CN117343102A

CN117343102A - Compound, organic electroluminescent device and display device

Info

Publication number: CN117343102A
Application number: CN202310798163.8A
Authority: CN
Inventors: 夏政焕; 金源晔; 金桓辉
Original assignee: SK CORP
Current assignee: SK CORP
Priority date: 2022-07-04
Filing date: 2023-07-03
Publication date: 2024-01-05
Also published as: KR20240003993A

Abstract

According to the present invention, there are provided a compound that can be applied to an electron transport layer, a hole blocking layer, a charge generation layer, and the like of an organic electroluminescent device, a composition for an organic electroluminescent device containing the compound, an organic electroluminescent device using the compound, and a display apparatus including the organic electroluminescent device.

Description

Compound, organic electroluminescent device and display device

[ field of technology ]

The present invention relates to a novel organic compound useful as a material of an organic electroluminescent device, an organic electroluminescent device including the same, and a display apparatus.

[ background Art ]

Recently, as a full-color flat panel display, a display using an organic electroluminescent device has been attracting attention, and is used in a display device such as a smart phone, a Television (TV), an automobile, a Virtual Reality (VR) head-mounted device, or the like.

The organic electroluminescent device has a structure including a pair of electrodes composed of a positive electrode and a negative electrode and an organic material layer portion provided between the pair of electrodes and having one or more organic compound layers. The organic material layer portion includes a light emitting layer or a charge transporting/injecting layer that transports or injects charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

In order to further expand the application field of displays using organic electroluminescent devices, it is required to reduce the power consumption (lower voltage and higher external quantum efficiency) of the devices and to increase the lifetime thereof. In particular, it is required to reduce power consumption and increase the lifetime of the blue light emitting device, and for this reason, various materials for electron transport/injection layers are being studied.

For example, an organic electroluminescent device using a pyridine derivative or a bipyridine derivative (patent document 1), a benzimidazole or benzothiazole derivative (patent documents 2 to 4), a pyrimidine derivative or a triazine derivative (patent document 5) as a material for an electron transporting/injecting layer is known.

However, in the case of such existing materials for electron transport/injection layers, further improvements are required in terms of luminous efficiency, driving voltage and lifetime.

In particular, in the conventional organic electroluminescent device, excitons and/or holes generated at the light emitting layer are diffused to the electron transporting layer to emit light at an interface with the electron transporting layer, thus causing problems of reduced light emitting efficiency and shortened lifetime.

On the other hand, an organic electroluminescent device having a plurality of light emitting stacked portions between a pair of electrodes (so-called tandem structure) includes a charge generation layer formed between the light emitting stacked portions, and due to this structure, there are problems of high driving voltage, low efficiency, and shortened lifetime.

[ Prior Art literature ]

[ patent literature ]

(patent document 1) Japanese laid-open patent No. 2003-123983

(patent document 2) U.S. patent publication 2003/215667

(patent document 3) International publication No. 2003/060956

(patent document 4) International publication No. 2008/117976

(patent document 5) registered patent publication No. 2084906

[ invention ]

[ problem ]

The present invention is directed to provide a novel compound having high stability to electrons and high electron mobility and capable of suppressing diffusion of excitons and/or holes to an electron transport layer and being suitable for an n-type charge generation layer in a tandem structure, an organic electroluminescent device containing the same and having high efficiency, low driving voltage and long lifetime, and a display device using the same.

[ solution to the problem ]

In order to achieve the above object, the present invention provides a compound including a structure represented by the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1 described above, a compound having the formula,

x may be O or S, and,

Y ₁ can be O, S, or CR ₁ R ₂ ，

R ₁ To R ₄ May be the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, trifluoromethyl, nitro, halo, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, substituted or unsubstituted C ₃ -C ₃₀ Cycloalkyl, substituted or unsubstituted C ₂ -C ₃₀ Alkenyl, substituted or unsubstituted C ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₁ -C ₂₀ Is optionally substituted C ₃ -C ₂₀ Aralkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C ₃ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Substituted or unsubstituted C ₁ -C ₃₀ Alkylsilyl, substituted or unsubstituted C ₆ -C ₃₀ Arylsilyl group of (C), substituted or unsubstituted C ₃ -C ₃₀ And R is a member of the group consisting of heteroarylsilyl groups ₁ And R is ₂ A plurality of R ₃ And R is ₄ Can combine with adjacent groups to form a substituted or unsubstituted ring,

m and n may be integers of 0 to 4,

* May be the connection location with an adjacent atom.

In addition, the present invention provides an organic electroluminescent device in which the compound is included in an organic material layer, and a display apparatus including the organic electroluminescent device.

[ beneficial effects ]

The novel compound including the structure represented by chemical formula 1 of the present invention, particularly when used as a material for an electron transport layer and/or a hole blocking layer (electron transport auxiliary layer), can produce an organic electroluminescent device having more excellent light emitting properties, low driving voltage, high efficiency and long life compared to the existing materials, and further can produce a full-color display panel having greatly improved properties and lifetime.

[ description of the drawings ]

Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device having one light emitting stack according to an embodiment of the present invention.

Fig. 2 and 3 are schematic cross-sectional views of an organic electroluminescent device having a plurality of light emitting stacks according to other embodiments of the present invention.

[ detailed description ] of the invention

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known configurations or functions incorporated herein will be omitted when it may obscure the subject matter of the present invention instead.

< description of the Compounds of the invention >

The compound according to the present invention includes a structure represented by the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1 described above, a compound having the formula,

x may be O or S, and,

Y ₁ can be O, S, or CR ₁ R ₂ ，

m and n may be integers of 0 to 4,

* May be the connection location with an adjacent atom.

The substituents in the present invention will be described in detail below.

The position where the substituent is not bonded to the compound described in the present specification may be bonded with hydrogen or deuterium.

In the present specification, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is substituted with another substituent, and the substituted position is not limited as long as it is a position where a hydrogen atom is substituted, that is, a position where a substituent can be substituted, and when two or more are substituted, two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" means substituted by a group selected from deuterium; a halogen group; a nitrile group; cyano group; a phosphine oxide group; an alkyl group; alkenyl groups; alkynyl; cycloalkyl; a heteroalkyl group; an aryl group; a heterocyclic group; an aralkyl group; a heteroaralkyl group; aralkenyl; alkylaryl groups; alkenyl aryl; an alkoxy group; an aryloxy group; aryl phosphine oxide group; a silyl group; an alkylamino group; an aralkylamine group; an arylamine group; an alkylarylamino group; and a substituent of at least one of the heteroaromatic amine groups, or a substituent formed by joining at least two of the substituents. For example, "a substituent linking two or more substituents" may be a biphenyl group. In other words, biphenyl may be aryl and may be interpreted as a substituent in which two phenyl groups are linked.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be, for example, 1 to 100, 1 to 80, 1 to 50, or 1 to 20. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be, for example, 2 to 100, 2 to 80, 2 to 50, or 2 to 30. Specific examples of alkenyl groups include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, styryl and the like, but are not limited thereto.

In the present specification, the number of carbon atoms of the alkynyl group is not particularly limited, but may be 2 to 50, 2 to 30, or 2 to 20. Specifically, the alkynyl group may be an unsaturated aliphatic hydrocarbon group including a triple bond such as an ethynyl group (ethynyl group), etc., but is not limited thereto.

In the present specification, the number of carbon atoms of the cycloalkyl group is not particularly limited, but may be 3 to 100, 3 to 60, or 3 to 30. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

In the present specification, a heteroalkyl group or a heterocycloalkyl group means an alkyl group or a cycloalkyl group having one or more carbon atoms each substituted with a heteroatom. The heteroatoms are selected from O, S, N, P, B, si and Se, preferably from O, S or N.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but may be 6 to 80, 6 to 60, 6 to 50, or 6 to 30. In particular, the monocyclic aryl group may be phenyl Biphenyl or terphenyl, but are not limited thereto. The polycyclic aryl group may be naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,Radical, fluorenyl, etc., but are not limited thereto.

In the present specification, a fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When fluorenyl is substituted, it may beEtc. But the present disclosure is not limited thereto.

In the present specification, examples of the aryl phosphine oxide group include a substituted or unsubstituted monoaryl phosphine oxide group, a substituted or unsubstituted diaryl phosphine oxide group, or a substituted or unsubstituted triarylphosphine oxide group. The aryl group in the arylphosphine oxide group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine oxide group comprising at least two aryl groups may comprise a monocyclic aryl group, a polycyclic aryl group, or both monocyclic and polycyclic aryl groups.

In the present specification, aralkyl or heteroaralkyl refers to an alkyl group substituted with an aryl or heteroaryl group. The number of carbon atoms is not limited, but may be 3 to 20.

In the present specification, the silyl group may be represented by-SiR _a R _b R _c Is represented by the formula (I), and R is _a 、R _b And R is _c Each may be hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group. The silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like. The number of carbon atoms is not limited, but when R _a 、R _b 、R _c And the number of carbon atoms may be 1 to 30 when each is a substituted or unsubstituted alkyl group, 6 to 30 when each is a substituted or unsubstituted aryl group, and when dividedIn the case of substituted or unsubstituted heteroaryl groups, the number of carbon atoms may be 3 to 30.

In this specification, the heterocyclic group is an aromatic or aliphatic heterocyclic group including at least one of N, O, S as a hetero element, and the number of carbon atoms thereof is not particularly limited, but may be 2 to 80, 2 to 60, or 2 to 40. Specific examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridylpyrimidinyl, pyridylpyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, carbolinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthroline (phenanthroline) group, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.

In this specification, for heteroaryl, the description of aromatic heterocyclic groups in heterocyclic groups may be applied. The number of carbon atoms is not particularly limited and may be 3 to 30. Heteroaryl groups may include the following structures.

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 may be 1 to 50, 1 to 30, or 1 to 20. Specifically, the alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, i-propoxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group is the same as the above-described examples of the aryl group. Specifically, the aryloxy group includes phenoxy group, p-tolyloxy group, m-tolyloxy group, 3, 5-dimethyl-phenoxy group, 2,4, 6-trimethylphenoxy group, p-t-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthracenyloxy group, 2-anthracenyloxy group, 9-anthracenyloxy group, 1-phenanthrenyloxy group, 3-phenanthrenyloxy group, 9-phenanthrenyloxy group and the like, and the arylthio group includes phenylthio group, 2-methylphenylthioxy group, 4-t-butylphenylthioxy group and the like, but is not limited thereto.

In this specification, an alkylamino group, an aralkylamino group, an arylamino group, an alkylarylamino group, and a heteroarylamino group are amino groups substituted with an alkyl group, an aralkyl group, an aryl group, an alkylaryl group, and a heteroaryl group, respectively, and here, the description of the above alkyl group and aryl group can be applied for the alkyl group and the aryl group, and the description of the aromatic heterocyclic group in the above heterocyclic group can be applied for the heteroaryl group. Specific examples of the amine group include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, anilino, naphthylamino, dianiline, anthracenyl, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthracenyl, diphenylamino, phenylnaphthylamino, xylylamine, phenylethylamine, triphenylamine, and the like.

In the present specification, arylene means an aryl group having two bonding positions, that is, a divalent group. The above description of aryl groups may be applied, except that each of them is a divalent group.

In the present specification, heteroarylene means a heteroaryl group having two bonding positions, i.e., a divalent group. The above description of the aromatic heterocyclic groups may be applied in addition to each of them being a divalent group.

In the present specification, adjacent groups are bonded to each other to form a ring means that adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; a substituted or unsubstituted aromatic heterocycle; or a fused ring thereof.

In this specification, an "adjacent group" refers to a substituent substituted on an atom directly connected to an atom substituted with a substituent, a substituent sterically closest to the substituent, or another substituent substituted on an atom substituted with the substituent. For example, two substituents substituted in the ortho position (ortho) to the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent groups".

In the present specification, an aliphatic hydrocarbon ring is a ring rather than an aromatic group, and refers to a ring composed of only carbon and hydrogen atoms.

In the present specification, examples of the aromatic hydrocarbon ring include phenyl, naphthyl, anthracenyl, and the like, but are not limited thereto.

In the present specification, an aliphatic heterocyclic ring means an aliphatic ring containing at least one of N, O or S atoms as a hetero atom.

In the present specification, an aromatic heterocycle means an aromatic ring containing at least one of N, O or S atoms as a hetero atom.

In the present specification, the aliphatic ring, the aromatic ring, the aliphatic heterocyclic ring, and the aromatic heterocyclic ring may be monocyclic or polycyclic.

The compound including the structure of chemical formula 1 has an alkylphosphine oxide structure, and thus can realize an organic electroluminescent device having high luminous efficiency, excellent thermal stability, low driving voltage, and improved lifetime when used in an organic electroluminescent device.

According to an embodiment of the present invention, there is provided a compound represented by the following chemical formula 2.

[ chemical formula 2]

In the chemical formula 2 described above, the chemical formula,

X、m、R ₁ to R ₄ And may be as defined in formula 1 above,

L ₁ to L ₃ May be the same or different from each other and are each independently selected from the group consisting of a single bond, or a substituted or unsubstituted C ₁ -C ₁₀ Alkylene, substituted or unsubstituted C ₆ -C ₃₀ Arylene, substituted or unsubstituted C ₂ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Cyclic alkylene of (C), substituted or unsubstituted C ₂ -C ₂₀ Is selected from the group consisting of heterocycloalkylene,

Ar ₁ can be selected from the group consisting of substituted and unsubstituted C ₁ -C ₂₀ Alkyl, substituted or unsubstituted C ₃ -C ₃₀ Cycloalkyl, substituted or unsubstituted C ₂ -C ₃₀ Alkenyl, substituted or unsubstituted C ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₁ -C ₂₀ Is optionally substituted C ₃ -C ₂₀ Aralkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C ₃ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Substituted or unsubstituted C ₁ -C ₃₀ Alkylsilyl, substituted or unsubstituted C ₆ -C ₃₀ Arylsilyl group of (C), substituted or unsubstituted C ₃ -C ₃₀ Is selected from the group consisting of heteroarylsilyl groups,

p may be an integer of 1 to 5,

p is 2 or more, a plurality of L ₃ Or Ar ₁ Each independently may be the same or different.

According to one embodiment of the present invention, ar of the chemical formula 2 ₁ At least one of them comprises an electron-withdrawing group (electron-withdrawing group; EWG) or C ₇ Or higher Polycyclic Aromatic-hydroxy (PAH).

According to one embodiment of the invention, the electron withdrawing group is C including N ₃ -C ₃₀ Heteroaryl or CN.

According to an embodiment of the present invention, p of the chemical formula 2 is 2.

According to an embodiment of the present invention, p of the chemical formula 2 is 4 or 5.

For example, the compounds of the present invention include the compounds described below.

/>

Hereinafter, an organic electroluminescent device having one light emitting stack portion and an organic electroluminescent device having a plurality of light emitting stack portions according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device having a structure in which one light emitting stack is formed between a pair of electrodes according to an embodiment of the present invention, and fig. 2 and 3 are schematic cross-sectional views of an organic electroluminescent device having a structure in which a plurality of light emitting stacks are formed between a pair of electrodes.

< organic electroluminescent device having Structure of one light-emitting Stacking portion >

The organic electroluminescent device 1 shown in fig. 1 has a positive electrode 110 (first electrode) provided on a substrate 100, a hole injection layer 120 provided on the positive electrode 110, a hole transport layer 130 provided on the hole injection layer 120, a light emitting layer 140 provided on the hole transport layer 130, an electron transport layer 150 provided on the light emitting layer 140, an electron injection layer 160 provided on the electron transport layer 150, and a negative electrode 170 (second electrode) provided on the electron injection layer 160. In fig. 1, an organic material layer portion including a layer between the positive electrode 110 and the negative electrode 170 constitutes one light emitting stack portion.

Further, the organic electroluminescent device 1 may have a structure in which a stacked structure is inverted (so-called an inverted device), for example, the structure having a negative electrode provided on the substrate 100, an electron injection layer provided on the negative electrode, an electron transport layer provided on the electron injection layer, a light emitting layer provided on the electron transport layer, a hole transport layer provided on the light emitting layer, a hole injection layer provided on the hole transport layer, and a positive electrode provided on the hole injection layer.

In the organic electroluminescent device 1 of the present invention, not all of the above-described layers are necessary, the minimum structural unit is composed of the positive electrode 110, the light emitting layer 140, and the negative electrode 170, and at least one of the hole injection layer 120, the hole transport layer 130, the electron transport layer 150, and the electron injection layer 160 may be omitted.

For example, the stacked structure of the organic electroluminescent device may be, in addition to the above-described structure of "positive electrode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/negative electrode", "positive electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/negative electrode", "positive electrode/electron injection layer/electron transport layer/electron injection layer/negative electrode", "positive electrode/hole transport layer/electron injection layer/light emitting layer/negative electrode", "positive electrode/hole transport layer/light emitting layer/electron injection layer/negative electrode", "positive electrode/hole injection layer/light emitting layer/electron injection layer/negative electrode", and the like.

In addition, in order to adjust the balance of the concentration of holes and electrons in the light emitting layer 140, separate layers (e.g., a hole blocking layer (electron transport auxiliary layer) and/or an electron blocking layer (hole transport auxiliary layer) and the like) may be added in a region between the positive electrode 110 and the light emitting layer 140 (hole transport region) and a region between the light emitting layer 140 and the negative electrode 170 (electron transport region).

In this case, the organic electroluminescent device 1 may have a stacked structure of "positive electrode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/negative electrode", "positive electrode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/negative electrode", and "positive electrode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/negative electrode", etc.

The layers may be formed of a single layer or a plurality of layers.

Hereinafter, the substrate 100 used for the manufacture of the organic electroluminescent device 1 and the respective layers constituting the organic electroluminescent device 1 will be described in detail.

The substrate 100 is a support for supporting the organic electroluminescent device 1, and glass, metal, polymer, semiconductor (silicon), or the like is generally used. The substrate 100 is formed in a plate, film or sheet shape according to the purpose, and for example, a glass plate, a metal foil, a polymer film, a polymer sheet, or the like can be used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, polysulfone, and the like are preferable. In the case of manufacturing a flexible display, as the substrate 100, a plate formed by coating a polymer material (for example, polyimide) having high thermal stability and flexibility on a glass plate (also referred to as carrier glass) may be used.

In the case of a glass substrate, soda lime glass, alkali-free glass, or the like is used, and the thickness is sufficient for maintaining mechanical strength, and thus, for example, 0.2mm or more is sufficient. The upper limit value of the thickness is, for example, 2mm or less, preferably 1mm or less. Since the glass is excellent in terms of the material of the glass, alkali-free glass is preferable because of the small amount of ions eluted from the glass, but glass having SiO implemented therein can be commercially available and used ₂ Etc. soda lime glass of barrier coatings. In addition, in order to improve the gas barrier property, a gas barrier film such as a dense silicon oxide film may be provided on at least one plane of the substrate 100, and particularly, when a polymer plate, film or sheet having low gas barrier property is used as the substrate 100, the gas barrier film is preferably provided.

The positive electrode 110 is an electrode for injecting holes, and the material of the positive electrode is preferably a material with a large work function so that holes can be smoothly injected into the organic material layer.

Examples of the material for forming the positive electrode 110 include inorganic compounds and organic compounds. As the inorganic compound, for example, a metal (aluminum, gold, silver, nickel, palladium, chromium, vanadium, copper, zinc, etc.) or an alloy thereof, a metal oxide (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide (IZO), etc.), such as ZnO: al or SNO, may be included ₂ Combinations of metals and oxides of Sb, metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass or Nesa glass, etc. As the organic compound, for example, poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene may be included]And (PEDOT) and other conductive polymers such as polythiophene, polypyrrole, polyaniline and the like. In addition, a material appropriately selected from materials used as a positive electrode of an organic electroluminescent device may be used.

The hole injection layer 120 is used to efficiently inject holes moving from the positive electrode 110 into the light emitting layer 140 or the hole transport layer 130.

The hole transport layer 130 serves to efficiently transport holes injected from the positive electrode 110 or holes injected from the positive electrode 110 through the hole injection layer 120 to the light emitting layer 140. Each of the hole injection layer 120 and the hole transport layer 130 is formed by laminating and mixing one or two or more hole injection/transport materials or by a mixture of a hole injection/transport material and a polymer binder. In addition, an inorganic salt such as iron (iii) chloride may be added to the hole injection/transport material to form a layer.

As the hole injection/transport material, a material having high hole injection efficiency and efficiently transporting the injected holes is preferable. For this reason, a material which has a small ionization potential, a large mobility of the hole , excellent stability, and is less likely to generate impurities which become traps at the time of manufacture and use is preferable.

As a material for forming the hole injection layer 120 and the hole transport layer 130, any compound selected from among compounds currently generally used as charge transport materials for holes, p-type semiconductors, known compounds for hole injection layers and hole transport layers of organic electroluminescent devices, can be used in the photoconductive material.

Examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (polymers having aromatic tertiary amino groups in the main chain or side chains, 1-bis (4-di-p-toluidine phenyl) cyclohexane, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diaminobiphenyl, N' -diphenyl-N, N '-dinaphthyl-4, 4' -diaminobiphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine, N '-dinaphthyl-N, N' -diphenyl-4, 4 '-diphenyl-1, 1' -diamine, N ⁴ ,N ⁴ ' -diphenyl-N ⁴ ,N ⁴ '-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]-4,4' -diamine, N ⁴ ,N ⁴ ,N ⁴ ',N ⁴ '-tetrakis [1,1' -biphenyl]-4-yl) - [1,1' -biphenyl]Triphenylamine derivatives such as 4,4 '-diamine, 4' -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives and the like), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine and the like), pyrazoline derivatives, hydrazone compounds, Benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9, 12-hexaazabenzophenanthrene-2, 3,6,7,10, 11-hexacyano, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, and the like. In the polymer system, polycarbonate or a styrene derivative, polyvinylcarbazole, polysilane, or the like having the above monomer in a side chain is preferable, but there is no particular limitation as long as a compound capable of forming a thin film necessary for manufacturing a light-emitting element, injecting holes from a positive electrode, and transporting holes is possible.

Furthermore, it is known that the conductivity of organic semiconductors is strongly influenced by doping. Such an organic semiconductor matrix material is composed of a compound having good electron donating property or good electron accepting property. For doping of electron-donating materials, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetracyanodimethane-1, 4-benzoquinone dimethane (F4 TCNQ) and the like are known (for example, refer to document "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, applied physical flash (appl. Applied physical flash, lett.), 73 (22), 3202-3204 (1998) and document" J.Blochwitz, M.Pheiffer, T.Fritz, applied physical flash, 73 (6), 729-731 (1998) ", which generate so-called holes by electron transfer in electron-donating substrates (hole-transporting materials), the conductivity of which varies significantly depending on the number and mobility of the holes, as matrix materials having hole-transporting properties, for example, benzidine derivatives (TPD and the like) or starburst amine derivatives (TDATA and the like) or specific metal phthalocyanines (ZnPc and the like) are known (japanese patent publication 2005-167175).

A hole buffer layer may be additionally provided between the hole injection layer 120 and the hole transport layer 130, and may include a hole injection or transport material known in the art.

The light-emitting layer 140 emits light by recombining holes injected from the positive electrode 110 and electrons injected from the negative electrode 170 between electrodes to which an electric field is applied. The material used for forming the light-emitting layer 140 is not particularly limited as long as it is a compound (light-emitting compound) that emits light by being excited by recombination of holes and electrons, and can be formed in a stable thin film shape, and is preferably a compound that exhibits strong light-emitting (fluorescence) efficiency in a solid state.

The light emission mechanism of the light emitting layer 140 is classified into fluorescence and phosphorescence. Fluorescence is a mechanism in which excitons in a singlet state among excitons generated by a combination of holes and electrons fall to a ground state and emit light, and phosphorescence is a mechanism in which excitons in a triplet state fall to a ground state and emit light. In the case of phosphorescence, since 25% of singlet excitons and 75% of triplet excitons capable of being converted into triplet excitons by intersystem crossing are both involved in luminescence, unlike fluorescence in which only 25% of singlet excitons are involved in luminescence, 100% of quantum efficiency can theoretically be achieved.

The light emitting layer 140 may be a single layer or a plurality of layers, and may include a host and a dopant to improve color purity and quantum efficiency. In the light emitting layer 140 having such a structure, excitons generated in the host are transferred to the dopant to emit light. The host material and the dopant material may be either one type or a combination of plural types. The dopant material may be included in the entire host material or may be partially included in the host material. The doping method may be formed by a co-deposition method with the host material, but may be performed simultaneously after premixing with the host material, or may be formed by a wet film forming method after mixing an organic solvent with the host material.

The amount of the host material to be used varies depending on the type of the host material, and may be set according to the characteristics of the host material. The standard of the amount of the host material to be used is 50 to 99.999 wt%, 80 to 99.95 wt%, or 90 to 99.9 wt% of the entire material for the light-emitting layer.

The amount of the dopant material to be used varies depending on the type of the dopant material, and may be set according to the characteristics of the dopant material. The dopant material is used in an amount of 0.001 to 50 wt%, 0.05 to 20 wt%, or 0.1 to 10 wt% based on the entire material for the light emitting layer. For example, in the above range, it is preferable to prevent the concentration quenching phenomenon.

The host material includes a condensed aromatic ring derivative or a heterocyclic ring-containing compound, and the like. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and the heterocyclic ring-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, fretfulin derivatives, and the like, but are not limited thereto.

When the light emitting layer emits red light, as a dopant, a phosphorescent material such as PIQIr (acac) (bis (1-phenylisoquinoline) iridium acetylacetonate), PQIr (acac) (bis (1-phenylquinoline) iridium acetylacetonate) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium) and PtOEP (octaethylporphyrin platinum) (octaethylporphyrin platinum) or a fluorescent material such as Alq3 (tris (8-hydroxyquinoline) aluminum) may be used, but not limited thereto. When the light emitting layer emits green light, as a dopant, a phosphorescent material such as Ir (ppy) 3 (2-phenylpyridine) iridium) (fac tris (2-phenylpyridine) iridium) or a fluorescent material such as Alq3 (tris (8-hydroxyquinoline) aluminum) may be used, but is not limited thereto. When the light emitting layer emits blue light, as the light emitting dopant, a phosphorescent material such as (4, 6-F2 ppy) 2Irpic or a fluorescent material such as spiro-DPVBi, spiro-6P, distyrylbenzene (DSB), distyrylarylene (DSA), PFO-based polymer, and PPV-based polymer may be used, but is not limited thereto.

For example, as the blue light emitting dopant, a polycyclic aromatic compound represented by the following formula (BD-YX 2) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (BD-YX 2) may be used.

In the formula (BD-YX 2), the A ring, the B ring, and the C ring are each independently an aromatic ring or a heteroaromatic ring, and at least one hydrogen in these rings may be substituted,

y1 is B, P, P = O, P = S, al, ga, as, si-R, or Ge-R, and R of the Si-R and Ge-R is aryl, alkyl, or cycloalkyl,

x1 and X2 are each independently>O、>N-R、>C(-R) ₂ 、>S, or>Se, said>R of N-R is aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted, or cycloalkyl which may be substituted, said>C(-R) ₂ R of (2) is hydrogen, optionally substituted aryl, optionally substituted alkyl, optionally substituted cycloalkyl, and>r of N-R and the said>C(-R) ₂ At least one of R of (C) may be bonded to at least one of the A ring, B ring, and C ring via a linking group or a single bond.

At least one hydrogen in the compound or structure represented by the formula (BD-YX 2) may be substituted with deuterium, cyano, or halogen,

at least one of the A ring, B ring, C ring, aryl, and heteroaryl in the compound or structure represented by the formula (BD-YX 2) may be condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane may be substituted, and at least one-CH 2-in the alkane may be substituted with-O-.

In particular, the aromatic or heteroaromatic ring as the a ring, B ring, and C ring in the formula (BD-YX 2) is preferably a 5-membered ring or a 6-membered ring commonly bonded to the fused bicyclic structure of the above-described formula center constituted by Y1, X1, and X2.

The electron injection layer 160 is used to effectively inject electrons moving from the anode electrode 170 into the light emitting layer 140 or the electron transport layer 150.

The electron transport layer 150 serves to efficiently transport electrons injected from the anode 170 or electrons injected from the anode 170 through the electron injection layer 160 to the light emitting layer 140. As a material of the electron transport layer 150, a compound having an electron accepting property and a high electron mobility is suitable. In addition, as a material of the electron transport layer 150, it should have a lowest unoccupied orbital (Lowest Unoccupied Molecular Orbital; LUMO) energy level suitable for injecting electrons into the light emitting layer 140, and preferably a difference in energy level from a highest occupied molecular orbital (Highest Occupied Molecular Orbital; highest occupied molecular orbital) between the light emitting layer 140 is large to prevent holes from reaching the electron transport layer 150 from the light emitting layer 140.

The electron transport layer 150 and the electron injection layer 160 are formed by stacking and mixing one or two or more electron transport/injection materials, respectively.

The electron injection/transport layer that performs the functions of the electron injection layer and the electron transport layer together is a layer for injecting electrons from the anode and transporting the electrons to the light emitting layer 140, and it is preferable and preferable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this reason, a material which has high electron affinity, high electron mobility, and excellent stability and is less likely to cause impurities that become traps during production and use is preferable. The electron injection/transport layer according to the present embodiment may have a function of a layer capable of effectively blocking movement of holes.

As a material for forming the electron transport layer 150 or the electron injection layer 160, any compound selected from among compounds which are currently generally used as electron transport compounds, electron injection layers for organic electroluminescent devices, and known compounds of electron transport layers may be used in the electrically conductive material. In the present invention, as the electron transport material and/or the electron injection material, one or more compounds including the structure represented by chemical formula 1 may be used.

In general, the material for the electron transport layer 150 or the electron injection layer 160 may contain at least one of a compound composed of an aromatic ring or a plurality of aromatic rings composed of at least one atom selected from the group consisting of carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, a pyrrole derivative and a condensed ring derivative thereof, and a metal complex having electron accepting nitrogen. Specifically, it may include fused ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4' -bis (diphenylvinyl) biphenyl, pyrenone derivatives, oxatea ortho-ketone derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone or diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of the metal complex having an electron accepting nitrogen include, for example, a hydroxyzole complex such as a hydroxyphenyl-oxazolyl complex, a azomethionyl complex, a tolenone metal complex, a flavonol metal complex, a benzoquinoline metal complex and the like. Although these materials are used alone, they may be used in combination with other materials.

In addition, examples of the other electron-transporting compound include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, pyrenone derivatives, oxanaphthacene derivatives, naphthalimide derivatives, anthraquinone derivatives, dibenzoquinone derivatives, diphenoquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-t-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene and the like), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole and the like), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinyl metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzoxazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenyl derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2, 2' -bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene and the like), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazole-2-yl) and the like), benzopyridine derivatives (benzopyridine) and the like), benzopyridine derivatives (2, benzopyridine derivatives) and the like, benzopyridine derivatives (3, 4' -naphthyridine derivatives and the like), the derivatives (2, 62, benzopyridine derivatives) and the like, the derivatives (1, 4-naphthyridine derivatives) and the like, the derivatives (1, 3-naphthyridine derivatives) and the derivatives and the like Aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bisstyryl derivatives, and the like.

In addition, metal complexes having electron accepting nitrogen, for example, a hydroxyzole complex such as a quinolinyl metal complex or a hydroxyphenyl-oxazolyl complex, a azomethine complex, a tolenone metal complex, a flavonol metal complex, a benzoquinoline complex, or the like can also be used.

Although the above materials are used alone, they may be used in combination with other materials.

Among the above materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinolinyl metal complexes are preferable.

The electron transport layer or the electron injection layer may further include a material capable of reducing a material forming the electron transport layer or the electron injection layer. As long as such a reducing material has a certain reducing property, various materials can be used, and for example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals is preferably used.

As a preferable reducing material, examples may include alkali metals such as Li (work function 2.3 eV), na (work function 2.36 eV), K (work function 2.28 eV), rb (work function 2.16 eV) or Cs (work function 1.95 eV), or alkaline earth metals such as Ca (work function 2.9 eV), sr (work function 2.0 to 2.5 eV) or Ba (work function 2.52 eV), and particularly preferably work functions equal to or less than 2.9 eV. Of these, the more preferred reducing material is an alkali metal of K, rb or Cs, even more preferred is Rb or Cs, and most preferred is Cs. These alkali metals have particularly high reducing power, and by adding a small amount to a material forming an electron transport layer or an electron injection layer, an improvement in light emission luminance or an extension in lifetime of an organic EL device can be achieved. In addition, as the reducing material having a work function of 2.9eV or less, a combination of two or more of these alkali metals is also preferable, and particularly a combination including Cs, for example, cs and Na, cs and K, cs and Rb or a combination of Cs, na and K is preferable. By including Cs, the reducing ability can be effectively exerted, and by adding to a material forming the electron transport layer or the electron injection layer, improvement of the light emission luminance and prolongation of the lifetime of the organic EL device can be achieved.

In addition, as another preferable reducing material, an organometallic compound represented by the following structural formula is included.

In the case of the structural formula (i) described above,

Ar ₆ is hydrogen, deuterium, halogen, nitrile, nitro, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkenyl, substituted or unsubstituted silyl, substituted or unsubstituted boron, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,

the curves represent the bonds required to form a five-or six-membered ring with M and 2 or 3 atoms substituted or unsubstituted with one or more substituents as defined for Ar6,

m is an alkali metal or alkaline earth metal.

More preferably, M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, more preferably, M is lithium. For example, the reducing organometallic compound represented by the structural formula is unsubstituted lithium quinolinate.

The above-described reducing material may be used as a mixture or composition in one layer with the material forming the electron transport layer or the electron injection layer, or may be formed and used as a separate layer continuous with the electron transport layer or the electron injection layer.

The anode electrode 170 is used to inject electrons into the light emitting layer 140 through the electron injection layer 160 and the electron transport layer 150.

As a material forming the anode 170, a material having a small work function is preferable to efficiently inject electrons into the organic material layer. Specific examples of the negative electrode material are preferably metals such as tin, indium, calcium, aluminum, silver, lithium, sodium, potassium, titanium, yttrium, gadolinium, lead, cesium, magnesium, and the like, or alloys thereof (magnesium-silver alloy, magnesium-indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, and the like), and the like. Lithium, sodium, potassium, cesium, calcium, magnesium or alloys containing these low work function metals are effective in order to increase electron injection efficiency and improve device characteristics. However, these low work function metals are in many cases often unstable in the atmosphere. To improve this, for example, a method of using an electrode having high stability by doping a small amount of lithium, cesium, or magnesium into an organic material layer is known. As the other dopant, an inorganic salt such as lithium fluoride, cesium fluoride, lithium oxide, cesium oxide, or the like can be used. But the present invention is not limited thereto.

The organic material layer may further include an electron blocking layer (or a hole transport auxiliary layer) between the hole transport layer 130 and the light emitting layer 140, and may further include a hole blocking layer (or an electron transport auxiliary layer) between the electron transport layer 150 and the light emitting layer 140.

The electron blocking layer and the hole blocking layer are layers that prevent excitons generated in the light emitting layer 140 from diffusing into the electron transport layer 150 or the hole transport layer 130 adjacent to the light emitting layer 140 or prevent electrons or holes from flowing into the hole transport layer 130 or the electron transport layer 150 without recombination in the light emitting layer 140. Thus, the number of excitons contributing to light emission in the light-emitting layer increases, and the light-emitting efficiency of the device can be improved and the driving voltage can be reduced. Further, by preventing an irreversible decomposition reaction due to oxidation in which holes diffuse into the electron transport layer 150 that moves electrons through reduction (electron acceptor), durability and stability of the device can be improved, and lifetime of the device can be effectively improved.

The electron blocking layer or the hole blocking layer may use materials known in the art, and the compound including the structure represented by chemical formula 1 of the present invention may preferably be used as a material of the hole blocking layer (or the electron transport auxiliary layer).

The organic material layer may further include a light emitting auxiliary layer (not shown) between the electron blocking layer and the light emitting layer 140. The light emitting auxiliary layer may serve to transport holes to the light emitting layer 140 and adjust the thickness of the organic material layer. For the light-emitting auxiliary layer, a material known in the art as a hole transport material can be used.

The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer, and the like may be formed independently of each other, but may be used as a polymer binder by dispersing in a solvent-soluble resin such as polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutylmethacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethylcellulose, vinyl acetate resin, ABS resin, polyurethane resin, or a cured resin such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicone resin.

< organic electroluminescent device having Structure of plural light-emitting stacks >

Fig. 2 illustrates a structure of an organic electroluminescent device 2 having a plurality of light emitting stacks according to an embodiment of the present invention, two light emitting stacks 230 and 240 are formed at an organic material layer portion between a positive electrode 210 and a negative electrode 220.

Here, the light emitting stacked portions 230 and 240 are not particularly limited as long as they have a light emitting function. For example, each of the light emitting stacks 230 and 240 may include one or more light emitting layers, and may include one or more organic material layers different from the light emitting layers. The light emitting stacks 230 and 240 may include, for example, at least one of a hole transport layer, a hole injection layer, a hole transport/injection layer, a buffer layer, an electron blocking layer, an electron transport layer, an electron injection layer, an electron transport/injection layer, a hole blocking layer, and the like included in the light emitting stack of the organic electroluminescent device 1 described with reference to fig. 1 as one or more organic material layers other than the light emitting layer.

In other words, each of the light emitting stacks 230 and 240 may have a stack structure of the light emitting stacks shown in fig. 1, and may emit light of different wavelengths from each other. For example, the light emitting stack part 230 may emit blue light, the light emitting stack part 240 may emit yellow-green light, and thus the organic electroluminescent device 2 may emit white light.

A charge generation layer 250 is formed between the two light emitting stacks 230 and 240 of the organic electroluminescent device 2, and the charge generation layer 250 makes it possible to emit light of a predetermined color gamut from each light emitting stack portion by generating charges (holes and/or electrons) and injecting them into the adjacent light emitting stacks.

Specifically, the charge generation layer 250 includes an n-type charge generation layer 251 and a p-type charge generation layer 252, the n-type charge generation layer 251 is formed adjacent to the light emitting stack 230 adjacent to the positive electrode 210 to generate/inject electrons to the light emitting stack 230, and the p-type charge generation layer 252 is formed adjacent to the light emitting stack 240 adjacent to the negative electrode 220 to generate/inject holes to the light emitting stack 240. Accordingly, both holes and electrons are supplied to each light emitting stack portion, so that light can be emitted independently in a predetermined color.

The n-type charge generation layer 251 may be a layer capable of injecting n-type charge, generating n-type charge, or injecting/generating n-type charge, and the p-type charge generation layer 252 may be a layer capable of injecting p-type charge, generating p-type charge, or injecting/generating p-type charge.

The n-type charge generation layer 251 may be formed of an organic material layer doped with an alkali metal such as Li or an electron-deficient metal such as an alkaline earth metal as a dopant or a mixed composition layer with an organic metal compound containing an alkali metal such as Li or an alkaline earth metal, and the p-type charge generation layer 252 may be formed of an organic material semiconductor layer including an organic material. One or more compounds of the present invention having the structure represented by chemical formula 1 may be used as a material of the n-type charge generation layer 251.

Fig. 2 shows a case where only two light emitting stacks are provided in the organic material layer portion between the positive electrode 210 and the negative electrode 220, but the present invention is not limited thereto and may have three or more light emitting stacks.

For example, fig. 3 shows a structure of an organic electroluminescent device in which three light emitting stacks 230, 240, and 260 are provided in an organic material layer portion between a positive electrode 210 and a negative electrode 220, and charge generation layers 250 and 270 are provided between the light emitting stacks. In this structure, the light emitting stack portion 260 may include light emitting layers that emit light of the same or different color gamut as the other light emitting stack portions 230 and 240. Similar to the charge generation layer 250, the charge generation layer 270 may include an n-type charge generation layer 271 and a p-type charge generation layer 272.

When three or more light emitting stacks are formed between the positive electrode 210 and the negative electrode 220, the amounts of charge supplied according to the positions of the light emitting stacks may be different from each other, and the amounts of charge supplied to the plurality of light emitting stacks may be adjusted to be balanced by adjusting the amounts of dopants or the like of charge generation layers (e.g., n-type charge generation layers) formed between the light emitting stacks.

In this specification, n-type means n-type semiconductor characteristics. In other words, n-type is a property of receiving or transmitting electrons through the lowest unoccupied molecular orbital (lowest unoccupied molecular orbital; LUMO) energy level, which may be defined as a material property in which electron mobility is greater than hole mobility. Conversely, p-type refers to p-type semiconductor characteristics. In other words, p-type is a property of injecting or transporting holes through the highest occupied molecular orbital (highest occupied molecular orbital; HOMO) energy level, which can be defined as a material property in which hole mobility is greater than electron mobility. In this specification, the organic material layer having n-type characteristics may be referred to as an n-type organic material layer. In addition, the organic material layer having the p-type characteristic may be referred to as a p-type organic material layer. Furthermore, n-type doping means doping to have n-type characteristics.

In this specification, adjacent is the arrangement relation of nearest layers between adjacent layers. For example, two adjacent layers refer to a configuration relationship between two layers disposed closest to each other among the plurality of layers. Here, adjacent may mean a case where two layers are in physical contact, as the case may be, and other layers not mentioned may be interposed between the two layers. For example, the light emitting stack portion adjacent to the negative electrode refers to a light emitting stack portion disposed closest to the negative electrode among the light emitting stack portions. In addition, although physical contact may be made between the negative electrode 220 and the light emitting stack 240 and between the positive electrode 210 and the light emitting stack 230, other layers may be disposed between the negative electrode 220 and the light emitting stack 240 and between the positive electrode 210 and the light emitting stack 230. For example, a separate p-type charge generation layer may be formed between the positive electrode 210 and the light emitting stack 230.

< method for producing organic electroluminescent device >

The layers forming the organic electroluminescent device are formed by deposition method and resistance addingThe thin film is formed by a thermal deposition method, an electron beam deposition method, a sputtering method, a molecular lamination method, a printing method, a spin coating method, a casting method, a coating method, or the like. The film thickness of each layer thus formed is not particularly limited and may be appropriately set according to the nature of the material, but is generally in the range of about 2nm to about 5 μm. The film thickness can be generally measured by a crystal oscillation type film thickness measuring device or the like. In the case of forming a thin film using a deposition method, deposition conditions thereof differ depending on the type of material, the target crystal structure and association structure of the film, and the like. The deposition conditions are generally preferably selected from the range of +50 ℃ to +400 ℃ and a vacuum degree of 10- ⁶ Pa to 10- ³ Pa, deposition rate 0.01 nm/sec to 50 nm/sec, substrate temperature-150 ℃ to +300 ℃ and film thickness 2nm to 5 μm.

Next, as an example of a method for manufacturing an organic electroluminescent device, a method for manufacturing an organic electroluminescent device composed of a positive electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a negative electrode, each composed of a host material and a dopant material, will be described.

A positive electrode is produced by forming a thin film of a positive electrode material on a suitable substrate by a deposition method or the like, and then forming a thin film of a hole injection layer and a hole transport layer on the positive electrode. A host material and a dopant material are co-deposited (codeposition) thereon to form a thin film to form a light emitting layer, and an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film composed of a material for a negative electrode is formed by a deposition method or the like to form a negative electrode, thus obtaining a desired organic electroluminescent device. In the production of the organic electroluminescent device, the production order may be reversed, and the negative electrode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the positive electrode may be produced in this order.

< application example of organic electroluminescent device >

Further, the present invention can be applied to a display device having an organic electroluminescent device, a lighting device having an organic electroluminescent device, or the like.

In this embodiment, a display device or a lighting device having an organic electroluminescent device can be manufactured by a known method in which such an organic electroluminescent device is connected to a known driving device (for example, a drain electrode or a source electrode of a thin film transistor) or the like, and can be driven by a known driving method such as direct current driving, pulse driving, and alternating current driving, as appropriate.

As the display device, for example, a panel display such as a color flat panel display, a flexible display such as a flexible color organic Electroluminescence (EL) display, or the like can be included (for example, refer to japanese patent laid-open No. 10-335066 publication, japanese patent laid-open No. 2003-321546 publication, japanese patent laid-open No. 2004-281706 publication, or the like). The display method of the display may include, for example, a matrix method and/or a segmentation method. Furthermore, the matrix display and the segmented display may coexist in the same panel.

In the matrix, pixels for display are arranged in two dimensions such as a grid shape or a mosaic shape, and characters or images are displayed by a group of pixels. The shape or size of the pixels is determined according to the purpose thereof. For example, a square-shaped pixel having a side length of 300 μm or less is generally used for displaying images and characters on personal computers (Personal Computer: PC), displays and televisions, and in the case of a large display such as a display panel, a pixel of the order of mm is used on one side. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, pixels of red, green, and blue are arranged and displayed. In this case, there are typically an increment type and a stripe type. Also, as a method of driving the matrix, any one of a line sequential driving method and an active matrix may be used. Although the line sequential driving has an advantage of simple structure, the active matrix may be excellent if the operation characteristics are taken into consideration, and thus it is also required to be used differently according to purposes.

In the segmentation method (type), a pattern is formed to display predetermined information, and a predetermined area is made to emit light. For example, it may include time and temperature display in a digital wristwatch or thermometer, operation state display of an acoustic device or an electric cooker, etc., panel display of an automobile, etc.

Examples of the lighting device include lighting devices such as indoor lighting and backlight of a liquid crystal display device and the like (for example, refer to japanese patent publication No. 2003-257621, japanese patent publication No. 2003-277741, japanese patent publication No. 2004-119211 and the like). The backlight is mainly used for improving the visibility of a display device which does not emit light itself, and is used for a liquid crystal display device, a wristwatch, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, in a backlight for a liquid crystal display device, particularly for a PC application in which thinning is problematic, since the existing method is composed of a fluorescent lamp or a light guide plate, a backlight using the light emitting device according to the present embodiment is characterized by being thin and light when difficulty in thinning is considered.

[ example ]

The present invention will be described more specifically by examples below, but the present invention is not limited thereto.

[ Synthesis example of core 1 ]

2-chloro-5, 10-trimethyl-10H-acridine phosphine 5-oxide (100 g,0.343 mol), 4',4',5 '-octamethyl-2, 2' -bis (1, 3, 2-dioxapentaborane) (105.2 g, 0.495mol), pd (dppf) Cl ₂ (7.55 g,0.31 mmol), KOAc (67.5 g,1.375 mol), and X-Phos (16.39 g,3.44 mmol) and heated under reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound core 1 (93.3 g, yield: 71%) was obtained by using column chromatography.

H-NMR：δ1.20(s，12H)，1.69(s，6H)，1.98(s，3H)，7.38(d，1H)，7.43(s，1H)，7.41(t，1H)，7.54(t，1H)，7.76(m，2H)，7.85(d，1H)

[ Synthesis of core 2 to core 12 ]

The objective compound cores 2 to 12 described later were produced in the same manner as in the synthesis example of core 1, except that 3-chloro-5, 10-trimethyl-10H-acridine 5-oxide, 2-chloro-5-methylpara [ acridine phosphine-10, 9 '-fluorene ] 5-oxide, 3-chloro-5-methylpara [ acridine phosphine-10, 9' -fluorene ] 5-oxide, 2 '-chloro-5-methylpara [ acridine phosphine-10, 9' -fluorene ] 5-oxide, 2-chloro-5-methylpara [ acridine phosphine-10, 1 '-cyclohexane ] 5-oxide, 3-chloro-10-methyldibenzo [ b, e ] [1,4] thiophosphine (thiaphosphine) 10-oxide, 2-chloro-10-methylparaben 10-oxide, 3-chloro-5-methylparaben [ acridine-10, 1' -cyclohexane ] 5-oxide, 3-chloro-10-methylparaben [ 2, 4] thiophosphine [ b, e ] [1,4] thiophene ] 10-oxide were used instead of the core 10-chloro-5-methyl-acridine-10-oxide.

Synthesis example 1 Synthesis of Compound A-3

In THF (200 ml) and H ₂ A core 1 (10 g,26 mmol), 9- (4-chlorophenyl) -10-phenylanthracene (11.45 g,37 mmol), pd (OAc) were placed in a mixed solvent of O (50 ml) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound A-3 (10.24 g, yield: 67%) was obtained by using column chromatography. [ LCMS]：584

In the same manner, compounds A-7, A-15, and A-249 were produced by using 9- ([ 1,1 '-biphenyl ] -4-yl) -10- (4-chlorophenyl) anthracenyl, or 5- (10- (4-chlorophenyl) anthracen-9-yl) -2-phenylpyridine, or 4-chloro-5' -phenyl-1, 1':3',1 "-terphenyl, respectively, in place of 9- (4-chlorophenyl) -10-phenylanthracene.

Synthesis of Compound C-49

In THF (200 ml) and H ₂ A core 1 (10 g,26 mmol), 4- (4-chlorophenyl) -2, 6-diphenylpyrimidine (10.76 g,37 mmol), pd (OAc) were placed in a mixed solvent of O (50 ml) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound C-49 (9.86 g, yield: 67%) was obtained by using column chromatography.

[LCMS]：562

In the same manner, by using 2- (4-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (4-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -3-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (4-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 4- (4- (10-chloroanthracen-9-yl) phenyl) -2, 6-diphenylpyrimidine, 2- (4- (10-chloroanthracen-9-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- (3- (10-chloroanthracen-9-yl) phenyl) -2, 6-diphenylpyrimidine, 2- (3- (10-chloroanthracen-9-yl) -4, 6-dichlorophenyl-3, 5-triazine, respectively, the compounds C-53, C-57, C-61, C-65, C-69, E-169, E-173, F-49, F-53, C-169, C-173, C-177, C-181, C-185, and C-189 may be obtained by substituting 4- (4-chlorophenyl) -2, 6-diphenylpyrimidine with 2- (3-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (3-chlorophenyl) -2- ([ 1,1' -biphenyl ] -4-yl) -4- (3-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1 '-biphenyl ] -4-yl) -4- (3-chlorophenyl) -4-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3-chlorophenyl) -6- (3-chlorophenyl) -6-chlorophenyl.

Synthesis of Compound F-143

In THF (200 ml) and H ₂ A core 1 (10 g,26 mmol), 3- (3-chlorophenyl) -5, 10-trimethyl-10H-acridine phosphine 5-oxide (11.51 g,37 mmol), pd (OAc) were placed in a mixed solvent of O (50 ml) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound F-143 (10.28 g, yield: 67%) was obtained by using column chromatography. [ LCMS]：586

In the same manner, by using 2- (3-chlorophenyl) -5, 10-trimethyl-10H-acridinephosphine 5-oxide instead of 3- (3-chlorophenyl) -5, 10-trimethyl-10H-acridinephosphine 5-oxide, compound F-189 can be obtained.

Synthesis of Compound A-65

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was put into core 2 (10 g,26 mmol), 9- (4-chlorophenyl) -10-phenylanthracene (11.45 g,37 mmol), pd (OAc) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound A-65 (10.24 g, yield: 67%) was obtained by using column chromatography. [ LCMS ]：584

In the same manner, by using 2- (3-chlorophenyl) -5, 10-trimethyl-10H-acridine phosphine 5-oxide instead of 9- (4-chlorophenyl) -10-phenylanthracene, the compound F-189 can be obtained or obtained.

Synthesis of Compound C-3

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was put into core 2 (10 g,26 mmol), 4- (4-chlorophenyl) -2, 6-diphenylpyrimidine (10.76 g,37 mmol), pd (OAc) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound C-3 was obtained by using column chromatography (9.86 g, yield: 67%).

[LCMS]：562

In the same way as the above-mentioned method, by using 4- (3- (10-chloroanthracene-9-yl) phenyl) -2, 6-diphenylpyrimidine, 2- (4-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (3- (10-chloroanthracene-9-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine, 5- (3-chlorophenyl) -2, 3-diphenylpyrazine, 4- (3' -chloro- [1,1 '-biphenyl ] -3-yl) -2, 6-diphenylpyrimidine, 4- (4' -chloro- [1,1 '-biphenyl ] -3-yl) -2, 6-diphenylpyrimidine, 4- (3' -chloro- [1,1 '-biphenyl ] -4-yl) -2, 6-diphenylpyrimidine, 4- (3-chlorophenyl) -2, 6-diphenylpyrimidine, 2- ([ 1' -biphenyl ] -4-yl) -4- (4-chlorophenyl) -6-phenyl-1, 5-triazine, 4- (3-chlorophenyl) -2, 3-diphenyl pyrimidine, 4- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -2, 6-diphenyl pyrimidine, 4- (3-chlorophenyl) -1, 3-diphenyl pyrimidine, 4-diphenyl-1, 3-diphenyl-pyrimidine, 3-diphenyl-pyrimidine, respectively 2- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (4 '-chloro- [1,1' -biphenyl ] -3-yl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (3 '-chloro- [1,1' -biphenyl ] -4-yl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (3-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -3-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine, 4- (3-chlorophenyl) -2-phenylquinazoline, 4- ([ 1,1' -biphenyl ] -4-yl) -6- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -2-phenylpyrimidine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (4' -chloro- [1,1 '-biphenyl ] -3-yl) -2-phenylpyrimidine, 4- ([ 1,1' -biphenyl ] -6-chlorophenyl) -2-phenyl ] -4-chlorophenyl) -pyrimidine, 4- ([ 1,1' -biphenyl ] -4-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (4-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 4- (3-chlorophenyl) -2-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3 ' -chloro- [1,1' -biphenyl ] -3-yl) -6-phenyl-1, 3, 5-triazine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (4 ' -chloro- [1,1' -biphenyl ] -3-yl) -6-phenyl-1, 3, 5-triazine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -6-phenyl-1, 3, 5-triazine, 4- ([ 1,1' -biphenyl ] -3-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, 5- (4-chlorophenyl) -2, 3-diphenylpyrazine, 4- (4-chlorophenyl) -2-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine, 4- ([ 1,1' -biphenyl ] -3-yl) -6- (3 ' -chloro- [1,1' -biphenyl ] -3-yl) -2-phenylpyrimidine, 4- ([ 1,1' -biphenyl ] -3-yl) -6- (4 ' -chloro- [1,1' -biphenyl ] -3-yl) -2-phenylpyrimidine, 4- ([ 1,1' -biphenyl ] -3-yl) -6- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 2- ([ 4- (10-chloroanthracene-9-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3 ' -chloro- [1,1' -biphenyl ] -3-yl) -6-phenyl-1, 5-triazine, 2- ([ 1,1 '-biphenyl ] -3-yl) -4- (4' -chloro- [1,1 '-biphenyl ] -3-yl) -6-phenyl-1, 3, 5-triazine, 5- (4- (10-chloroanthracen-9-yl) phenyl) -2, 3-diphenylpyrazine, 5- (3' -chloro- [1,1 '-biphenyl ] -4-yl) -2, 3-diphenylpyrazine, 4- (3' -chloro- [1,1 '-biphenyl ] -4-yl) -2-phenylbenzo [4,5] thieno [3,2-D ] pyrimidine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3 '-chloro- [1,1' -biphenyl ] -4-yl) -6-phenyl-1, 3, 5-triazine, or 5- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -2, 3-diphenylpyrazine instead of 4- (4-chlorophenyl) -2, 6-diphenylpyrimidine, compounds F-3, C-7, F-7, C-11, C-195, E-3, D-123, D-3, C-123, C-15, C-199, E-7, D-127, D-7, C-127, C-131, C-19, C-203, E-11, and, D-131, D-11, C-135, C-23, C-207, E-15, D-135, D-15, C-139, C-75, E-19, D-139, D-19, C-143, C-83, E-23, D-143, E-127, E-195, D-75, D-87, D-23, and E-75.

Synthesis of Compound F-139

In THF (200 ml) and H ₂ A core 2 (10 g,26 mmol), 3- (3-chlorophenyl) -5, 10-trimethyl, was placed in a mixed solvent of O (50 ml)base-10H-acridine phosphine 5-oxide (11.51 g,37 mmol), pd (OAc) ₂ (0.17 g,0.023 mmol), X-Phos (1.24 g,26 mmol), and CS ₂ CO ₃ (17 g,104 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound F-139 was obtained by using column chromatography (10.28 g, yield: 67%).

[LCMS]：586

Synthesis of Compound A-67

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was charged with core 4 (10 g,19 mmol), 9- (4-chlorophenyl) -10-phenylanthracene (8.68 g,28 mmol), pd (OAc) ₂ (0.13 g,0.017 mmol), X-Phos (0.94 g,19 mmol), and CS ₂ CO ₃ (12.9 g,79 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound A-67 (9.38 g, yield: 67%) was obtained by using column chromatography.

[LCMS]：706

In the same manner, by using 9- ([ 1,1' -biphenyl ] -4-yl) -10- (4-chlorophenyl) anthracenyl instead of 9- (4-chlorophenyl) -10-phenylanthracene, compound A-71 can be obtained.

Synthesis example 8 Synthesis of Compound C-99

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was charged with core 3 (10 g,19 mmol), 5- (4-chlorophenyl) -2, 3-diphenylpyrazine (8.15 g,28 mmol), pd (OAc) ₂ (0.13 g,0.017 mmol), X-Phos (0.94 g,19 mmol), and CS ₂ CO ₃ (12.9 g,79 mmol) and heated at reflux for 12 hours. Reverse-rotationAfter termination, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound C-99 (9.12 g, yield: 67%) was obtained by using column chromatography. [ LCMS]：686

In the same manner, by using 4- (4-chlorophenyl) -2-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine, 4- (3-chlorophenyl) -2-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine, 5- (3-chlorophenyl) -2, 3-diphenylpyrazine, 4- (3-chlorophenyl) -2, 6-diphenylpyrimidine, 2- (3-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -3-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, or 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, respectively, instead of 2- (3-chlorophenyl) -2-phenylpyrimidine, compounds C-107, C-231, C-219, C-171, C-175, C-179, C-183, C-187, and C-191.

Synthesis of Compound A-68

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was put into core 5 (10 g,19 mmol), 9- (4-chlorophenyl) -10-phenylanthracene (8.68 g,28 mmol), pd (OAc) ₂ (0.13 g,0.017 mmol), X-Phos (0.94 g,19 mmol), and CS ₂ CO ₃ (12.9 g,79 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, compound a-68 (9.38 g, yield: 67%) was obtained by using column chromatography. [ LCMS]：706

In the same manner, by using 9- ([ 1,1' -biphenyl ] -4-yl) -10- (4-chlorophenyl) anthracenyl instead of 9- (4-chlorophenyl) -10-phenylanthracene, compound A-72 can be obtained.

Synthesis of Compound E-146

In THF (200 ml) and H ₂ A mixed solvent of O (50 ml) was put into core 5 (10 g,19 mmol), 4- (4- (10-chloroanthracene-9-yl) phenyl) -2, 6-diphenylpyrimidine (12.34 g,28 mmol), pd (OAc) ₂ (0.13 g,0.017 mmol), X-Phos (0.94 g,19 mmol), and CS ₂ CO ₃ (12.9 g,79 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Filtering. After removing the solvent of the filtered organic layer, the objective compound F-146 (11.43 g, yield: 67%) was obtained by using column chromatography. [ LCMS ]：861

In the same manner, by using 2- (4- (10-chloroanthracene-9-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 5- (3-chlorophenyl) -2, 3-diphenylpyrazine, 5- (3 '-chloro- [1,1' -biphenyl ] -4-yl) -2, 3-diphenylpyrazine, 4- (3-chlorophenyl) -2, 6-diphenylpyrimidine, 2- (3-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -4-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, 4- ([ 1,1 '-biphenyl ] -3-yl) -6- (3-chlorophenyl) -2-phenylpyrimidine, or 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine, respectively, instead of the anthracene-9-phenyl-pyrimidine, compounds E-150, C-210, D-90, C-146, and, C-150, C-154, C-158, C-162, and C-166.

Synthesis of Compound D-107

In THF (200 ml) and H ₂ A core 3 (10 g,19 mmol) and 5- (3 '-chloro- [1,1' -biphenyl) were placed in a mixed solvent of O (50 ml)]-4-yl) -2, 3-diphenylpyrazine (9.96 g,28 mmol), pd (OAc) ₂ (0.13 g,0.017 mmol), X-Phos (0.94 g,19 mmol), and CS ₂ CO ₃ (12.9 g,79 mmol) and heated at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with dichloromethane and put into MgSO ₄ Proceeding with And (5) filtering. After removing the solvent of the filtered organic layer, the objective compound D-107 (10.1 g, yield: 67%) was obtained by using column chromatography. [ LCMS]：760

In the same manner, by using 4- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -2-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine, 4- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -2, 6-diphenylpyrimidine, 2- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -4, 6-diphenyl-1, 3, 5-triazine, 4- ([ 1,1' -biphenyl ] -4-yl) -6- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -4- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -6-phenyl-1, 3, 5-triazine, 4- ([ 1,1' -biphenyl ] -3-yl) -6- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -2-phenylpyrimidine, 2- ([ 1,1' -biphenyl ] -3-yl) -4- (3 ' -chloro- [1,1' -biphenyl ] -4-yl) -6-phenyl-triazine, 2- ([ 1,1' -biphenyl ] -3-yl) -4-phenyl-pyrimidine, 2- ([ 1,1' -biphenyl ] -4-yl) -2-phenyl-pyrimidine, 2, 1' -biphenyl ] -4-yl, 1-phenyl-yl, 5-yl, respectively, 4- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -2, 6-diphenylpyrimidine, or 2- (3 '-chloro- [1,1' -biphenyl ] -3-yl) -4, 6-diphenyl-1, 3, 5-triazine instead of 5- (3 '-chloro- [1,1' -biphenyl ] -4-yl) -2, 3-diphenylpyrazine, compounds D-119, D-51, D-55, D-59, D-63, D-67, D-71, E-51, and E-55 can be obtained.

Other compounds of the present invention can be synthesized by appropriately changing the compounds of the raw materials in accordance with the method of the above synthesis example.

Production of blue organic electroluminescent devices [ examples 1 to 88 ]

Among the compounds synthesized in the synthesis examples, the following [ table 1] was subjected to sublimation purification in a generally known method with high purity, and then a blue organic electroluminescent device was produced as follows.

First, indium Tin Oxide (ITO) coated thereon is washed with distilled water and ultrasonic waves to a thickness ofIs a glass substrate of a film. When the washing with distilled water is completed, ultrasonic washing with solvents such as isopropyl alcohol, acetone, methanol, etc., and drying are performed, and then transferred to a UV ozone washer (Power sonic405, hwashin Tech), after which the substrate is washed with UV for 5 minutes, and transferred to a vacuum evaporator.

Transparent to ITO prepared as aboveForming positive electrode (ITO)/hole injection layer on the electrodeThe weight ratio of compound HTL1 to P1 is 97: 3) Hole transport layer (cavity)>Compound HTL 1)/electron blocking layer (+.>Compound HTL 2)/light-emitting layer (+.>The weight ratio of compound BH to BD is 97: 3) Electron transport auxiliary layer (")>Compound xETL 1)/electron transport layer (+.>The weight ratio of the example compound, or ETL1 (comparative) to one of N1 to N3, carried in table 1 is 7:3 to 3: 7) (specifically, the weight ratio to N1 is 50:50 Electron injection layer () >Yb)/negative electrodeThe weight ratio of magnesium to silver is 10: 1) Cover layer ()>Compound CPL) to manufacture an organic electroluminescent device.

The structure of the compound used at this time is as follows.

Comparative examples 1 to 4 fabrication of blue organic electroluminescent device

In comparative example 1, except thatA blue organic electroluminescent device was fabricated in the same manner as in example 1, except that Alq3 was deposited instead of the compound of example as the electron transport layer material.

In comparative example 2, toETL1 was deposited as an electron transport layer material instead of the compound of the examples.

In comparative example 3, in the absence of N1, inOnly the compounds of the examples were deposited as electron transport layer materials to manufacture blue organic electroluminescent devices.

In comparative example 4, except thatA blue organic electroluminescent device was fabricated in the same manner as in example 1, except that ETL2 was deposited instead of the compound of example as an electron transport layer material.

The blue organic electroluminescent devices fabricated in examples 1 to 88 and comparative examples 1 to 4 were measured to have a current density of 10mA/cm ² The driving voltage, current efficiency and light emission peak were shown below, and the lifetime results of the device are shown in table 1 below.

[ Table 1 ]

/>

As shown in table 1, it can be seen that the blue organic electroluminescent devices of examples 1 to 88 in which the compound of the present invention was applied as an electron transport layer exhibited more excellent performance in terms of driving voltage, emission peak, current efficiency and lifetime than the blue organic electroluminescent devices of comparative examples 1, comparative example 2, comparative example 3 and comparative example 4 in which the existing Alq3, compound ETL1, ETL1 without N1 were applied as electron transport layer materials, respectively.

Production of blue organic electroluminescent device

Among the compounds synthesized in the synthesis examples, the following [ table 2] was subjected to sublimation purification in a generally known manner with high purity, and then a blue organic electroluminescent device was produced as follows.

On the ITO transparent electrode prepared as above, a positive electrode (ITO)/hole injection layer is formedThe weight ratio of compound HTL1 to P1 is 97: 3) Hole transport layer (cavity)>Compound HTL 1)/electron blocking layer (+.>Compound HTL 2)/light-emitting layer (+.>The weight ratio of the compound BH to BD is 99: 1)/

Electron transport auxiliary layerCompound xETL 1)/electron transport layer (+.>The weight ratio of ETL1 to one of N1 to N3 is 7:3 to 3: 7) (specifically, the weight ratio to N1 is 50:50 N-type charge

Generating layer [ ]The weight ratio of the compound of Table 2 to Li is 99:1)/p-type charge generation layer (>The weight ratio of compound HTL1 to P1 is 97: 3) Hole transport layer (cavity)>Compound HTL 1)/electron blocking layer (+.>Compound HTL 2)/light-emitting layer (+.>The weight ratio of the compound BH to BD is 99: 1) Electron transport auxiliary layer (")>Compound xETL 1)/electron transport layer (+.>The weight ratio of ETL1 to one of N1 to N3 is 7:3 to 3: 7) (specifically, the weight ratio to N1 is 50:50 Electron injection layer ()> Yb)/negative electrode ()>The weight ratio of magnesium to silver is 10: 1) Cover layer ()>Compound CPL) to manufacture an organic electroluminescent device.

The structure of the compound used at this time is as follows.

Manufacture of blue organic electroluminescent devices [ comparative examples 5 to 7 ]

In comparative example 5, except thatA blue organic electroluminescent device was fabricated in the same manner as in example 89, except that Alq3 was deposited instead of the compound of example as the n-type charge generation layer material. />

In comparative example 6, toThe thickness deposition of (2) is indicated as 99: nCGL1 of 1 and Li instead of the compound of the embodiment as an n-type charge generation layer material.

In comparative example 7, toIs deposited only nCGL1 as n-type charge generating layer material.

The blue organic electroluminescent devices fabricated in examples 89 to 164 and comparative examples 5 to 7 were measured to have a current density of 10mA/cm ² The lower driving voltage and current efficiency, and the results thereof are shown in table 2 below.

[ Table 2 ]

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As shown in the table 2, it can be seen that the blue organic electroluminescent devices of examples 88 to 164 in which the compound of the present invention was applied as an n-type charge generation layer exhibited more excellent performance in terms of driving voltage and current efficiency than the blue organic electroluminescent devices of comparative examples 5 to 7 in which the existing Alq3 and compound nCGL1 were respectively applied as n-type charge generation layer materials.

[ reference numerals ]

100: substrate board

110: positive electrode (first electrode)

120: hole injection layer

130: hole transport layer

140: light-emitting layer

150: electron transport layer

160: electron injection layer

170: negative electrode (second electrode)

230, 240, 260: light emitting stack

250, 270: charge generation layer

Claims

1. A compound comprising a structure represented by the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1 described above, a compound having the formula,

x is O or S, and the X is O or S,

Y ₁ o, S, or CR ₁ R ₂ ，

R ₁ To R ₄ Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, trifluoromethyl, nitro, halo, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, substituted or unsubstituted C ₃ -C ₃₀ Cycloalkyl, substituted or unsubstituted C ₂ -C ₃₀ Alkenyl, substituted or unsubstituted C ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₁ -C ₂₀ Is optionally substituted C ₃ -C ₂₀ Aralkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C ₃ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Substituted or unsubstituted C ₁ -C ₃₀ Alkylsilyl, substituted or unsubstituted C ₆ -C ₃₀ Arylsilyl group of (C), substituted or unsubstituted C ₃ -C ₃₀ And R is a member of the group consisting of heteroarylsilyl groups ₁ And R is ₂ A plurality of R ₃ And R is ₄ And adjacent groups combine with each other to form a substituted or unsubstituted ring,

m and n are integers from 0 to 4,

* Is the connection site with the adjacent atom.

2. The compound of claim 1, represented by the following chemical formula 2:

[ chemical formula 2]

In the chemical formula 2 described above, the chemical formula,

X、m、R ₁ to R ₄ Is as defined in formula 1 above,

L ₁ to L ₃ Are identical or different from each other and are each independently selected from the group consisting of single bonds, or substituted or unsubstituted C ₁ -C ₁₀ Alkylene, substituted or unsubstituted C ₆ -C ₃₀ Arylene, substituted or unsubstituted C ₂ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Cyclic alkylene of (C), substituted or unsubstituted C ₂ -C ₂₀ Is selected from the group consisting of heterocycloalkylene,

Ar ₁ selected from the group consisting of substituted and unsubstituted C ₁ -C ₂₀ Alkyl, substituted or unsubstituted C ₃ -C ₃₀ Cycloalkyl, substituted or unsubstituted C ₂ -C ₃₀ Alkenyl, substituted or unsubstituted C ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₁ -C ₂₀ Is optionally substituted C ₃ -C ₂₀ Aralkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C ₃ -C ₃₀ Heteroaryl, substituted or unsubstituted C ₃ -C ₂₀ Substituted or unsubstituted C ₁ -C ₃₀ Alkylsilyl, substituted or unsubstituted C ₆ -C ₃₀ Arylsilyl group of (C), substituted or unsubstituted C ₃ -C ₃₀ Is selected from the group consisting of heteroarylsilyl groups,

p is an integer of 1 to 5,

p is 2 or more, a plurality of L ₃ Or Ar ₁ Each independently being the same or different.

3. The composition of claim 2, wherein Ar of chemical formula 2 ₁ At least one of which comprises an electron withdrawing group or C ₇ Or higher polycyclic aromatic groups.

4. A compound according to claim 3, wherein the electron withdrawing group is C including N ₃ -C ₃₀ Heteroaryl or CN.

5. The composition of claim 2, wherein p of chemical formula 2 is 2.

6. The composition of claim 2, wherein p of chemical formula 2 is 4 or 5.

7. An organic electroluminescent device comprising:

the first electrode is arranged to be electrically connected to the first electrode,

a second electrode opposite to the first electrode, and

an organic material layer portion formed between the first electrode and the second electrode,

wherein the organic material layer portion includes one or more organic material layers, and the organic material layer includes the compound according to any one of claims 1 to 6.

8. The organic electroluminescent device of claim 7, wherein,

the first electrode is a positive electrode and,

the second electrode is a negative electrode and,

the organic material layer includes:

(i) The light-emitting layer is formed of a light-emitting layer,

(ii) A hole transport region interposed between the first electrode and the light emitting layer and including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, and

(iii) An electron transport region interposed between the light emitting layer and the second electrode and including at least one of a hole blocking layer, an electron transport layer, an electron injection layer, and an electron injection/transport layer,

the electron transport region includes the compound.

9. The organic electroluminescent device of claim 8, wherein the electron transport layer or the hole blocking layer comprises the compound.

10. The organic electroluminescent device according to claim 8, wherein any one of the electron transport layer, the electron injection layer, or the electron injection/transport layer further contains at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal.

11. The organic electroluminescent device of claim 10, wherein any of the electron transport layer, the electron injection layer, or the electron injection/transport layer comprises an organometallic compound represented by the following structural formula:

In the case of the structural formula (i) described above,

the curves represent the bonds required to form a five-or six-membered ring with M and 2 or 3 atoms, which are bonded to Ar ₆ Is substituted or unsubstituted with one or more substituents identical to the definition of (a),

m is an alkali metal or alkaline earth metal.

12. The organic electroluminescent device of claim 11, wherein M is an alkali metal selected from lithium, sodium, potassium, rubidium, or cesium.

13. The organic electroluminescent device of claim 12, wherein M is lithium.

14. The organic electroluminescent device according to claim 7, wherein the organic material layer portion comprises a plurality of light emitting stacked portions each including a light emitting layer, and a charge generation layer formed between the plurality of light emitting stacked portions,

The charge generation layer includes the compound.

15. The organic electroluminescent device of claim 14, wherein the charge generation layer comprises an n-type charge generation layer, and the n-type charge generation layer comprises the compound.

16. The organic electroluminescent device of claim 15, wherein the n-type charge generation layer further comprises an alkali metal or an alkaline earth metal.

17. A display device having the organic electroluminescent device as claimed in claim 7, the first electrode of the organic electroluminescent device being electrically connected to the source or drain of the thin film transistor.