Patent Application
20250122168
The present disclosure claims the priority of Chinese patent application No. CN202310071951.7 filed on Jan. 11, 2023, and Chinese patent application No. CN202310184175.1 filed on Mar. 1, 2023, the contents of which are incorporated here by reference in their entirety as part of the present disclosure.
The present disclosure relates to the technical field of organic compounds, in particular to an organic compound, and a composition, an organic electroluminescent device and an electronic apparatus including the same.
With the development of electronic technology and the advancement of material science, the application range of electronic components for realizing electroluminescence is becoming more and more extensive. The electronic component generally includes a cathode and an anode which are oppositely disposed, and a functional layer disposed between the cathode and the anode. The functional layer is composed of a plurality of organic or inorganic film layers and generally includes an organic light-emitting layer, a hole transport layer located between the organic light-emitting layer and the anode, and an electron transport layer located between the organic light-emitting layer and the cathode. Taking an organic electroluminescent device as an example, the organic electroluminescent device generally includes an anode, a hole transport layer, an organic light-emitting layer, an electron transport layer and a cathode which are sequentially stacked. When a voltage is applied to the cathode and the anode, an electric field is generated between the two electrodes, electrons on the cathode side move towards the organic light-emitting layer and holes on the anode side also move towards the organic light-emitting layer under the action of the electric field. The electrons and the holes are combined in the organic light-emitting layer to form excitons, the excitons are in an excited state and release energy outwards, and then the organic light-emitting layer emits light outwards.
The prior art discloses a host material for the organic light-emitting layer that can be prepared in the organic electroluminescent device. However, it is still necessary to continue to develop new materials to further improve the performance of the electronic components.
In order to solve the above problems, an object of the present disclosure is to provide an organic compound, and a composition, an organic electroluminescent device, and an electronic apparatus including the same. The organic compound can improve the performance of the organic electroluminescent device and the electronic apparatus, such as reducing the driving voltage of the device, and improving the efficiency and service life of the device.
According to a first aspect of the present disclosure, provided is an organic compound, having a structure as shown in a formula 1:
According to a second aspect of the present disclosure, provided is a composition, including a first compound disclosed in the first aspect of the present disclosure and a second compound having a structure as shown in a formula 2:
According to a third aspect of the present disclosure, provided is an organic electroluminescent device, including an anode and a cathode which are oppositely disposed, and a functional layer disposed between the anode and the cathode, where the functional layer includes the organic compound disclosed in the first aspect of the present disclosure or the composition disclosed in the second aspect of the present disclosure.
According to a fourth aspect of the present disclosure, provided is an electronic apparatus, including the organic electroluminescent device disclosed in the third aspect of the present disclosure.
A core structure of the organic compound of the present disclosure is phenylcarbazole connected to a triazine group through a nitrogen atom, and one of benzene rings on the carbazole ring is fully deuterated and the other benzene ring is connected to pentadeuterophenyl. Pentadeuterophenyl is introduced as a substituent on one side of the carbazole group, and thus, molecular symmetry is reduced while expanding the aromatic conjugation range of the molecular structure, so that a material has better energy transfer characteristics, and the crystallinity can be reduced; the specific asymmetric deuteration of the carbazole group can effectively improve the stability of the molecular structure and can further reduce the molecular symmetry, thus significantly improving the photoelectric stability and film-forming properties of the material. The organic compound of the present disclosure has good carrier transport characteristics, energy transfer characteristics and photoelectric stability, and is suitable for use as a host material of an organic light-emitting layer in an organic electroluminescent device, and the organic electroluminescent device using the organic compound as the host material has significantly improved service life characteristics while maintaining a low driving voltage and high luminous efficiency.
Other features and advantages of the present disclosure will be described in detail in the subsequent detailed description.
The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification, and together with the detailed description below, serve to explain the present disclosure, but do not constitute limitations on the present disclosure.
In view of the above problems existing in the prior art, an object of the present disclosure is to provide an organic compound, an organic electroluminescent device including the same, and an electronic device. The organic compound can improve the performance of the organic electroluminescent device and the electronic device, such as reducing the driving voltage of the device, and improving the efficiency and service life of the device.
According to a first aspect of the present disclosure, provided is an organic compound, having a structure as shown in a formula 1:
In the present disclosure, the adopted description modes “each . . . is independently”, “ . . . is respectively and independently” and “ . . . is each independently” can be interchanged, and should be understood in a broad sense, which means that in different groups, specific options expressed between the same symbols do not influence each other, or in a same group, specific options expressed between the same symbols do not influence each other. For example, the meaning of
where each q is independently 0, 1, 2 or 3, and each R″ is independently selected from hydrogen, deuterium, fluorine and chlorine″ is as follows: a formula Q-1 represents that q substituents R″ exist on a benzene ring, each R″ can be the same or different, and options of each R″ do not influence each other; and a formula Q-2 represents that each benzene ring of biphenyl has q substituents R″, the number q of the substituents R″ on the two benzene rings can be the same or different, each R″ can be the same or different, and options of each R″ do not influence each other.
In the present disclosure, the term such as “substituted or unsubstituted” means that a functional group described behind the term may have or may not have a substituent (in the below, the substituent is collectively referred to as Rc in order to facilitate description). For example, the “substituted or unsubstituted aryl” refers to aryl having the substituent Rc or unsubstituted aryl. Where the above substituent, i.e., Rc, for example, can be deuterium, cyano, a halogen group, alkyl, haloalkyl, deuteroalkyl, aryl, deuteroaryl, haloaryl, heteroaryl, cycloalkyl, or the like. The number of the substituents may be one or more.
In the present disclosure, “a plurality of” means two or more, e.g., two, three, four, five, six, etc.
In the present disclosure, the number of carbon atoms of a substituted or unsubstituted functional group refers to the number of all carbon atoms. For example, if L1 is a substituted arylene with 12 carbon atoms, then the number of all carbon atoms of the arylene and substituents on the arylene is 12.
In the present disclosure, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl can be monocyclic aryl (e.g., phenyl) or polycyclic aryl, in other words, the aryl can be monocyclic aryl, fused aryl, two or more monocyclic aryl linked by carbon-carbon bonds, monocyclic aryl and fused aryl which are linked by a carbon-carbon bond, or two or more fused aryl linked by carbon-carbon bonds. That is, unless otherwise indicated, two or more aromatic groups conjugatedly linked by carbon-carbon bonds may also be considered as the aryl in the present disclosure. The fused aryl may include, for example, bicyclic fused aryl (e.g., naphthyl), tricyclic fused aryl (e.g., phenanthryl, fluorenyl, and anthryl), and the like. The aryl does not contain heteroatoms such as B, N, O, S, P, Se, and Si. Examples of the aryl can include, but are not limited to, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, biphenyl, terphenyl, triphenylene, perylenyl, benzo[9,10]phenanthryl, pyrenyl, benzofluoranthenyl, chrysenyl, spirobifluorenyl, and the like. In the present disclosure, the arylene involved refers to a divalent group formed by further loss of one hydrogen atom from the aryl.
In the present disclosure, terphenyl includes
In the present disclosure, the number of carbon atoms of substituted aryl refers to the total number of carbon atoms of the aryl and substituents on the aryl, e.g., a substituted aryl with 18 carbon atoms means that the total number of carbon atoms of the aryl and substituents is 18.
In the present disclosure, the number of carbon atoms of the substituted or unsubstituted aryl may be 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 25, or 30. In some embodiments, the substituted or unsubstituted aryl is a substituted or unsubstituted aryl with 6 to 30 carbon atoms, in other embodiments, the substituted or unsubstituted aryl is a substituted or unsubstituted aryl with 6 to 25 carbon atoms, in other embodiments, the substituted or unsubstituted aryl is a substituted or unsubstituted aryl with 6 to 20 carbon atoms, and in other embodiments, the substituted or unsubstituted aryl is a substituted or unsubstituted aryl with 6 to 12 carbon atoms.
In the present disclosure, fluorenyl may be substituted by one or more substituents, where any two adjacent substituents may be bonded to each other to form a ring structure. In the case where the above fluorenyl is substituted, the substituted fluorenyl may be
or the like, but is not limited to this.
In the present disclosure, aryl as a substituent of L, L1, L2, Ar1 and Ar2 is, for example, but is not limited to, phenyl, naphthyl or the like.
In the present disclosure, heteroaryl refers to a monovalent aromatic ring containing 1, 2, 3, 4, 5 or 6 heteroatoms in the ring or its derivative, and the heteroatom may be one or more of B, O, N, P, Si, Se and S. The heteroaryl may be monocyclic heteroaryl or polycyclic heteroaryl, in other words, the heteroaryl may be a single aromatic ring system or a plurality of aromatic ring systems linked by carbon-carbon bonds, and any one aromatic ring system is a monocyclic aromatic ring or a fused aromatic ring. For example, the heteroaryl may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, and the like, but is not limited to this.
In the present disclosure, the number of carbon atoms of the substituted or unsubstituted heteroaryl may be selected from 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, the substituted or unsubstituted heteroaryl is a substituted or unsubstituted heteroaryl with 5 to 20 carbon atoms, and in other embodiments, the substituted or unsubstituted heteroaryl is a substituted or unsubstituted heteroaryl with 12 to 18 carbon atoms.
In the present disclosure, the substituted heteroaryl may be that one or two or more hydrogen atoms in the heteroaryl are substituted by groups such as deuterium atom, halogen group, —CN, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, haloalkyl, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl refers to the total number of carbon atoms of the heteroaryl and substituents on the heteroaryl.
In the present disclosure, the alkyl with 1 to 10 carbon atoms may include linear alkyl with 1 to 10 carbon atoms and branched alkyl with 3 to 10 carbon atoms. The number of carbon atoms of the alkyl can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and specific examples of the alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and the like.
In the present disclosure, the halogen group may be, for example, fluorine, chlorine, bromine, or iodine.
In the present disclosure, specific examples of trialkylsilyl include, but are not limited to, trimethylsilyl and the like.
In the present disclosure, specific examples of haloalkyl includes, but are not limited to, trifluoromethyl.
In the present disclosure, specific examples of deuteroalkyl include, but are not limited to, trideuteromethyl.
In the present disclosure, the number of carbon atoms of cycloalkyl with 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, and adamantyl.
In the present disclosure, an unpositioned connecting bond refers to a single bond “
” extending from a ring system, which means that one end of the connecting bond can be connected with any position in the ring system through which the bond penetrates, and the other end of the connecting bond is connected with the remaining part of a compound molecule. For example, as shown in the following formula (f), naphthyl represented by the formula (f) is connected to other positions of a molecule through two unpositioned connecting bonds penetrating a dicyclic ring, and its meaning includes any one possible connecting mode represented by formulae (f-1) to (f-10).
For another example, as shown in the following formula (X′), dibenzofuranyl represented by the formula (X′) is connected with other positions of a molecule through one unpositioned connecting bond extending from the middle of a benzene ring on one side, and its meaning includes any one possible connecting mode represented by formulae (X′-1) to (X′-4).
In some specific embodiments of the present disclosure, the organic compound is selected from compounds shown in a Formula AA, a Formula BB, a Formula CC or a Formula DD:
In some embodiments of the present disclosure, L, L1 and L2 are the same or different, and are respectively and independently selected from a single bond or a substituted or unsubstituted arylene with 6 to 12 carbon atoms.
Optionally, substituent(s) in L, L1 and L2 are the same or different, and are respectively and independently selected from deuterium, a halogen group, a cyano, an alkyl with 1 to 5 carbon atoms, or a phenyl.
In other embodiments of the present disclosure, L, L1 and L2 are the same or different, and are respectively and independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
Optionally, L, L1 and L2 are the same or different, and are respectively and independently selected from deuterium, a fluorine, a cyano, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl, or a phenyl.
Further optionally, L, L1 and L2 are the same or different, and are respectively and independently selected from a single bond or the group consisting of:
In particular, L, L1 and L2 are the same or different, and are respectively and independently selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, Ar1 and Ar2 are the same or different, and are respectively and independently selected from a substituted or unsubstituted aryl with 6 to 20 carbon atoms, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothienyl.
Optionally, substituent(s) in Ar1 and Ar2 are the same or different, and are respectively and independently selected from deuterium, a halogen group, a cyano, an alkyl with 1 to 5 carbon atoms, a phenyl, or a pentadeuterophenyl.
In other embodiments of the present disclosure, Ar1 and Ar2 are the same or different, and are respectively and independently selected from a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothienyl.
Optionally, substituent(s) in Ar1 and Ar2 are the same or different, and are respectively and independently selected from deuterium, fluorine, a cyano, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl, a phenyl, or a pentadeuterophenyl.
In other embodiments of the present disclosure, Ar1 and Ar2 are the same or different, and are respectively and independently selected from a substituted or unsubstituted group W, where the unsubstituted group W is selected from the group consisting of:
Optionally, Ar1 and Ar2 are the same or different, and are respectively and independently selected from the group consisting of:
In particular, Ar1 and Ar2 are the same or different, and are respectively and independently selected from the group consisting of:
In some embodiments of the present disclosure,
are respectively and independently selected from the group consisting of:
In particular,
are respectively and independently selected from the group consisting of:
In some embodiments of the present disclosure,
in the formula 1 is selected from the group consisting of:
In particular,
in the formula 1 is selected from the group consisting of:
In some embodiments of the present disclosure, the organic compound is selected from the group consisting of the following compounds:
In a second aspect of the present disclosure, also provided is a composition, including a first compound and a second compound, where
the first compound has the structure shown in the formula 1, and the second compound has a structure shown in a formula 2:
In some embodiments of the present disclosure, the second compound has a structure represented by a Formula 2-3-3:
In some embodiments of the present disclosure, in the second compound, each R4, each R5, each R6, and each R7 are respectively and independently selected from hydrogen, deuterium, a fluorine, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl, a phenyl, a naphthyl, a biphenyl, or a pentadeuterophenyl.
In some embodiments of the present disclosure, in the second compound, each R4, each R5, each R6, and each R7 are respectively and independently selected from hydrogen, deuterium, a fluorine, a cyano, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl, a the group consisting of:
In some embodiments of the present disclosure, in the second compound, L4 and L5 are respectively and independently selected from a single bond, a substituted or unsubstituted arylene with 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene with 12 to 20 carbon atoms.
Optionally, substituent(s) in L4 and L5 are respectively and independently selected from deuterium, a halogen group, a cyano, an alkyl with 1 to 5 carbon atoms, or a phenyl.
In other embodiments of the present disclosure, in the second compound, L4 and L5 are respectively and independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or substituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted dibenzofurylene, a substituted or unsubstituted dibenzothienylene, or a substituted or unsubstituted carbazolylene.
Optionally, substituent(s) in L4 and L5 are respectively and independently selected from deuterium, a fluorine, a cyano, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl or a phenyl.
In some embodiments of the present disclosure, in the second compound, L4 and L5 are respectively and independently selected from a single bond, or a substituted or unsubstituted group U, where the unsubstituted group U is selected from the group consisting of:
Optionally, L4 and L5 are respectively and independently selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, in the second compound, Ar4 and Ar5 are respectively and independently selected from a substituted or unsubstituted aryl with 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl with 12 to 20 carbon atoms.
Optionally, substituent(s) in Ar4 and Ar5 are respectively and independently selected from deuterium, a halogen group, an alkyl with 1 to 5 carbon atoms, a phenyl, or a pentadeuterophenyl.
In other embodiments of the present disclosure, in the second compound, Ar4 and Ar5 are respectively and independently selected from a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothienyl, a substituted or unsubstituted carbazolyl, or a substituted or unsubstituted triphenylene.
Optionally, substituent(s) in Ar4 and Ar5 are respectively and independently selected from deuterium, a fluorine, a cyano, a halogen group, a methyl, an ethyl, a n-propyl, an isopropyl, a tert-butyl, a phenyl, or a pentadeuterophenyl.
In some embodiments of the present disclosure, in the second compound, Ar4 and Ar5 are respectively and independently selected from a substituted or unsubstituted group G, where the unsubstituted group G is selected from the group consisting of:
where
Optionally, in the second compound, Ar4 and Ar5 are respectively and independently selected from the group consisting of:
In some embodiments of the present disclosure,
are respectively and independently selected from the group consisting of:
In particular,
are respectively and independently selected from the group consisting of:
In some embodiments of the present disclosure, the second compound is selected from the group consisting of the following compounds:
Optionally, the composition is a mixture of the first compound and the second compound. For example, the mixture may be formed by uniformly mixing the first compound with the second compound through mechanical stirring.
The relative amounts of the two types of compounds in the composition are not particularly limited in the present disclosure and can be selected according to the specific application of the organic electroluminescent device. Typically, the mass percentage of the first compound may be 1% to 99% and the mass percentage of the second compound may be 1% to 99% based on the total weight of the composition. For example, a mass ratio of the first compound to the second compound in the composition may be 1:99, 20:80, 30:70, 40:60, 45:65, 50:50, 55:45, 60:40, 70:30, 80:20, 99:1 or the like.
In some embodiments of the present disclosure, the composition consists of the first compound and the second compound, where the mass percentage of the first compound is 20% to 80% and the mass percentage of the second compound is 20% to 80% based on the total weight of the composition.
In some preferred embodiments, in the composition, the mass percentage of the first compound is 30% to 60% and the mass percentage of the second compound is 40% to 70% based on the total weight of the composition, and in this case, when the composition is applied to an organic electroluminescent device, the device can have both high luminous efficiency and long service life. Preferably, the mass percentage of the first compound is 40% to 60% and the mass percentage of the second compound is 40% to 60% based on the total weight of the composition. More preferably, the mass percentage of the first compound is 40% to 50% and the mass percentage of the second compound is 50% to 60%.
The present disclosure also provides use of the composition as a host material for a light-emitting layer of an organic electroluminescent device.
In a third aspect of the present disclosure, also provided is an organic electroluminescent device, including an anode and a cathode which are oppositely disposed, and at least one functional layer between the anode and the cathode, the functional layer including the organic compound shown in the formula 1 according to the present disclosure or the composition containing the first compound and the second compound.
In one embodiment of the present disclosure, the functional layer includes an organic light-emitting layer including the organic compound shown in the formula 1 according to the present disclosure.
In one embodiment of the present disclosure, the functional layer includes an organic light-emitting layer including the composition containing the first compound and the second compound provided in the present disclosure.
In one embodiment of the present disclosure, the organic electroluminescent device is a phosphorescent device.
In one specific embodiment of the present disclosure, the organic electroluminescent device is a green organic electroluminescent device.
In some embodiments of the present disclosure, the organic electroluminescent device sequentially includes an anode (an ITO substrate), a hole transport layer, a hole auxiliary layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, a cathode (a Mg—Ag mixture), and an organic capping layer.
In one specific embodiment of the present disclosure, as shown in
Optionally, the anode 100 includes the following anode materials which are optionally materials having a large work function that facilitate hole injection into the functional layer. Specific examples of the anode materials include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or an alloy of them; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combined metals and oxides, such as ZnO:Al or SnO2:Sb; or a conductive polymer such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but are not limited to this. A transparent electrode including indium tin oxide (ITO) as the anode is preferably included.
Optionally, the hole transport layer 320 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole multimers, carbazole-linked triarylamine compounds, or other types of compounds, which are not particularly limited in the present disclosure. For example, in some embodiments of the present disclosure, the hole transport layer 320 consists of HT-01.
Optionally, the hole auxiliary layer 330 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole multimers, carbazole-linked triarylamine compounds, or other types of compounds, which are not particularly limited in the present disclosure. For example, in some embodiments of the present disclosure, the hole auxiliary layer 330 consists of HT-02. The hole auxiliary layer is also referred to as a second hole transport layer, a hole buffer layer, a hole adjustment layer, or an electron blocking layer.
Optionally, the organic light-emitting layer 340 may consist of a single light-emitting material or may include a host material and a guest material. Optionally, the organic light-emitting layer 340 is composed of the host material and the guest material, and holes and electrons which are injected into the organic light-emitting layer 340 may be recombined in the organic light-emitting layer 340 to form excitons, and the excitons transfer energy to the host material, and the host material transfers energy to the guest material, thus enabling the guest material to emit light.
The guest material of the organic light-emitting layer 340 may be a compound having a condensed aryl ring or its derivative, a compound having a heteroaryl ring or its derivative, an aromatic amine derivative, or other materials, which is not particularly limited in the present disclosure.
In some embodiments of the present disclosure, in the green organic electroluminescent device, the organic light-emitting layer 340 includes the organic compound described in the present disclosure, the second compound, and a guest material Ir(ppy)3.
The electron transport layer 350 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials, and the electron transport materials may be selected from a benzimidazole derivative, an oxadiazole derivative, a quinoxaline derivative, or other electron transport materials, which are not particularly limited in the present disclosure. For example, in some embodiments of the present disclosure, the electron transport layer 350 may consist of ET-01 and LiQ.
Optionally, the cathode 200 includes a cathode material which is a material having a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or an alloy of them; or multilayer materials such as LiF/Al, Liq/Al, LiO2/Al, LiF/Ca, LiF/Al and BaF2/Ca, but are not limited to this. A metal electrode including silver and magnesium is preferably included as the cathode.
Optionally, the hole injection layer 310 may also be disposed between the anode 100 and the hole transport layer 320 to enhance the ability to inject holes into the hole transport layer 320. The hole injection layer 310 may be made of a benzidine derivative, a starburst arylamine compound, a phthalocyanine derivative, or other materials, which is not particularly limited in the present disclosure. In some embodiments of the present disclosure, the hole injection layer 310 may consist of CuPC and HT-01.
Optionally, the electron injection layer 360 may also be disposed between the cathode 200 and the electron transport layer 350 to enhance the ability to inject electrons into the electron transport layer 350. The electron injection layer 360 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic substance. In some embodiments of the present disclosure, the electron injection layer 360 may include ytterbium (Yb).
In a fourth aspect of the present disclosure, also provided is an electronic apparatus, including the organic electroluminescent device described in the present disclosure.
For example, as shown in
The present disclosure will be described in detail below in conjunction with the examples, but the following description is intended to explain the present disclosure, and not to limit the scope of the present disclosure in any way.
Under nitrogen protection, 2,3-dichloronitrobenzene (20.0 g; 104.2 mmol), d5-pinacol phenylboronate (47.9 g; 229.2 mmol), tetrakis(triphenylphosphine) palladium (4.8 g; 4.2 mmol), potassium carbonate (57.6 g; 416.7 mmol), tetrabutylammonium bromide (13.4 g; 41.2 mmol), toluene (320 mL), ethanol (80 mL), and deionized water (80 mL) were added into a round bottom flask, a mixed solution was heated to 75° C. to 80° C., and a reaction was carried out under stirring for 72 hours. The reaction solution was cooled to room temperature, deionized water was added into the reaction solution, liquid separation was performed, an organic phase was washed with water and dried over anhydrous magnesium sulfate, and a solvent was removed under reduced pressure; and the obtained crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane mixed solvent as an eluent to obtain an Intermediate IM-a-no (17.7 g; yield: 60%) as a colorless oily substance.
Referring to the synthesis method for the Intermediate IM-a-no, by substituting a Reactant A for 2,3-dichloronitrobenzene, intermediates shown in Table 1 below were synthesized:
Under nitrogen protection, the Intermediate IM-a-no (16.0 g; 56.1 mmol), triphenylphosphine (36.8 g; 140.2 mmol), and o-dichlorobenzene (150 mL) were added into a round bottom flask, a mixed solution was heated to 175° C. to 180° C. with stirring, and a reaction was carried out for 36 hours. The reaction solution was cooled to room temperature, deionized water was added into the reaction solution, liquid separation was performed, an organic phase was washed with water and dried over anhydrous magnesium sulfate, and a solvent was removed under reduced pressure at a high temperature; and the obtained crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane mixed solvent as an eluent to obtain an Intermediate IM-a-nh (9.2 g; yield: 65%) as a white solid.
Referring to the same method as that for the Intermediate IM-a-nh, intermediates shown in Table 2 below were synthesized by substituting a Reactant B for the Intermediate IM-a-no:
Under nitrogen protection, the Intermediate IM-a-nh (5.0 g; 19.8 mmol), 2-chloro-4-(dibenzofuran-3-yl)-6-phenyl-1,3,5-triazine (10.6 g; 29.7 mmol) and N,N-dimethylformamide (50 mL) were added into a round bottom flask, a mixed solution was cooled to −5° C. to 0° C. with stirring, and sodium hydride (0.6 g; 23.4 mmol) was added, and a reaction was carried out under stirring at −5° C. to 0° C. for 1 hour, then the temperature was raised to 20° C. to 25° C., and a reaction was carried out for 24 hours. The reaction was stopped, the reaction solution was washed with water, and liquid separation was performed, an organic phase was dried over anhydrous magnesium sulfate, and a solvent was removed under reduced pressure to obtain a crude product; and the crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane mixed solvent as an eluent, and then purified by recrystallization using a toluene/n-heptane mixed solvent to obtain a Compound A5 (8.0 g; yield: 70%) as a white solid.
Referring to the synthesis method for the Compound A5, by substituting a Reactant C for the Intermediate IM-a-nh and substituting a Reactant D for 2-chloro-4-(dibenzofuran-3-yl)-6-phenyl-1,3,5-triazine, compounds shown in Table 3 below were synthesized:
Under nitrogen protection, the Intermediate IM-a-nh (5.0 g; 19.8 mmol), 2-(biphenyl-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (8.7 g; 20.8 mmol), tris(dibenzylideneacetone) dipalladium (0.2 g; 0.2 mmol), 2-dicyclohexylphosphine-2′,4′,6′-triisopropylbiphenyl (0.4 g; 0.2 mmol), sodium tert-butoxide (2.9 g; 29.7 mmol) and xylene (50 mL) were added into a round bottom flask, and a mixed solution was subjected to a reaction under stirring at 135° C. to 140° C. for 16 hours. The reaction solution was cooled to room temperature, the reaction solution was washed with water, liquid separation was performed, an organic phase was dried over anhydrous magnesium sulfate, and a solvent was removed under reduced pressure to obtain a crude product; and the crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane mixed solvent as an eluent, and then purified by recrystallization using a toluene/n-heptane mixed solvent to obtain a Compound A45 (9.4 g; yield: 75%) as a white solid.
Referring to a method similar to that of the Compound A45, compounds shown in Table 4 below were synthesized by using a Reactant E in the table below instead of the Intermediate IM-a-nh and using a Reactant F in the table below instead of 2-(biphenyl-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine:
Mass spectrum data of some compounds are shown in Table 5 below:
NMR data of some compounds are shown in Table 6 below:
1HNMR (CD2Cl2, 400 MHz): 9.09-9.05 (m, 3H),
1HNMR (CD2Cl2, 400 MHz): 8.87 (d, 2H), 8.79-8.77
1HNMR (CD2Cl2, 400 MHz): 9.65 (s, 1H), 8.85
An anode was pretreated by the following process: surface treatment was performed with UV ozone and O2:N2 plasma on an ITO/Ag/ITO substrate with a thickness of 110 Å, 1100 Å, and 100 Å to increase the work function of the anode, and the surface of the ITO substrate was washed with an organic solvent to remove impurities and oil stains from the surface of the ITO substrate.
CuPC and HT-01 were co-evaporated on an experimental substrate (the anode) at an evaporation rate ratio of 2%: 98% to form a hole injection layer (HIL) with a thickness of 110 Å, and then HT-01 was vacuum-evaporated on the hole injection layer to form a hole transport layer with a thickness of 1230 Å.
HT-02 was evaporated on the hole transport layer to form a hole auxiliary layer with a thickness of 360 Å.
A composition GH-1-1 and Ir(ppy)3 were co-evaporated on the hole auxiliary layer at an evaporation rate ratio of 100%: 10% to form an organic light-emitting layer (a green organic light-emitting layer) with a thickness of 300 Å.
ET-01 and LiQ were mixed in a weight ratio of 1:1 and evaporated to form an electron transport layer having a thickness of 340 Å, Yb was evaporated on the electron transport layer to form an electron injection layer with a thickness of 15 Å, and magnesium and silver were co-evaporated on the electron injection layer at an evaporation ratio of 1:9 to form a cathode with a thickness of 120 Å.
In addition, CP-01 was evaporated on the above cathode to form an organic capping layer (CPL) with a thickness of 700 Å, thus realizing the manufacture of an organic light-emitting device.
When the organic light-emitting layer was formed, by using a host material composition GH-X-Y shown in Table 7 instead of the composition GH-1-1 in Example 1, an organic electroluminescent device was manufactured by the same method as that in Example 1.
An organic electroluminescent device was manufactured by the same method as that in Device Example 1 except that GH-X-Y was used when the organic light-emitting layer was formed.
In the above Examples and Comparative examples, the host material composition GH-X-Y used was obtained by mixing a first compound shown in Table 7 below with a second compound shown in Table 7 below, with a specific composition shown in Table 7. A mass ratio refers to a ratio of the mass percent content of the first compound to the mass percent content of the second compound shown in the table. Taking the composition GH-1-1 as an example, it can be seen with reference to Table 7 that GH-1-1 was formed by mixing the compound A5 with a compound 49 in a mass ratio of 40:60; and for another example, a host material GH-D1-1 in Comparative example 1 was formed by mixing a compound I with a compound 5 in a mass ratio of 40:60.
The second compound employed is shown below, and according to the description of a patent document JP3139321B2, Compound 5 was obtained; according to a patent document CN103518271B, Compound 12 was obtained; according to a patent document U.S. Pat. No. 9,564,595B2, Compound 35 was obtained; according to the description of a patent document CN104205393B, Compound 36 was obtained; and according to the description of a patent document KR1020220013910A, Compound 49 was obtained.
Structural formulas of other main materials employed in Examples 1 to 83 and Comparative examples 1 to 6 are shown below:
As for the organic electroluminescent devices manufactured above, the current-voltage-luminance (IVL) of the devices was specifically tested under the condition of 10 mA/cm2, and the T95 device service life was tested under the condition of 20 mA/cm2, and the test results are shown in Table 7.
As can be seen from the above table, the current efficiency of the devices in Examples 1 to 84 was improved by at least 10.1% and the service life of the devices in Examples 1 to 84 was improved by at least 16.0% compared with Comparative examples 1 to 6.
Compared with Comparative examples 1 and 2, when the organic compound shown in the formula 1 according to the present disclosure is used as a green electron type host material, the manufactured device has significantly improved service life characteristics when the driving voltage and the efficiency are close. The reason may be that specific sites in the phenylcarbazole core structure in the compounds of the present disclosure are deuterated, making photoelectric stability of the compounds improved compared with the compound I.
Compared with Comparative examples 3 and 4, when the organic compound shown in the formula 1 according to the present disclosure is used as a green electron type host material, the manufactured device has a remarkably reduced driving voltage and improved luminous efficiency. The reason may be that compared with the carbazole group with hole characteristics in the compound II, the compound of the present disclosure uses a neutral or electronic group to connect the triazine group, so that the molecule has better electron injection and transport characteristics, resulting in enhanced carrier injection and recombination efficiency.
Compared with Comparative example 5, the service life of the device is improved for the compounds of the present disclosure compared with the compound III in Comparative example. The reason may be that compared with the compound III, a specific site in the carbazole group is deuterated in the compound of the present disclosure, thus improving photoelectric stability of the compounds.
Compared with Comparative example 6, both the service life and the efficiency of the device are improved for the compounds of the present disclosure compared with the compound IV in Comparative example. The reason may be that compared with the compound IV, only one of the benzene rings on the carbazole group is perdeuterated in the compounds of the present disclosure, which can effectively control the local symmetry of the molecular structure and reduce the intermolecular force, thus improving the amorphous stability and film-forming properties of the material.
It will be easy for those skilled in the art to think of other embodiments of the present disclosure after considering the specification and practicing the present disclosure disclosed here. The present disclosure is intended to cover any variations, uses, or adaptive changes of the present disclosure, and these variations, uses, or adaptive changes follow the general principles of the present disclosure and include common general knowledge or conventional technical means in the art not disclosed in the present disclosure. The specification and examples are only considered as exemplary, and the true scope and spirit of the present disclosure are indicated by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310071951.7 | Jan 2023 | CN | national |
| 202310184175.1 | Mar 2023 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2023/123855 | 10/10/2023 | WO |
