atmosphere to a 500-mL three-neck flask, heated to reflux and stirred for 16 hours. After being cooled to room temperature, the reaction solution was extracted with dichloromethane (100 mL×3 times). The resulting organic phases were combined and then dried with anhydrous magnesium sulfate, followed by filtration and then distillation under reduced pressure to remove the solvent, obtaining a crude product. The crude product was purified by silica gel column chromatography with n-heptane as a mobile phase, yielding white solid Sub-al (12.53 g, yield 82%).
Sub-a2 to Sub-a7 were synthesized respectively following the synthesis method of Sub-a1, except that 7-bromo-2-phenylbenzooxazole was replaced with a corresponding reactant A shown in Table 1, and that 3-chlorophenylboronic acid was replaced with a corresponding reactant B.
CAS: 1268137-13-8
CAS: 1679-18-1
CAS: 1268137-13-8
CAS: 3900-89-8
CAS: 63503-60-6
CAS: 63503-60-6
CAS: 63503-60-6
CAS: 1679-18-1
9-bromo-11H-benzo[A]carbazole (14.81 g, 50 mmol), 4-iodobiphenyl (16.81 g, 60 mmol), cuprous iodide (1.90 g, 10 mmol), 18-crown-6 (1.32 g, 5 mmol), 1,10-phenanthroline (3.96 g, 20 mmol), potassium carbonate (15.20 g, 110 mmol), and N,N-dimethylformamide (150 mL) were added sequentially under a nitrogen atmosphere to a 250-mL three-neck flask, and heated to reflux and stirred overnight. After being cooled to room temperature, the reaction solution was poured into 250 mL of deionized water, and then filtered. The filter cake was collected, dissolved in dichloromethane, and dried with anhydrous sodium sulfate, followed by filtration and then distillation under reduced pressure to remove the solvent, obtaining a crude product. The crude product was purified by silica gel column chromatography with n-heptane/dichloromethane as a mobile phase, yielding white solid Sub-b1 (18.45 g, yield 65%).
Sub-b2 to Sub-b9 were synthesized respectively following the synthesis method of Sub-b1, except that 9-bromo-11H-benzo[A]carbazole was replaced with a corresponding reactant C shown in Table 2, and that 4-iodobiphenyl was replaced with a corresponding reactant D.
CAS: 131409-18-2
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RM-1 (CAS: 1374003-98-1, 9.31 g, 25 mmol) and 200 mL of benzene-D6 were added under a nitrogen atmosphere to a 100-mL three-neck flask, and heated to 60° C., followed by addition of trifluoromethanesulfonic acid (22.51 g, 150 mmol), and heating to boil for a reaction under stirring for 24 hours. After the reaction solution was cooled to room temperature, 50 mL of deuteroxide was added, followed by stirring for 10 minutes, and then addition of a saturated aqueous solution of K3PO4 to neutralize the reaction solution. The resulting organic layers (50 mL×3 times) were extracted with dichloromethane. The organic phases were combined and then dried with anhydrous sodium sulfate, followed by filtration and then distillation under reduced pressure to remove the solvent, obtaining a crude product. The crude product was purified by silica gel column chromatography using n-heptane/dichloromethane as a mobile phase, yielding white solid Sub-b10 (6.10 g, yield 64%).
Sub-b11 was synthesized following the synthesis method of Sub-b10, except that RM-1 was replaced with reactant E shown in Table 2.
CAS: 2415099-58-8
Sub-a1 (15.28 g, 50 mmol), 4-benzidine((8.46 g, 50 mmol), tris(dibenzylideneacetonyl)bis-palladium (0.916 g, 1 mmol), 2-dicyclohexylphosphino-2′,4′,6′ triisopropylbiphenyl (XPhos, 0.95 g, 2 mmol), sodium tert-butoxide (9.61 g, 100 mmol), and toluene (150 mL) were sequentially added under a nitrogen atmosphere to a 250-mL three-neck flask, heated to reflux and stirred overnight. After being cooled to room temperature, the reaction solution was poured into 250 mL of deionized water, stirred thoroughly for 30 minutes, and filtered. The resulting filter cake was rinsed with deionized water to neutral, and then rinsed with absolute ethanol (100 mL). The filter cake was collected and recrystallized with toluene, obtaining gray-green solid Sub-c1 (17.10 g; yield 78%).
Sub-c2 to Sub-c37 were synthesized respectively following the synthesis method of Sub-c1, except that Sub-a1 was replaced with a corresponding reactant F shown in Table 3, and that 4-benzidine was replaced with a corresponding reactant G.
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Sub-b11
1020718-93-7
Sub-c1 (10.96 g, 25 mmol), 5-bromo-7-phenyl-7H-benzo[c]carbazole (10.24 g, 27.5 mmol), tris(dibenzylideneacetonyl)bis-palladium (0.46 g, 0.5 mmol), 2-biscyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos, 0.41 g, 1 mmol), sodium tert-butoxide (4.80 g, 50 mmol), and xylene (100 mL) were sequentially added under a nitrogen atmosphere to a 250-mL three-neck flask, heated to reflux and stirred overnight. After being cooled to room temperature, the reaction solution was extracted with dichloromethane (100 mL×3 times). The resulting organic phases were combined and then dried with anhydrous magnesium sulfate, followed by filtration and distillation under reduced pressure to remove the solvent, obtaining a crude product. The crude product was purified by silica gel column chromatography with n-heptane as a mobile phase, yielding white solid Compound 5 (11.50 g, yield 63%), m/z=730.3[M+H]+. Compounds of the present disclosure shown in Table 4 were synthesized respectively following the synthesis method of Compound 5, except that Sub-c1 was replaced with a corresponding reactant H shown in Table 4, and that 5-bromo-7-phenyl-7H-benzo[c]carbazole was replaced with a corresponding reactant J.
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87
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175
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1H-NMR NMR Data of Compounds:
Fabrication and Evaluation of Organic Electroluminescent Devices
First, anode pretreatment was performed by the following processes. A surface of an ITO/Ag/ITO substrate, with thicknesses of ITO/Ag/ITO being 100 Å, 1000 Å, and 100 Å, respectively, was treated using ultraviolet ozone and O2:N2 plasma to increase the work function of the anode, and then cleaned with an organic solvent to remove impurities and oil on the ITO substrate.
Compound PD was deposited by vacuum evaporation on the experimental substrate (anode) to form a hole injection layer (HIL) with a thickness of 100 Å, and then α-NPD was deposited by vacuum evaporation on the hole injection layer to form a hole transport layer with a thickness of 1080 Å.
Compound HT-1 was deposited by vacuum evaporation on the hole transport layer to form a hole adjustment layer with a thickness of 690 Å.
Next, Compound 5, Compound RH—N, and Compound RD-1 were co-deposited by evaporation on the hole adjustment layer in a mass ratio of 49%: 49%: 2% to form a red light-emitting layer (EML) with a thickness of 400 Å.
Compound ET-1 and Compound LiQ were mixed in a 1:1 weight ratio and deposited by evaporation on the light-emitting layer to form an electron transport layer (ETL) with a thickness of 350 Å; Yb was deposited by evaporation on the electron transport layer to form an electron injection layer (EIL) with a thickness of 10 Å; and then magnesium (Mg) and silver (Ag) were mixed in a rate ratio of 1:9, and deposited by vacuum evaporation on the electron injection layer to form a cathode with a thickness of 130 Å.
Further, Compound CP-1 was deposited by vacuum evaporation on the above cathode to form a capping layer with a thickness of 820 Å, completing the fabrication of a red organic electroluminescent device.
Organic electroluminescent devices were fabricated respectively by the same method as used in Example 1, except that Compound 5 in Example 1 was replaced with a corresponding Compound X shown in the following Table 5 when a light-emitting layer was formed.
Organic electroluminescent devices were fabricated respectively by the same method as used in Example 1, except that Compound 5 in Example 1 was replaced with a corresponding one of Compound A, Compound B, Compound C, and Compound D when a light-emitting layer was formed.
Structures of the compounds used in the Examples and Comparative Examples are as follows:
The red organic electroluminescent devices fabricated in Examples 1 to 44 and
Comparative Examples 1 to 4 were tested for their performance. Specifically, the IVL characteristics of the devices were tested under the condition of 10 mA/cm2, and the T95 lifetime of the devices was tested under the condition of 20 mA/cm2. Test results are shown in Table 5.
As can be seen from the above Table 5, compared with Comparative Examples 1 to 4, the Examples, in which the compounds of the present disclosure are used as the host material of the red organic electroluminescent devices, the operating voltage is decreased by at least 0.1V, and the efficiency is increased by at least 11.6%, and the service life is increased by at least 15.13%.
The structure of each of the arylamine compounds of the present disclosure includes benzocarbazolyl and benzoxazolyl or benzothiazolyl groups. The benzocarbazolyl group has an excellent hole transport property, and the benzoxazolyl or benzothiazolyl group has a relatively large conjugation plane, which is conducive to intermolecular accumulation and can further improve hole mobility in the compounds of the present disclosure. A triarylamine compound, when used as a hole transport-type host material, can be oxidized to form free radical cations. The benzoxazolyl or benzothiazolyl group linked, directly or indirectly via a benzene ring, to the nitrogen atoms of the arylamine can stabilize theses free radical cations and improve the electrochemical stability of the compounds. Therefore, the compounds of the present disclosure, when used as a hole transport-type host material in a mixed-type host material, can significantly improve the efficiency of a device and significantly prolong service life thereof.
The above describes in detail the preferred embodiments of the present disclosure with reference to the accompanying drawings. The present disclosure, however, is not limited to those specific details provided in the above embodiments. A variety of simple variations may be made to the technical solutions of the present disclosure within the scope of the technical conception of the present disclosure, and all such simple variations are within the protection scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210794941.1 | Jul 2022 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/134759 | 11/28/2022 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2024/007511 | 1/11/2024 | WO | A |
| Number | Date | Country |
|---|---|---|
| 113105420 | Jul 2021 | CN |
| 113773314 | Dec 2021 | CN |
| 115109051 | Sep 2022 | CN |
| 20210050474 | May 2021 | KR |
| WO-2021230714 | Nov 2021 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20240298529 A1 | Sep 2024 | US |
