CN113056463A - Compound and organic light emitting device including the same - Google Patents

Abstract

The present specification relates to a compound of chemical formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device including the same

Technical Field

The present specification relates to a compound and an organic light emitting device including the same.

The present application claims priority of korean patent application No. 10-2019-0009971, filed by 25.1.2019 to the korean patent office, the entire contents of which are incorporated herein by reference.

Background

An organic light-emitting device is a light-emitting device using an organic semiconductor material, and requires communication of holes and/or electrons between an electrode and the organic semiconductor material. Organic light emitting devices can be broadly classified into the following two types according to the operation principle. The first type is a light emitting device in which an exciton (exiton) is formed in an organic layer by a photon flowing from an external light source into the device, the exciton is separated into an electron and a hole, and the electron and the hole are transferred to different electrodes to be used as a current source (voltage source). The second type is a light-emitting device in which holes and/or electrons are injected into an organic semiconductor material layer forming an interface with an electrode by applying a voltage or current to 2 or more electrodes, and the light-emitting device operates by the injected electrons and holes.

In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode with an organic layer therebetween. Here, in order to improve the efficiency and stability of the organic light emitting device, the organic layer is often formed of a multilayer structure composed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic layer, electrons are injected from a cathode into the organic layer, an exciton (exiton) is formed when the injected holes and electrons meet, and light is emitted when the exciton falls back to a ground state. Such an organic light emitting device is known to have characteristics of self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and the like.

Materials used as the organic layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron inhibiting substances, electron transport materials, electron injection materials, and the like, according to functions. The light-emitting materials include blue, green, and red light-emitting materials, and yellow and orange light-emitting materials required for realizing a more natural color, depending on the light-emitting color.

In addition, for the purpose of an increase in color purity and an increase in luminous efficiency based on energy transfer, as a light emitting material, a host/dopant system may be used. The principle is that when a small amount of a dopant having a smaller energy band gap and excellent light emission efficiency than a host mainly constituting a light emitting layer is mixed in the light emitting layer, excitons generated in the host are transferred to the dopant to emit light with high efficiency. In this case, since the wavelength of the host is shifted to the wavelength range of the dopant, light having a desired wavelength can be obtained according to the kind of the dopant used.

In order to fully utilize the excellent characteristics of the organic light emitting device, the materials constituting the organic layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron suppressing material, an electron transporting material, and an electron injecting material, are stable and effective, and therefore, development of new materials is continuously required.

Disclosure of Invention

Technical subject

The present specification describes compounds and organic light emitting devices comprising the same.

Means for solving the problems

One embodiment of the present specification provides a compound represented by the following chemical formula 1.

[ chemical formula 1]

In the above-described chemical formula 1,

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

ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group,

one of A and B is substituted or unsubstituted benzene and the other is substituted or unsubstituted naphthalene,

r1 and R2 are each independently hydrogen, deuterium, a halogen group, cyano, or substituted or unsubstituted alkyl,

r1 is an integer from 0 to 4,

r2 is an integer of 0 to 2,

when r1 and r2 are 2 or more, the structures in parentheses of 2 or more are the same or different from each other.

Another embodiment provides an organic light emitting device, including: the organic light-emitting device includes a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the compound.

Effects of the invention

The compound represented by chemical formula 1 of the present invention may be used as a material for an organic layer of an organic light emitting device.

The organic light emitting device including the compound represented by chemical formula 1 according to an embodiment of the present specification can achieve an improvement in efficiency.

The organic light emitting device including the compound represented by chemical formula 1 according to an embodiment of the present specification can achieve an improvement in lifetime characteristics.

Drawings

Fig. 1 illustrates an organic light emitting device according to an embodiment of the present specification.

Fig. 2 illustrates an organic light emitting device according to another embodiment of the present description.

Fig. 3 illustrates an organic light emitting device according to another embodiment of the present description.

[ description of symbols ]

1: substrate

2: anode

3: luminescent layer

4: cathode electrode

5: hole injection layer

6: hole transport layer

7: luminescent layer

8: electron transport layer

9: electron blocking layer

10: electron transport and injection layer

Detailed Description

The present specification will be described in more detail below.

The present specification provides a compound represented by the above chemical formula 1.

The organic light emitting device including the compound represented by chemical formula 1 according to an embodiment of the present specification can achieve an improvement in efficiency.

The organic light emitting device including the compound represented by chemical formula 1 according to an embodiment of the present specification can achieve an improvement in lifetime characteristics.

The compound represented by chemical formula 1 of the present application is composed of a quinoxaline unit functioning as an electron acceptor and a carbazole unit to which a ring functioning as an electron donor is fused. Since such two units are directly bonded, charges are received and supplied inside the molecule, and the band gap becomes small.

In addition, since the naphthalene ring is located at one of a or B of chemical formula 1 of the present application, the triplet energy is reduced, and as a result, both the singlet energy and the triplet energy are small, and thus, energy transfer to the red dopant is facilitated, thereby being suitable for use as a host of the red light emitting layer.

Further, oxygen or sulfur atoms are positioned at the meta position based on the nitrogen of carbazole and fused to form a ring, and the ortho position does not push electrons well to the nitrogen electron, and the meta position acts as a suitable electron donor compared to the para position which pushes electrons too far to the nitrogen electron. Meanwhile, the fused ring has a stable structure compared with a carbazole unit with a substituent group.

In addition, the Ar unit and the condensed ring carbazole unit are substituted at an ortho (ortho) position based on the quinoxaline unit to be opposite by structural interference with each other, and the structure becomes more stable due to pi-pi interaction between the two, thereby exhibiting a long-life characteristic.

In the present specification, when a part of "includes" a certain component is referred to, unless otherwise stated, it means that the other component may be further included without excluding the other component.

In the present specification, when it is stated that a certain member is "on" another member, it includes not only a case where the certain member is in contact with the other member but also a case where the other member exists between the two members.

In the context of the present specification,

indicates a site to which another substituent or a binding moiety binds.

In the present specification, examples of the substituent are described below, but the substituent is not limited thereto.

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 the hydrogen atom can be substituted, that is, the substituent can be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same as or different from each other.

In the present specification, the term "substituted or unsubstituted" means substituted with 1 or 2 or more substituents selected from deuterium (-D), a halogen group, a nitrile group, a nitro group, a hydroxyl group, a silyl group, a boron group, an alkoxy group, an alkyl group, a cycloalkyl group, an aryl group, and a heterocyclic group, or a substituent in which 2 or more substituents among the above-exemplified substituents are linked, or does not have any substituent. For example, "a substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.

In the present specification, as examples of the halogen group, there are fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).

In the present specification, the silyl group may be represented by the formula of-SiYaYbYc, and the above Ya, Yb and Yc may each be hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

In the present specification, a boron group may be represented by the chemical formula of-BYdYe, and the above Yd and Ye may each be hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The boron group includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, pentyl, n-pentyl, hexyl, n-hexyl, heptyl, n-heptyl, octyl, and n-octyl.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples thereof include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, and styryl.

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 the number of carbon atoms is preferably 1 to 20. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, etc., but is not limited thereto.

The alkyl group, the alkoxy group, and other substituents including the alkyl group in the present specification are all included in a linear or branched form.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms, and according to one embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the above cycloalkyl group is 3 to 6. Specifically, there are, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 20 carbon atoms. According to an embodiment, theThe aryl group has 6 to 30 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, but is not limited thereto. The polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylene group, a triphenyl group, a perylene group,

Fluorenyl, triphenylene, and the like, but are not limited thereto.

In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure.

When the fluorenyl group is substituted, the compound may be

Isospirofluorene group;

(9, 9-dimethylfluorenyl group) and

and substituted fluorenyl groups such as (9, 9-diphenylfluorenyl) and the like. But is not limited thereto.

In the present specification, the heterocyclic group is a cyclic group containing 1 or more of N, O, P, S, Si and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the number of carbon atoms of the heterocyclic group is 2 to 20. Examples of the heterocyclic group include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, quinolyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, carbazolyl, benzocarbazolyl, benzonaphthofuryl, benzonaphthothienyl, indenocarbazolyl, indolocarbazolyl, and the like.

In the present specification, the heteroaryl group is an aromatic group, and the above description of the heterocyclic group can be applied thereto.

According to an embodiment of the present description, X is O or S.

According to one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

According to one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

According to an embodiment of the present description, Ar is substituted or unsubstituted phenyl; substituted or unsubstituted naphthyl; substituted or unsubstituted biphenyl; a substituted or unsubstituted terphenyl group; substituted or unsubstituted carbazolyl; a substituted or unsubstituted fluorenyl group; substituted or unsubstituted dibenzofuranyl; substituted or unsubstituted dibenzothienyl; or a substituted or unsubstituted 2-ring heterocyclic group containing N, O or S.

According to one embodiment of the present specification, Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted triphenylfuran group, a substituted or unsubstituted perylene group

An azole group, or a substituted or unsubstituted benzothiazolyl group.

According to an embodiment of the present specification, Ar is a phenyl group substituted or unsubstituted with an alkyl group or an aryl group, a naphthyl group substituted or unsubstituted with an alkyl group or an aryl group, a biphenyl group substituted or unsubstituted with an alkyl group or an aryl group, a terphenyl group substituted or unsubstituted with an alkyl group or an aryl group, a carbazolyl group substituted or unsubstituted with an alkyl group or an aryl group, a fluorenyl group substituted or unsubstituted with an alkyl group or an aryl group, a dibenzofuranyl group substituted or unsubstituted with an alkyl group or an aryl group, a dibenzothiophenyl group substituted or unsubstituted with an alkyl group or an aryl group, a benzoxazolyl group substituted or unsubstituted with an alkyl group or an aryl group, or a benzothiazolyl group substituted or unsubstituted with an alkyl group or an aryl group.

According to an embodiment of the present specification, Ar is phenyl, naphthyl, biphenyl, terphenyl, carbazolyl substituted or unsubstituted with phenyl, fluorenyl substituted or unsubstituted with methyl, dibenzofuranyl, dibenzothiophenyl, or benzothiazolyl.

According to an embodiment of the present specification, Ar is phenyl, naphthyl, biphenyl, terphenyl, carbazolyl substituted or unsubstituted with phenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, or benzothiazolyl.

According to one embodiment of the present description, Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

According to an embodiment of the present specification, Ar is a phenyl group, a naphthyl group, a biphenyl group, a dimethylfluorenyl group, a carbazolyl group substituted with a phenyl group or unsubstituted, a dibenzofuranyl group, or a dibenzothiophenyl group.

According to an embodiment of the present specification, Ar may be represented by any one of the following structures.

In the above-described structure, the first and second electrodes,

b1 to B13 are each independently hydrogen, deuterium, a halogen group, cyano, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl,

b1 is an integer from 0 to 5,

b2 is an integer from 0 to 9,

b3 is an integer from 0 to 13,

b4 to b7 are each an integer of 0 to 7,

b8 is an integer from 0 to 8,

b9 is an integer from 0 to 4,

b10 is an integer from 0 to 7,

when b1 to b10 are 2 or more, the structures in parentheses of 2 or more are the same as or different from each other.

According to an embodiment of the present specification, Ar may be represented by any one of the following structures.

In the above structure, the dotted line indicates the bonding position.

According to an embodiment of the present specification, Ar may be represented by any one of the following structures.

In the above structure, the dotted line indicates the bonding position.

According to an embodiment of the present description, B1 to B10 are hydrogen.

According to an embodiment of the present description, each of B11 to B13 is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

According to an embodiment of the present specification, each of B11 to B13 is independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to an embodiment of the present specification, each of B11 to B13 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to one embodiment of the present specification, B11 is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.

According to an embodiment of the present description, B11 is a substituted or unsubstituted phenyl.

According to an embodiment of the present description, B11 is phenyl.

According to an embodiment of the present description, B12 and B13 are each independently a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms.

According to an embodiment of the present description, B12 and B13 are methyl.

According to an embodiment of the present description, b1 to b10 are 0 or 1.

According to an embodiment of the present description, b1 to b10 are 0.

According to one embodiment of the present description, one of a and B is substituted or unsubstituted benzene and the other is substituted or unsubstituted naphthalene.

According to one embodiment of the present disclosure, one of a and B is benzene and the other is naphthalene.

According to an embodiment of the present disclosure, the chemical formula 1 may be represented by any one of the following chemical formulas 2 to 7.

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

In the above-mentioned chemical formulae 2 to 7,

ar, X, R1, R2, R1 and R2 are the same as defined in chemical formula 1,

a1 and A2 are each independently hydrogen, deuterium, a halogen group, cyano, or substituted or unsubstituted alkyl,

a1 is an integer of 0 to 6,

a2 is an integer from 0 to 4,

when a1 and a2 are 2 or more, the structures in parentheses of 2 or more are the same as or different from each other.

According to an embodiment of the present description, R1, R2, a1, and a2 are each independently hydrogen, deuterium, a halogen group, cyano, or substituted or unsubstituted alkyl.

According to an embodiment of the present description, R1, R2, a1 and a2 are each independently hydrogen, deuterium, a halogen group, a cyano group, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

According to an embodiment of the present description, R1, R2, a1 and a2 are each independently hydrogen, deuterium, or a substituted or unsubstituted alkyl group of 1 to 15 carbon atoms.

According to an embodiment of the present description, R1, R2, a1 and a2 are each independently hydrogen, or a substituted or unsubstituted alkyl group of 1 to 15 carbon atoms.

According to one embodiment of the present description, R1 is hydrogen.

According to one embodiment of the present description, R2 is hydrogen.

According to an embodiment of the present description, a1 is hydrogen.

According to an embodiment of the present description, a2 is hydrogen.

According to one embodiment of the present description, r1 is an integer from 0 to 4.

According to one embodiment of the present description, r1 is an integer from 0 to 1.

According to one embodiment of the present description, r2 is an integer from 0 to 2.

According to one embodiment of the present description, r2 is an integer from 0 to 1.

According to an embodiment of the present specification, when r1 and r2 are 2 or more, structures in parentheses of 2 or more are the same as or different from each other.

According to an embodiment of the present specification, when r1 is 2 or more and r2 is 2, structures in parentheses are the same or different from each other.

According to an embodiment of the present specification, when R1 is 2 or more, 2 or more R1 are the same as or different from each other.

According to an embodiment of the present specification, when R2 is 2, 2R 2 are the same as or different from each other.

According to one embodiment of the present specification, a1 is an integer from 0 to 6.

According to one embodiment of the present specification, a1 is an integer from 0 to 1.

According to one embodiment of the present description, a2 is an integer from 0 to 4.

According to one embodiment of the present specification, a2 is an integer from 0 to 1.

According to an embodiment of the present disclosure, the chemical formula 1 may be represented by any one of the following compounds.

The compound represented by chemical formula 1 in the present specification can produce a nucleation structure as shown in the following reaction formula. The substituents may be combined according to a method known in the art, and the kind, position and number of the substituents may be changed according to a technique known in the art.

< reaction formula >

In the above reaction formula, X and Ar are the same as defined in chemical formula 1, and Z is each independently a halogen group.

In the present specification, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure as described above. In the present specification, the HOMO and LUMO levels of the compound can also be adjusted by introducing various substituents into the core structure having the above-described structure.

In addition, an organic light emitting device according to the present specification is characterized by comprising: the organic light-emitting device includes a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the above-mentioned compound.

The organic light emitting device of the present specification can be manufactured by a general method and material for manufacturing an organic light emitting device, in addition to forming 1 or more organic layers using the compound represented by the above chemical formula 1.

In the case of manufacturing an organic light emitting device in which an organic layer including the organic compound represented by chemical formula 1 is formed, the organic compound layer may be formed not only by a vacuum evaporation method but also by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic layer of the organic light-emitting device in the present specification may have a single-layer structure, or may have a multilayer structure in which 2 or more organic layers are stacked. For example, the organic light emitting device of the present invention may have a structure including 1 or more layers of a hole transport layer, a hole injection layer, an electron blocking layer, a layer which simultaneously performs hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and a layer which simultaneously performs electron transport and injection as an organic layer. However, the structure of the organic light emitting device of the present specification is not limited thereto, and a smaller or larger number of organic layers may be included.

In the organic light emitting device of the present specification, the organic layer includes a hole transport layer or a hole injection layer, and the hole transport layer or the hole injection layer may include a compound represented by the above chemical formula 1.

In another organic light emitting device of the present specification, the organic layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by the above chemical formula 1.

In another organic light emitting device of the present specification, the organic layer includes a light emitting layer, and the light emitting layer may include a compound represented by the chemical formula 1.

According to another embodiment, the organic layer includes a light emitting layer, and the light emitting layer may include the compound as a host of the light emitting layer.

In one embodiment of the present specification, the light emitting layer includes the compound represented by the chemical formula 1 as a host of the light emitting layer, and may further include a dopant. At this time, the content of the dopant may be comprised from 1 to 60 parts by weight, preferably from 1 to 20 parts by weight, and more preferably from 1 to 10 parts by weight, based on 100 parts by weight of the main body.

In this case, (4, 6-F) can be used as the dopant₂ppy)₂Examples of the fluorescent substance include phosphorescent substances such as Irpic, spiro-DPVBi (spiro-DPVBi), spiro-6P (spiro-6P), Distyrylbenzene (DSB), Distyrylarylene (DSA), PFO-based polymers, PPV-based polymers, anthracene-based compounds, pyrene-based compounds, and boron-based compounds, but are not limited thereto.

In one embodiment of the present disclosure, the first electrode is an anode, and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is an anode.

For example, the organic light emitting device may have a stacked structure as shown below, but is not limited thereto.

(1) Anode/hole transport layer/light emitting layer/cathode

(2) Anode/hole injection layer/hole transport layer/light emitting layer/cathode

(3) Anode/hole transport layer/light emitting layer/electron transport layer/cathode

(4) Anode/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode

(5) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode

(6) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(7) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(8) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode

(9) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(10) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode

(11) Anode/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/cathode

(12) Anode/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

(13) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode

(14) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

The structure of the organic light emitting device of the present specification may have the structure shown in fig. 1 to 3, but is not limited thereto.

Fig. 1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In the structure as described above, the above-described compound may be contained in the above-described light-emitting layer 3.

Fig. 2 illustrates a structure of an organic light-emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 are sequentially stacked on a substrate 1. In the structure as described above, the above-described compound may be contained in the above-described light-emitting layer 7.

Fig. 3 illustrates a structure of an organic light emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light emitting layer 7, an electron transport and injection layer 10, and a cathode 4 are sequentially stacked on a substrate 1. In the structure as described above, the above-described compound may be contained in the above-described light-emitting layer 7.

For example, the organic light emitting device according to the present specification may be manufactured as follows: the organic el device is manufactured by forming an anode by evaporating metal or a metal oxide having conductivity or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation (e-beam evaporation), then forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer on the anode, and then evaporating a substance that can be used as a cathode on the organic layer. In addition to these methods, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting device.

The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a layer that performs both electron injection and electron transport, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a layer that performs both electron injection and electron transport, and the like. The organic layer can be produced in a smaller number of layers by a solvent process (solvent process) other than the vapor deposition method, for example, spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method using various polymer materials.

The anode is an electrode for injecting holes, and a substance having a large work function is generally preferable as an anode substance so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as Zinc Oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); ZnO-Al or SnO₂Metal such as Sb and oxideA combination of substances; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.

The cathode is an electrode for injecting electrons, and a substance having a small work function is generally preferable as a cathode substance in order to easily inject electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; LiF/Al or LiO₂And a multilayer structure material such as Al, but not limited thereto.

The hole injection layer is a layer that functions to smoothly inject holes from the anode into the light-emitting layer, and the hole injection substance is a substance that can inject holes from the anode well at a low voltage, and preferably, the HOMO (highest occupied molecular orbital) of the hole injection substance is interposed between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrine), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers. The thickness of the hole injection layer may be 1 to 150 nm. When the thickness of the hole injection layer is 1nm or more, there is an advantage that the hole injection property can be prevented from being lowered, and when the thickness of the hole injection layer is 150nm or less, there is an advantage that the driving voltage can be prevented from being increased to increase the movement of holes when the thickness of the hole injection layer is too large.

The hole transport layer can function to smooth the transport of holes. The hole-transporting substance is a substance capable of receiving holes from the anode or the hole-injecting layer and transferring the holes to the light-emitting layer, and is preferably a substance having a high mobility to holes. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.

An electron blocking layer may be provided between the hole transport layer and the light-emitting layer. The electron blocking layer may be made of a material known in the art.

The light-emitting layer may emit red, green or blue light, and may be formed of a phosphorescent substance or a fluorescent substance. The light-emitting substance is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light region, and is preferably a substance having high quantum efficiency with respect to fluorescence or phosphorescence. As an example, there is an 8-hydroxyquinoline aluminum complex (Alq)₃) (ii) a A carbazole-based compound; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (b) is

Azole, benzothiazole and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) polymers; spiro (spiroo) compounds; polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a compound represented by chemical formula 1 of the present application, and specifically, may include a compound represented by chemical formula 1 of the present application as a host. Specifically, when the compound represented by chemical formula 1 of the present application is used as a host of a light-emitting layer, it can be used as a phosphorescent substance emitting red light.

When the light-emitting layer emits red light, as a light-emitting dopant, a phosphorescent material such as piqir (acac) (bis (1-phenylisoquinoline) acetylacetonatoiridium, bis (1-phenylisoquinoline) acetylacetonatoiridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonatoiridium, bis (1-phenylquinoline) acetylacetonatoiridium), PQIr (tris (1-phenylquinoline) iridium, tris (1-phenylquinoline) iridium), PtOEP (octylporphyrin, platinum octaethylporphyrin), or Alq (r) may be used₃(tris (8-hydroxyquinolino) aluminum), etc., but is not limited thereto.

The light emitting layer may further include a compound represented by the following chemical formula 8. Specifically, the light emitting layer may include a compound represented by the following chemical formula 8 as an additional host. At this time, the compound represented by chemical formula 1 may be contained in an amount of 10 to 70 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the entire body.

[ chemical formula 8]

In the chemical formula 8 as described above,

R_aand R_bThe same or different from each other, each independently is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

R_cand R_dThe same or different from each other, each independently is hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group containing 2 to 60 carbon atoms selected from any one or more of N, O and S,

r and s are each an integer of 0 to 7, and when R is 2 or more, R_cAre the same or different from each other, and when s is 2 or more, R_dThe same or different from each other.

According to an embodiment of the present description, R_cAnd R_dAre the same or different from each other, each independently hydrogen; deuterium; a halogen group; a cyano group; a nitro group; an amino group; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group containing 2 to 30 carbon atoms selected from any one or more of N, O and S.

According to an embodiment of the present description, R_cAnd R_dIs hydrogen.

According to an embodiment of the present description, R_aAnd R_bThe same or different from each other, each independently is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to an embodiment of the present description, R_aAnd R_bThe same or different from each other, each independently is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to an embodiment of the present description, R_aAnd R_bThe same or different from each other, each independently is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted benzothiazolyl group.

According to an embodiment of the present description, R_aAnd R_bThe same or different from each other, each independently is a phenyl group substituted or unsubstituted with an alkyl group or an aryl group, a biphenyl group substituted or unsubstituted with an alkyl group or an aryl group, a terphenyl group substituted or unsubstituted with an alkyl group or an aryl group, a naphthyl group substituted or unsubstituted with an alkyl group or an aryl group, a fluorenyl group substituted or unsubstituted with an alkyl group or an aryl group, a dibenzofuranyl group substituted or unsubstituted with an alkyl group or an aryl group, or a dibenzothiophenyl group substituted or unsubstituted with an alkyl group or an aryl group.

According to an embodiment of the present description, R_aAnd R_bIdentical to or different from each other, each independently is phenyl substituted or unsubstituted with methyl, phenyl or naphthyl; biphenyl substituted or unsubstituted with methyl, phenyl or naphthyl; terphenyl optionally substituted with methyl, phenyl or naphthyl; naphthyl substituted or unsubstituted with methyl, phenyl or naphthyl; fluorenyl substituted or unsubstituted with methyl, phenyl or naphthyl; dibenzofuranyl substituted or unsubstituted with methyl, phenyl or naphthyl; or dibenzothienyl substituted or unsubstituted with methyl, phenyl or naphthyl.

According to an embodiment of the present description, R_aAnd R_bAre the same or different from each other and are each independently a phenyl group or a naphthalene groupPhenyl substituted or unsubstituted, biphenyl, terphenyl, naphthyl substituted or unsubstituted by phenyl, dimethylfluorenyl, dibenzofuranyl or dibenzothienyl.

According to an embodiment of the present description, R_aAnd R_bMay each be represented by any of the following structures.

In the above-described structure, the first and second electrodes,

c1 to C13 are each independently hydrogen, deuterium, a halogen group, cyano, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl,

c1 is an integer from 0 to 5,

c2 is an integer from 0 to 9,

c3 is an integer from 0 to 13,

c4 to c7 are each an integer of 0 to 7,

c8 is an integer from 0 to 8,

c9 is an integer from 0 to 4,

c10 is an integer from 0 to 7,

when c1 to c10 are 2 or more, the structures in parentheses of 2 or more are the same as or different from each other.

According to an embodiment of the present description, C1 to C10 are hydrogen.

According to an embodiment of the present description, each of C11 to C13 is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

According to an embodiment of the present specification, each of C11 to C13 is independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to an embodiment of the present specification, C11 to C13 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to one embodiment of the present specification, C11 is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.

According to an embodiment of the present description, C11 is a substituted or unsubstituted phenyl.

According to an embodiment of the present description, C11 is phenyl.

According to an embodiment of the present description, C12 and C13 are each independently a substituted or unsubstituted alkyl group of 1 to 15 carbon atoms.

According to an embodiment of the present description, C12 and C13 are methyl.

According to an embodiment of the present description, R_aAnd R_bMay each be represented by any of the following structures.

The above-mentioned C1 to C3, C5 to C7, C10, C12, C13, C1 to C3, C5 to C7, and C10 are as defined above.

According to an embodiment of the present description, r and s are each an integer from 0 to 7.

According to an embodiment of the present description, r and s are each 0 or 1.

The chemical formula 8 may be represented by any one of the following compounds.

The electron transport layer can play a role in smoothly transporting electrons. The electron transport material is a material capable of injecting electrons from the cathode and transferring the electrons to the light-emitting layer, and is preferably a material having a high mobility to electrons. Specific examples thereof include Al complexes of 8-hydroxyquinoline and Al complexes containing Alq₃The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The thickness of the electron transport layer may be 1 to 50 nm. When the thickness of the electron transport layer is 1nm or more, there is an advantage that the electron transport property can be prevented from being lowered, and when the thickness of the electron transport layer is 50nm or less, there is an advantage that the driving voltage can be prevented from being increased to increase the movement of electrons when the thickness of the electron transport layer is too thick.

The electron injection layer can perform a function of smoothly injecting electrons. As the electron-injecting substance, the following compounds are preferred: a compound having an ability to transport electrons, having an effect of injecting electrons from a cathode, having an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and having an excellent thin-film-forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,

Azole,

Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), and gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.

The electron blocking layer is a layer that prevents holes from reaching the cathode and can be formed under the same conditions as those of the hole injection layer. Specifically, there are

An oxadiazole derivative or a triazole derivative, a phenanthroline derivative, BCP, an aluminum complex (aluminum complex), and the like, but the present invention is not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used. .

Modes for carrying out the invention

Hereinafter, in order to specifically explain the present specification, the detailed description will be given by referring to examples. However, the embodiments described in the present specification may be modified into various forms, and the scope of the present application is not to be construed as being limited to the embodiments described in detail below. The embodiments of the present application are provided to more fully explain the present specification to those skilled in the art.

[ Synthesis examples ]

Production example 1 Synthesis of intermediate A

1) Synthesis of intermediate A-1

In a three-neck flask, 2-bromodibenzo [ b, d ] is added]Furan (2-bromodenzo [ b, d ]]furan) (20.0g, 80.9mmol), bis (pinacolato) diboron (24.7g, 97.1mmol), Tris (dibenzylideneacetone) dipalladium (0) (Tris (d)ibenzylideneacetone)dipalladium(0))(Pd(dba)₂) (0.8g, 1.4mmol), tricyclohexylphosphine (PCy)₃) (0.9g, 1.6mmol), potassium acetate (KOAc) (15.9g, 161.9mmol) and 300ml of 1, 4-bis

The alkane (1,4-dioxane) was stirred under reflux for 12 hours under an argon atmosphere. After the reaction was completed and cooled to room temperature, the reaction mixture was transferred to a separatory funnel, water (200ml) was added thereto, and extraction was performed with ethyl acetate. The extract was washed with MgSO₄After drying, filtration and concentration, the sample was purified by silica gel column chromatography to obtain intermediate A-1(18.6g) (yield 78%, MS: [ M + H ]]⁺＝294)。

2) Synthesis of intermediate A-2

In a three-necked flask, intermediate A-1(18.0g, 61.2mmol) and 1-bromo-2-nitronaphthalene (1-bromo-2-nitroanthylene) (17.0g, 67.3mmol) were dissolved in 270ml of Tetrahydrofuran (THF), and potassium carbonate (potassium carbonate) (K) was added₂CO₃) (33.8g, 244.8mmol) was dissolved in 90ml of H₂O is added. To this was added tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylphoshine) palladium (0)) (Pd (PPh)₃)₄) (3.5g, 3.1mmol) was stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed and cooled to room temperature, the reaction solution was transferred to a separatory funnel and extracted with ethyl acetate (ethyl acetate). The extract was washed with MgSO₄After drying, filtration and concentration, recrystallization was carried out to obtain intermediate A-2(16.8g) (yield 81%, MS [ M + H ]]⁺＝339)。

3) Synthesis of intermediate A

In a two-necked flask, intermediate A-2(16.0g, 47.1mmol), triphenylphosphine (PPh) were added₃) (9.8g, 70.7mmol) and 160ml of o-dichlorobenzene (o-dichlorobenzzene) (o-DCB) were stirred under reflux for 24 hours. After the reaction is finished, cooling to normal temperature, then carrying out reduced pressure distillation to remove the solvent, and using CH₂Cl₂And (4) extracting. The extract was washed with MgSO₄After drying, filtration and concentration, the sample was purified by silica gel column chromatography to obtain intermediate A (10.0g) (yield 69%, MS [ M + H ]]⁺＝307)。

Production example 2 Synthesis of intermediate B

Intermediate B was produced by the same production method as that of intermediate a except that 1-bromo-2-nitronaphthalene was changed to 2-bromo-3-nitronaphthalene (2-bromo-3-nitronaphthalene) and used in production example 1. (MS [ M + H)]⁺＝307)

Production example 3 Synthesis of intermediate C

Intermediate C was produced by the same production method as that of intermediate a except that 1-bromo-2-nitronaphthalene was changed to 2-bromo-1-nitronaphthalene (2-bromo-1-nitronaphthalene) and used in production example 1. (MS [ M + H)]⁺＝307)

Production example 4 Synthesis of intermediate D

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 2-bromodibenzo [ b, d ]]Thiophene (2-bromodenzo [ b, d ]]thiophene), an intermediate was produced by the same production method as that of the intermediate a, except that it was usedD。(MS[M+H]⁺＝323)

Production example 5 Synthesis of intermediate E

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 2-bromodibenzo [ b, d ]]Thiophene (2-bromodenzo [ b, d ]]thiophene), and an intermediate E was produced by the same production method as that of the intermediate a except that 1-bromo-2-nitronaphthalene was changed to 2-bromo-3-nitronaphthalene (2-bromo-3-nitronaphthalene) and used. (MS [ M + H)]⁺＝323)

Production example 6 Synthesis of intermediate F

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 2-bromodibenzo [ b, d ]]Thiophene (2-bromodenzo [ b, d ]]thiophene), and an intermediate F was produced by the same production method as that of the intermediate a except that 1-bromo-2-nitronaphthalene was changed to 2-bromo-1-nitronaphthalene (2-bromo-1-nitronaphthalene). (MS [ M + H)]⁺＝323)

Production example 7 Synthesis of intermediate G

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 10-bromonaphtho [2,1-b ]]Benzofuran (10-bromounapthho [2,1-b ]]benzofuran) was used, and except that 1-bromo-2-nitronaphthalene was changed to 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene), intermediate G was produced by the same production method as that of intermediate a. (MS [ M + H)]⁺＝307)

Production example 8 Synthesis of intermediate H

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 2-bromonaphtho [2,3-b ]]Benzofuran (2-bromounapthho [2,3-b ]]benzofuran) and 1-bromo-2-nitronaphthalene was used instead of 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene), and except that intermediate H was produced by the same production method as that of intermediate a. (MS [ M + H)]⁺＝307)

Production example 9 Synthesis of intermediate I

In production example 1, 2-bromodibenzo [ b, d ]]Furan to 8-bromonaphtho [1,2-b ]]Benzofuran (8-bromounapthho [1,2-b ]]benzofuran) and 1-bromo-2-nitronaphthalene was used instead of 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene), and an intermediate I was produced by the same production method as that of the intermediate a. (MS [ M + H)]⁺＝307)

Production example 10 Synthesis of intermediate J

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 10-bromobenzo [ b]Naphtho [1,2-d ]]Thiophene (10-bromobenzozo [ b ]]naphtha[1,2-d]thiophene), and an intermediate J was produced by the same production method as that of the intermediate a except that 1-bromo-2-nitronaphthalene was used instead of 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene). (MS [ M + H)]⁺＝323)

Production example 11 Synthesis of intermediate K

In the manufacture ofIn example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 2-bromobenzo [ b]Naphtho [2,3-d ]]Thiophene (2-bromobenzozo [ b ]]naphtho[2,3-d]thiophene), and an intermediate K was produced by the same production method as that of the intermediate a except that 1-bromo-2-nitronaphthalene was used instead of 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene). (MS [ M + H)]⁺＝323)

Production example 12 Synthesis of intermediate L

In production example 1, 2-bromodibenzo [ b, d ]]Conversion of furan to 8-bromobenzo [ b]Naphtho [2,1-d ]]Thiophene (8-bromobenzozo [ b ]]naphtho[2,1-d]thiophene), and an intermediate L was produced by the same production method as that of the intermediate a except that 1-bromo-2-nitronaphthalene was used instead of 1-bromo-2-nitrobenzene (1-bromo-2-nitrobenzene). (MS [ M + H)]⁺＝323)

[ Synthesis example 1] Synthesis of Compound 1

In a three-necked flask, intermediate A (10.0g, 32.5mmol) and intermediate a (8.6g, 35.8mmol) were dissolved in 300ml of toluene (tolumen), and sodium tert-butoxide (NaOtBu) (4.7g, 48.8mmol) and bis (tri-tert-butylphosphine) palladium (0) (bis (tri-tert-butylphosphine) palladium (0)) (Pd (P-tBu)₃)₂(0.3g, 0.7mmol) and then stirred under reflux for 6 hours under argon atmosphere. After the reaction is finished, cooling to normal temperature, and adding H₂And O, transferring the reaction liquid to a separating funnel for extraction. The extract was washed with MgSO₄The reaction mixture was dried, concentrated, and purified by silica gel column chromatography and then purified by sublimation to obtain Compound 1(6.2g) (yield 37%, MS [ M + H ]]⁺＝511)。

[ Synthesis example 2] Synthesis of Compound 2

Compound 2 was produced by the same production method as that of compound 1 except that intermediate a was used instead of intermediate b in synthetic example 1. (MS [ M + H)]⁺＝561)

[ Synthesis example 3] Synthesis of Compound 3

Compound 3 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate c in synthetic example 1. (MS [ M + H)]⁺＝601)

[ Synthesis example 4] Synthesis of Compound 4

Compound 4 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate B in synthetic example 1. (MS [ M + H)]⁺＝511)

[ Synthesis example 5] Synthesis of Compound 5

Compound 5 was produced by the same production method as that of compound 1, except that in synthetic example 1, intermediate a was used instead of intermediate B, and intermediate a was used instead of intermediate d. (MS [ M + H)]⁺＝587)

[ Synthesis example 6] Synthesis of Compound 6

Compound 6 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate C in synthetic example 1. (MS [ M + H)]⁺＝511)

[ Synthesis example 7] Synthesis of Compound 7

Compound 7 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate D in synthetic example 1. (MS [ M + H)]⁺＝527)

[ Synthesis example 8] Synthesis of Compound 8

Compound 8 was produced by the same production method as that of compound 1, except that in synthetic example 1, intermediate a was used instead of intermediate D, and intermediate a was used instead of intermediate e. (MS [ M + H)]⁺＝643)

[ Synthesis example 9] Synthesis of Compound 9

Compound 9 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate E in synthetic example 1. (MS [ M + H)]⁺＝527)

Synthesis example 10 Synthesis of Compound 10

In Synthesis example 1Compound 10 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate E and intermediate a was used instead of intermediate f. (MS [ M + H)]⁺＝577)

[ Synthesis example 11] Synthesis of Compound 11

Compound 11 was produced by the same production method as that of compound 1, except that in synthetic example 1, intermediate a was used instead of intermediate E, and intermediate a was used instead of intermediate g. (MS [ M + H)]⁺＝633)

Synthesis example 12 Synthesis of Compound 12

Compound 12 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate F in synthetic example 1. (MS [ M + H)]⁺＝527)

[ Synthesis example 13] Synthesis of Compound 13

Compound 13 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate G in synthetic example 1. (MS [ M + H)]⁺＝511)

Synthesis example 14 Synthesis of Compound 14

In synthetic example 1, intermediate a was used instead of intermediate G, andcompound 14 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate h. (MS [ M + H)]⁺＝587)

[ Synthesis example 15] Synthesis of Compound 15

Compound 15 was produced by the same production method as that of compound 1, except that in synthetic example 1, intermediate a was used instead of intermediate G, and intermediate a was used instead of intermediate i. (MS [ M + H)]⁺＝600)

Synthesis example 16 Synthesis of Compound 16

Compound 16 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate H in synthetic example 1. (MS [ M + H)]⁺＝511)

[ Synthesis example 17] Synthesis of Compound 17

Compound 17 was produced by the same production method as that of compound 1, except that in synthesis example 1, intermediate a was used instead of intermediate H, and intermediate a was used instead of intermediate j. (MS [ M + H)]⁺＝627)

[ Synthesis example 18] Synthesis of Compound 18

In Synthesis example 1, intermediate A was changed to intermediate I and used, except thatExcept that, compound 18 was produced by the same production method as that of compound 1. (MS [ M + H)]⁺＝511)

[ Synthesis example 19] Synthesis of Compound 19

Compound 19 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate J in synthetic example 1. (MS [ M + H)]⁺＝527)

[ Synthesis example 20] Synthesis of Compound 20

Compound 20 was produced by the same production method as that of compound 1, except that in synthetic example 1, intermediate a was used instead of intermediate J, and intermediate a was used instead of intermediate k. (MS [ M + H)]⁺＝692)

Synthesis example 21 Synthesis of Compound 21

Compound 21 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate K in synthetic example 1. (MS [ M + H)]⁺＝527)

[ Synthesis example 22] Synthesis of Compound 22

Compound 22 was produced by the same production method as that of compound 1, except that intermediate a was used instead of intermediate L in synthetic example 1. (MS[M+H]⁺＝527)

[ Experimental example ]

Comparative example 1-1

Indium Tin Oxide (ITO) and a process for producing the same

The glass substrate coated with a thin film of (3) is put in distilled water in which a detergent is dissolved, and washed by ultrasonic waves. In this case, the detergent used was a product of fisher (Fischer Co.) and the distilled water used was distilled water obtained by twice filtration using a Filter (Filter) manufactured by Millipore Co. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the completion of the distilled water washing, the resultant was ultrasonically washed with a solvent of isopropyl alcohol, acetone, or methanol, dried, and then transported to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.

On the ITO transparent electrode thus prepared, HI-A and hexa-nitrile hexaazatriphenylene (HAT-CN) described below were reacted with each other

The hole injection layer is formed by sequentially performing thermal vacuum deposition. On the hole injection layer, as a hole transport layer, the following HT-A and

is vacuum-deposited, and then EB-A described below is deposited as an electron blocking layer

Thermal vacuum evaporation is performed to a thickness of (1). Next, as a light-emitting layer, the following host RH-A and 2 wt% of a dopant RD based on 100 parts by weight of the host were added

Vacuum evaporation is performed to a thickness of (1). N mutext, as an electron transporting and injecting layer, the following ET-A andliq in a ratio of 1:1

Is subjected to thermal vacuum deposition, and then Liq is added thereto

Vacuum evaporation is performed to a thickness of (1).

On the above electron transporting and injecting layer, magnesium and silver were sequentially added at a ratio of 10:1 and at a ratio of

Thickness of aluminum and

the cathode is formed by vapor deposition to produce an organic light-emitting device.

Examples 1-1 to examples 1-22 and comparative examples 1-2 to comparative examples 1-7

Organic light-emitting devices of examples 1-1 to 1-22 and comparative examples 1-2 to 1-7 were produced in the same manner as in comparative example 1-1, except that RH-A was replaced with a modification as shown in Table 1 in comparative example 1-1.

The organic light-emitting devices produced in examples 1-1 to 1-22 and comparative examples 1-1 to 1-7 were applied with current, and the voltage, efficiency, and lifetime were measured, and the results are shown in table 1 below. In this case, the voltage and efficiency were 10mA/cm²Determined by current density of (2), LT₉₇Means that the current density is 20mA/cm²Time when the initial brightness decreased to 97%.

[ Table 1]

The compound represented by chemical formula 1 of the present invention is composed of a quinoxaline unit functioning as an electron acceptor and a carbazole unit to which a ring functioning as an electron donor is fused. Since these two units are directly bonded, charges are exchanged in the molecule, and thus the band gap is reduced. Further, since the naphthalene ring is located on one of a and B, the triplet energy is low, and as a result, the singlet energy and the triplet energy are both small and the energy is favorably transferred to the red dopant, and thus the organic el device is suitably used as a host of a red light-emitting layer as shown in table 1.

If the band gap is too large because of no unit functioning as an electron acceptor as in RH-B, or if the triplet energy is too small because of a naphthalene unit simultaneously located at the A, B position in chemical formula 1 as in RH-F, energy transfer to the red dopant cannot be smoothly performed, and the results show that the voltage, efficiency, and lifetime are not good.

In the structure of chemical formula 1, when oxygen or sulfur atoms are positioned at the meta (meta) position based on the nitrogen of carbazole and fused to form a ring, and a heteroatom is present at the para (para) position as in RH-E, or a nitrogen atom is present as in RH-D, the electron donor property is too strong, and the HOMO (Highest Occupied Molecular Orbital) level is too high, so that hole injection is not smooth and the voltage is increased.

In addition, when compared with RH-a in which an electron donor characteristic is adjusted using carbazole as a substituent, in the case where a condensed ring structure is used to adjust the electron donor characteristic, the stability of the substance becomes higher than in the case of a structure in which carbazole is used as a substituent.

In chemical formula 1 of the present invention, Ar unit and the condensed ring carbazole unit are substituted at ortho position (ortho) with each other based on the quinoxaline unit to have a face-to-face characteristic with each other, and thus the structure is more stabilized by pi-pi interaction between the two, thereby exhibiting a long life characteristic. This can be seen by comparison with the RH-C structure which is applied with quinazoline units instead of quinoxaline units as electron acceptor structures.

In addition, when the electron donor unit and the electron carbazole derivative are linked through a linking group such as a phenyl group as in RH-G, the energy transfer to the dopant is not smooth and the efficiency and lifetime are reduced because the band gap is larger than that of the compound of chemical formula 1 of the present invention in which the electron donor unit and the electron carbazole derivative are directly bound.

Therefore, when the compound having the structure of chemical formula 1 is applied as a red light emitting layer host of an organic electroluminescent device in comparison with the results of comparative examples 1-1 to 1-7 to which similar structures are applied, an optimal device exhibiting characteristics of low voltage, high efficiency, and long lifetime can be obtained.

Example 2-1 to example 2-14 and comparative example 2-2 to comparative example 2-3

Organic light-emitting devices of examples 2-1 to 2-14 and comparative examples 2-1 to 2-3 were produced in the same manner as in comparative example 1-1, except that a mixture of 2 host compounds as shown in table 2 was used instead of RH-a in comparative example 1-1. In this case, when a mixture of 2 compounds is used as a host, the weight ratio between the host compounds is shown in parentheses.

[ Table 2]

As shown in table 2, when the compound of formula 1 is mixed with a compound having a biscarbazole structure such as PGH1 or PGH2 as a host, injection of holes into the light-emitting layer becomes smooth, and thus the voltage decreases, and the position where holes and electrons meet and emit light in the device becomes wider while moving toward the electron transport layer in the light-emitting layer, thereby increasing the lifetime of the device. Such an effect according to the change in the balance of holes and electrons inevitably prevents the reduction in efficiency of the device, but the compound of chemical formula 1 exhibits low-voltage, long-life device characteristics while minimizing the reduction in efficiency. In particular, it is found that the effect is more remarkably exhibited in the compound having the structure of chemical formula 1, as compared with comparative examples 2-1 to 2-3.

Claims (9)

1. A compound represented by the following chemical formula 1:

chemical formula 1

Wherein, in the chemical formula 1,

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

ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group,

one of A and B is a substituted or unsubstituted benzene and the other is a substituted or unsubstituted naphthalene,

r1 and R2 are each independently hydrogen, deuterium, a halogen group, cyano, or substituted or unsubstituted alkyl,

r1 is an integer from 0 to 4,

r2 is an integer from 0 to 2, an

When r1 and r2 are 2 or more, the structures in parentheses of 2 or more are the same or different from each other.

2. The compound according to claim 1, wherein the chemical formula 1 is represented by any one of the following chemical formulae 2 to 7:

chemical formula 2

Chemical formula 3

Chemical formula 4

Chemical formula 5

Chemical formula 6

Chemical formula 7

In the chemical formulae 2 to 7,

ar, X, R1, R2, R1 and R2 are the same as defined in chemical formula 1,

a1 and A2 are each independently hydrogen, deuterium, a halogen group, cyano, or substituted or unsubstituted alkyl,

a1 is an integer of 0 to 6,

a2 is an integer from 0 to 4, an

When a1 and a2 are 2 or more, the structures in parentheses of 2 or more are the same as or different from each other.

3. The compound of claim 1, wherein Ar of chemical formula 1 is represented by any one of the following structures:

in the above-described structure, the first and second electrodes are formed on the substrate,

b1 to B13 are each independently hydrogen, deuterium, a halogen group, cyano, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl,

b1 is an integer from 0 to 5,

b2 is an integer from 0 to 9,

b3 is an integer from 0 to 13,

b4 to b7 are each an integer of 0 to 7,

b8 is an integer from 0 to 8,

b9 is an integer from 0 to 4,

b10 is an integer from 0 to 7, an

When b1 to b10 are 2 or more, the structures in parentheses of 2 or more are the same as or different from each other.

4. The compound of claim 1, wherein the compound of formula 1 is selected from the group consisting of:

5. an organic light emitting device, comprising: a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the compound according to any one of claims 1 to 4.

6. The organic light emitting device of claim 5, wherein the organic layer comprises a light emitting layer and the light emitting layer comprises the compound.

7. The organic light-emitting device according to claim 5, wherein the organic layer comprises a light-emitting layer, and the light-emitting layer contains the compound as a host of the light-emitting layer.

8. The organic light emitting device according to claim 6, wherein the light emitting layer further comprises a compound represented by the following chemical formula 8:

chemical formula 8

In the chemical formula 8, the first and second organic solvents,

R_aand R_bThe same or different from each other, each independently is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

R_cand R_dAre the same or different from each other, each independently hydrogen; deuterium; a halogen group; a cyano group; a nitro group; an amino group; a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group containing 2 to 60 carbon atoms selected from any one or more of N, O and S, and

r and s are each an integer of 0 to 7, and when R is 2 or more, R_cAre the same or different from each other, and when s is 2 or more, R_dThe same or different from each other.

9. The organic light emitting device according to claim 8, wherein the chemical formula 8 is represented by any one of the following compounds:

Images