KR101980841B1

KR101980841B1 - Composition for organic optoelectronic device, organic optoelectronic device and display device

Info

Publication number: KR101980841B1
Application number: KR1020150145261A
Authority: KR
Inventors: 이한일; 강동민; 유은선; 장춘근; 정성현; 한수진
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-10-19
Filing date: 2015-10-19
Publication date: 2019-05-21
Also published as: KR20170045558A

Abstract

At least one first compound represented by Formula 1; And at least one second compound represented by the general formula (2a) or (2b), an organic optoelectronic device including the same, and a display device including the organic optoelectronic device.
Formulas 1 and 2 are as described in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for organic optoelectronic devices, organic optoelectronic devices, and display devices. BACKGROUND OF THE INVENTION [0002]

A composition for organic optoelectronic devices, an organic optoelectronic device and a display device.

An organic optoelectronic diode is an element that can switch between electric energy and light energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device that converts electrical energy into light by applying an electric current to the organic light emitting material. The organic light emitting diode usually has a structure in which an organic layer is interposed between an anode and a cathode.

One embodiment provides a composition for organic optoelectronic devices capable of realizing high efficiency and long life characteristics.

Another embodiment provides an organic optoelectronic device including the composition for the organic optoelectronic device.

Another embodiment provides a display device comprising the organic opto-electronic device.

According to one embodiment, there is provided a composition for an organic optoelectronic device comprising at least one first compound represented by the following general formula (1) and at least one second compound represented by the following general formula (2a) or (2b).

[Chemical Formula 1]

In Formula 1,

X ¹ to X ⁶ are each independently N, C or CR ^a ego,

At least one of X ¹ to X ⁶ is N,

R ^a is each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group,

L ¹ is a C6 to C30 arylene group which is substituted or unsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, or a C6 to C30 aryl group,

ET is a substituted or unsubstituted N-containing C2 to C30 heterocyclic group except for a substituted or unsubstituted carbazolyl group;

(2a)

(2b)

In the above general formulas (2a) and (2b)

L ² and L ³ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group or a combination thereof,

R ⁴ to R ¹¹ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, Lt; / RTI &

"Substitution" in the above general formulas (1), (2a) and (2b) means, unless otherwise defined, that at least one hydrogen atom is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, a C1 to C30 amine group, a C6 to C30 arylamine group, To C30 silyl groups, C1 to C30 alkyl groups, C3 to C30 cycloalkyl groups, C2 to C30 heterocycloalkyl groups, C6 to C30 aryl groups, C2 to C30 heterocyclic groups, C1 to C20 alkoxy groups, C1 to C10 trifluoroalkyl groups or Substituted by cyano group.

According to another embodiment, there is provided an organic optoelectronic device including the composition for an organic optoelectronic device.

According to another embodiment, there is provided a display device including the organic opto-electronic device.

An organic optoelectronic device with high efficiency and long life can be realized.

1 and 2 are cross-sectional views schematically showing an organic optoelectronic device according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, "substitution" means that at least one hydrogen in the substituent or compound is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a C1 to C30 amine group, a C6 to C30 arylamine group, C30 silyl group, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heterocyclic group, C1 to C20 alkoxy group, C1 to C10 trifluoroalkyl group, It means that it has been replaced by anger.

The substituted or unsubstituted C1 to C30 amine groups, C1 to C40 silyl groups, C1 to C30 alkyl groups, C1 to C10 alkylsilyl groups, C3 to C30 cycloalkyl groups, C2 to C30 heterocycloalkyl groups, C6 to C30 aryl groups, A C30 heterocyclic group, or a C1 to C20 alkoxy group may be connected to form a fused ring. For example, the substituted C6 to C30 aryl group may be connected to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring, and the substituted C6 to C30 aryl group may be adjacent to C1 to C30 An alkenyl group and the like to form a triphenylene ring, a naphthalene ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, a phenanthroline ring and the like.

Means one to three heteroatoms selected from the group consisting of N, O, S, P and Si in one functional group, and the remainder being carbon unless otherwise defined .

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a " saturated alkyl group " which does not contain any double or triple bonds.

The alkyl group may be an alkyl group of C1 to C30. More specifically, the alkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

As used herein, the term " aryl group " refers to a grouping of groups having one or more hydrocarbon aromatic moieties,

A structure in which all the elements of the hydrocarbon aromatic moiety have a p-orbital and these p-orbital forms a conjugation, such as a phenyl group and a naphthyl group,

A structure in which two or more hydrocarbon aromatic moieties are connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quarter-phenyl group,

Two or more hydrocarbon aromatic moieties may also include non-aromatic fused rings fused directly or indirectly. For example, a fluorenyl group and the like.

The aryl groups include monocyclic, polycyclic or fused ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

As used herein, the term " heterocyclic group " is a superordinate concept including a heteroaryl group, and includes N, O, and S substituents in the ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, Means at least one heteroatom selected from the group consisting of S, P and Si. When the heterocyclic group is a fused ring, the heterocyclic group or the ring may include one or more heteroatoms.

As used herein, the term " heteroaryl group " means that at least one heteroatom selected from the group consisting of N, O, S, P and Si is contained in the aryl group instead of carbon (C). Two or more heteroaryl groups may be directly connected through a sigma bond, or when the C2 to C60 heteroaryl group includes two or more rings, two or more rings may be fused with each other. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

The heteroaryl group may include, for example, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group and the like.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heterocyclic group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted naphthacenyl group, A substituted or unsubstituted thienyl group, a substituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, Substituted or unsubstituted thiophenyl groups, substituted or unsubstituted pyrrolyl groups, substituted or unsubstituted imidazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted isothiazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted isoxazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrazinyl group , A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted isoindolyl group, a substituted or unsubstituted indolyl group, Substituted or unsubstituted indanediyl groups, substituted or unsubstituted furyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted benzoquinolinyl groups, substituted or unsubstituted phthalazinyl A substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted dibenzoquinoxalinyl group, a substituted or unsubstituted quinazolinyl group, , A substituted or unsubstituted phenanthridinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted phenanthridinyl group, A substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted tetrazolyl group, a substituted or unsubstituted tetrazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted imidazopyridinyl group, a substituted Or a substituted or unsubstituted benzothiopyrimidinyl group, a substituted or unsubstituted benzothioquinolinyl group, a substituted or unsubstituted benzoquinoxalinyl group, a substituted or unsubstituted benzothiophenepyridinyl group, a substituted or unsubstituted benzothiopyrimidinyl group, A substituted or unsubstituted benzofuranylpyridazinyl group, a substituted or unsubstituted benzofuranpyrimidinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzofuranyl group , A substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzothiazine group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted phenoxaphthyl group, a substituted or unsubstituted benzothiophene group, A substituted or unsubstituted carbamoyl group, an unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

In the present specification, a single bond means a bond directly connected to a carbon atom or a hetero atom other than carbon. Specifically, L means a single bond, meaning that the substituent connected to L is directly connected to the center core do. That is, in the present specification, a single bond does not mean methylene or the like via carbon.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

The electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level so that electrons formed in the cathode are injected into the light emitting layer, electrons generated in the light emitting layer migrate to the cathode, And the like.

Hereinafter, a composition for an organic optoelectronic device according to one embodiment will be described.

The composition for an organic optoelectronic device according to an embodiment may include at least one first compound represented by the following formula 1 and at least one second compound represented by the following formula 2a or 2b.

[Chemical Formula 1]

In Formula 1, X ¹ to X ⁶ are each independently N, C or CR ^a , At least one of X ¹ to X ⁶ is N, and R ^a is each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a combination thereof, L ¹ is substituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, or a C6 to C30 aryl group Or an unsubstituted C6 to C30 arylene group, and ET is a substituted or unsubstituted N-containing C2 to C30 heterocyclic group other than a substituted or unsubstituted carbazolyl group;

(2a)

(2b)

L ² and L ³ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group, and R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C30 aryl group, C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, R ⁴ to R ¹¹ are each independently, hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

The composition for an organic optoelectronic device according to an embodiment of the present invention is characterized in that a first compound having an electron injecting and electron transporting property including a compound in which a nitrogen-containing heterocyclic ring is linked with an arylene linker, and a compound having three carbazole groups A second compound having excellent hole injection and hole transportability together with the light emitting layer can be used to reduce the driving voltage and realize an organic light emitting device with long life and high efficiency.

The first compound contains at least one of the linking groups X ¹ to X ⁶ and at least one nitrogen atom in each of the ET groups so that the substituents located at both ends of the linking group L ¹ are all susceptible to electrons when an electric field is applied The electron injection amount is increased and the electron transporting property is relatively strong.

In particular, various properties such as charge injection characteristics, deposition temperature, and glass transition temperature can be controlled depending on the number of N contained in both terminal substituents, the connecting direction of the linking group L ¹ , and the number of the connected arylene groups.

Accordingly, the driving voltage of the organic optoelectronic device to which the first compound is applied can be lowered and the efficiency can be improved.

The ET of formula (1) according to an embodiment of the present invention specifically includes a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted thiazolyl group , A substituted or unsubstituted isothiazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted isoxazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted isoxazolyl group, A substituted or unsubstituted indolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted thiazolyl group, , A substituted or unsubstituted pyridinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted benzoquinolinyl group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted quinolinyl group,A substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted dibenzoquinoxalinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted sienolinyl group, a substituted or unsubstituted phenanthraquinolinyl group, a substituted or unsubstituted quinazolinyl group, A substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted isobenzothiazole group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzoquinazolinyl group, a substituted or unsubstituted isobenzoxazolyl group, a substituted or unsubstituted triazole A substituted or unsubstituted imidazopyrimidinyl group, a substituted or unsubstituted imidazopyrimidinyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted imidazopyrimidinyl group, a substituted or unsubstituted imidazopyrimidinyl group, A substituted or unsubstituted benzoquinoxalinyl group, a substituted or unsubstituted benzothiophenepyridinyl group, a substituted or unsubstituted benzothiophenepyrimidinyl group, a substituted or unsubstituted benzoquinolinyl group, a substituted or unsubstituted benzoquinolinyl group, A furan pyridinyl group, or a substituted or unsubstituted benzofuran pyrimidinyl group.

Can be represented by any one of the following general formulas (I-1) to (I-IV) according to the specific structure of the ET group.

[Chemical Formula 1-I] [Chemical Formula 1-II]

[Chemical Formula 1-III] [Chemical Formula 1-IV]

In the above general formulas (I-1) to (I-IV)

L < ¹ > is as described above,

Z ¹ to Z ¹⁶ are each independently N or CR ^a , at least one of Z ¹ to Z ¹² is N, R ^a is as defined above,

W is O or S,

R ^a1 To R ^a4, R ^12, and R ¹³ are as defined for the R ^a.

For example, at least one of Z ⁴ to Z ⁶ in Formula 1-I may be N, and at least one of Z ⁴ and Z ⁵ in Formula 1-II may be N, and Z of Formula 1-III ⁴ to Z ⁸ may be N, and at least one of Z ⁹ to Z ¹² in the formula (1-IV) may be N.

The ET group of Formula 1 is more specifically a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted thiazinyl group, a substituted or unsubstituted benzothiophene pyrimidinyl group, a substituted or unsubstituted benzofuran pyrimidinyl group , A substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted phenanthrolinyl group, or a substituted or unsubstituted dibenzoquinoxalinyl group,

For example, a substituted or unsubstituted group listed in Group 1 below.

[Group 1]

In the group 1, * is a connection point.

Various characteristics such as charge injection characteristics, deposition temperature, and glass transition temperature can be controlled according to the number of N included in X ¹ to X ⁶ and ET group in the above formula (1).

Specifically, all of Z ¹ to Z ³ in the above general formulas (I-1) to (I-I) are all N, and at least one of Z ⁴ to Z ¹² may be N. That is, in the above general formulas (I-1) to (I-IV), the hexagonal ring represented by Z ¹ to Z ³ may be a substituted or unsubstituted triazinyl group.

Specifically, Z ¹ to Z ³ in the general formula (I- ¹⁾ are all N, and at least one of Z ⁴ to Z ⁶ may be N.

Specifically, Z ¹ to Z ³ in the general formula (1-II) are all N, and at least one of Z ⁴ and Z ⁵ may be N

Specifically, Z ¹ to Z ³ in the general formula (1-III) are all N, and at least one of Z ⁴ to Z ⁸ may be N.

Specifically, Z ¹ to Z ³ in the general formula (1-IV) are all N, and at least one of Z ⁹ to Z ¹² may be N.

When at least one of R ^a1 and R ^a2 in addition to Z ¹ to Z ³ is an N-containing heterocyclic group such as a pyridinyl group or a pyrimidinyl group, the number of N contained in X ¹ to X ⁶ in the above formula May exceed three.

For example, when the total number of N included in Chemical Formula 1 is adjusted to 4 or more, there is an advantageous aspect in electron injection characteristics. For example, the number of N's may be (3, 4), (3, 3), (3, 2), (4, 3), (5, 4) Especially when the number of N is (3, 3), it is advantageous in terms of the stability and mobility of injected electrons.

Depending on the number of N contained in X ¹ to X ⁶ and the position of N, the formula 1 may be represented by any one of the following formulas (1a) to (1g).

[Chemical Formula 1a] [Chemical Formula 1b] Chemical Formula 1c [Chemical Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

In the above formulas (1a) to (Ig), L ¹ and ET are as described above.

In one embodiment of the invention, R ^a and R ^a1 To R ^a4 are each independently hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

Specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted A naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group,

The substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted pyridinyl group, or a substituted or unsubstituted pyrimidinyl group.

More specifically, it may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted pyridinyl group.

Substituted or unsubstituted groups listed in group 2 below.

[Group 2]

In the above group 2, * is a connection point.

L ¹ in formula (1) according to an embodiment of the present invention is specifically a phenylene group substituted or unsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 to C30 aryl group; A biphenylene group substituted or unsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 to C30 aryl group; A terphenylene group substituted or unsubstituted with a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 to C30 aryl group; Or a quaterphenylene group substituted or unsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 to C30 aryl group.

In particular, various characteristics such as charge injection characteristics, deposition temperature, and glass transition temperature can be controlled according to the connection direction of the linking group L ¹ and the number of arylene groups connected thereto. For example, It is not.

[Group 3]

In the above group 3, * is a connection point with a neighboring atom.

When L ¹ is as defined above, the formula 1 may be in the form of a dimer containing two N-containing heterocycles, and the dimer form may be a triazine containing three N-containing heterocycles Compared with the trimer form, it is easy to control the hole mobility and the electron mobility according to the substituent characteristics, and it is expected that the effect of suppressing the formation of crystal phase between materials can be expected.

In particular, the higher the moiety ratio linked in para form in L ¹ , the stronger the molecule itself, and thus the higher the charge mobility.

In addition, the deposition temperature and the glass transition temperature can be controlled by controlling the proportion of the moiety in the form of meta or ortho in L ¹ . In particular, since the LUMO energy level can be controlled by controlling the number of aryl groups contained in L ¹ and the type and direction of substituent groups contained in the heterocycle, the charge injection characteristics can be controlled as desired.

The term " substituted " means, unless otherwise defined, at least one hydrogen is selected from the group consisting of deuterium, a halogen group, a hydroxy group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, An aryl group, or a C2 to C30 heterocyclic group.

The first compound represented by Formula 1 may be, for example, compounds listed in the following Group 4, but is not limited thereto.

[Group 4]

The first compound used in the light emitting layer has a strong electron transporting and injecting property, and in some cases, crystallinity of the material may increase.

Therefore, by using the first compound together with a material having high hole transporting and injecting properties rather than by using the first compound alone, a material in which transport and injection characteristics of holes / transportation and injection characteristics of electrons are balanced can be advantageous.

The compound having a strong hole transporting and injecting property may be a second compound represented by the above formula (2a) or (2b).

The second compound is a compound having bipolar characteristics with relatively high hole characteristics including a compound having three carbazolyl groups linked thereto, and is used in a light emitting layer together with the first compound to increase charge mobility and increase stability. It is possible to remarkably improve the luminous efficiency and the life characteristic.

The above-mentioned formulas (2a) and (2b) can be represented by any one of the following formulas (II-1) to (II-VII) depending on the positions at which two carbazole groups at both ends are connected to the intermediate carbazole group.

[Chemical Formula 2-I] [Chemical Formula 2-II]

[Chemical Formula 2-III] [Chemical Formula 2-IV]

[Chemical Formula 2-V] [Chemical Formula 2-VI]

[Chemical Formula 2-VII]

In the general formulas (II-1) to (II-VII), L ² and L ³ , R ¹ to R ¹¹ are as described above.

The formula (2-II) may be represented by, for example, the following formula (II-a) according to the position where two carbazole groups at both terminals are connected to each other.

[Chemical Formula 2-IIa]

The formula (2-ll) may be represented, for example, by the following formula (2-lia) according to the position at which two carbazole groups at both terminals are connected.

[Chemical Formula 2-Ilia]

In the above Formulas 2-IIa and 2-Illa, L ² and L ³ , R ¹ to R ¹¹ are as described above.

In one embodiment of the invention, Formula 2a and 2b of the L ² and L ³ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl A thienylene group, or a combination thereof,

Specifically, it may be a single bond, or a substituted or unsubstituted phenylene group.

In one embodiment of the present invention, each of R ¹ to R ³ in the above formula (2a) or (2b) is independently a methyl group, an ethyl group, a propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, A substituted phenyl group, a substituted or unsubstituted naphthyl group, or a combination thereof,

Specifically, it may be a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.

For example, in the most specific embodiment of the present invention, R ¹ to R ³ in the general formula (2a) or (2b) are all phenyl groups; R ¹ and R ³ are phenyl groups, R ² is a methyl group; Or R ¹ and R ³ may be a methyl group, and R ² may be a phenyl group.

In one embodiment of the present invention, each of R ⁴ to R ¹¹ in the above formula (2a) or (2b) is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

For example, all of the most specific embodiments of the present invention may be hydrogen.

The second compound represented by the above formula (2a) or (2b) may be, for example, a compound listed in the following group 5, but is not limited thereto.

[Group 5]

On the other hand, there is an advantage that charge mobility can be controlled by controlling the ratio of the second compound having the hole characteristic to the first compound.

The LUMO energy level of the second compound may be above -1.7 eV. Specifically, the LUMO energy level of the second compound may range from -1.7 to -0.850 eV. Here the energy level is calculated using the B3LYP / 6-31G method using Gaussian 09.

Also, the first compound and the second compound may be contained in a weight ratio of, for example, about 1: 9 to 9: 1, specifically 2: 8 to 8: 2, 3: 7 to 7: : 4, and 5: 5 by weight. By being included in the above range, the bipolar characteristic can be implemented more effectively, and the efficiency and lifetime can be simultaneously improved.

Specifically, the first compound and the second compound may be contained in the light emitting layer 32 as a host. For example, the first compound may be represented by the following formula 1-I or 1-II, (2-IIa) or (2-IIIa).

The light emitting layer 32 may further include at least one compound other than the first compound and the second compound described above as a host. For example, the light emitting layer 32 may further include a dopant. The dopant may be a material that emits light by mixing with the host in a trace amount and may be a metal complex such as a metal complex that emits light by multiple excitation that excites the triplet state. The dopant may be, for example, an inorganic, organic, or organic compound, and may include one or more species.

The dopant may be a red, green or blue dopant, for example a phosphorescent dopant. Examples of the phosphorescent dopant include organic metal compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh and Pd or combinations thereof. The phosphorescent dopant may be, for example, a compound represented by the following formula (Z), but is not limited thereto.

(Z)

L ₂ MX

In the above formula (Z), M is a metal, L and X are the same or different from each other and are ligands that complex with M.

M may be Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof, Lt; / RTI >

The composition may be applied to an organic layer of an organic optoelectronic device, for example, the composition may be applied to a light emitting layer. For example, as a host of a light emitting layer.

The composition may be formed by a dry film forming method or a solution process. The dry film forming method may be, for example, a chemical vapor deposition method, sputtering, plasma plating, or ion plating, and two or more compounds may be simultaneously deposited or a compound having the same deposition temperature may be mixed to form a film. The solution process may be, for example, ink jet printing, spin coating, slit coating, bar coating and / or dip coating.

Hereinafter, an organic optoelectronic device to which the above-described composition is applied will be described.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy into each other. The organic electroluminescent device is selected from the group consisting of an organic light emitting device, an organic photoelectric device, an organic solar cell, an organic transistor, It can be either.

The organic optoelectronic device may include an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer may include the above-described composition.

Here, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 is a cross-sectional view illustrating an organic light emitting device according to one embodiment.

1, an organic light emitting device 100 according to an embodiment includes an anode 110 and a cathode 120 facing each other, and an organic layer 105 disposed between the anode 110 and the cathode 120 .

The anode 110 may be made of a conductor having a high work function to facilitate, for example, hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 120 may be made of a conductor having a low work function, for example, to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 105 includes a light emitting layer 130 including the above-described composition.

2 is a cross-sectional view illustrating an organic light emitting device according to another embodiment.

Referring to FIG. 2, the organic light emitting diode 200 according to the present embodiment includes an anode 110 and a cathode 120 facing each other, and a cathode 120 disposed between the anode 110 and the cathode 120, as in the above- And an organic layer 105 formed on the substrate.

The organic layer 105 includes a light emitting layer 130 and an auxiliary layer 140 positioned between the light emitting layer 130 and the cathode 120. The auxiliary layer 140 may facilitate charge injection and movement between the cathode 120 and the light emitting layer 130. [ The auxiliary layer 140 may be, for example, an electron transporting layer, an electron injecting layer, and / or an electron transporting auxiliary layer.

1 and 2, the organic layer 105 may further include at least one auxiliary layer positioned between the anode 110 and the light emitting layer 130.

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

The starting materials and reactants used in the synthesis examples and examples of the present invention were purchased from Sigma-Aldrich or TCI unless otherwise noted.

Synthesis of first compound

Synthetic example 1: Synthesis of intermediate I-1

2-chloro-4,6-diphenyl-1,3,5-triazine (100 g, 374 mmol) from Shenzhen gre-syn chemical technology (http://www.gre-syn.com/) was dissolved in tetrahydrofuran ), And 3-chlorophenylboronic acid (64.3 g, 411 mmol) and tetrakis (triphenylphosphine) palladium (4.32 g, 3.74 mmol) were added thereto and stirred. Saturated water-saturated potassuim carbonate (138 g, 935 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain Intermediate I-1 (122 g, 95%).

HRMS (70 eV, EI +): m / z calcd for C21H14ClN3: 343.0876, found: 343.

Elemental Analysis: C, 73%; H, 4%

Synthetic example 2: Synthesis of intermediate I-2

Bis (pinacolato) diboron (106 g, 419 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 1.1 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (2.85 g, 3.49 mmol) and potassium acetate (103 g, 1,047 mmol) were heated at 150 ° C. for 20 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The obtained residue was purified by flash column chromatography to obtain intermediate I-2 (119 g, 78%).

HRMS (70 eV, EI +): m / z Calcd for C27H26BN3O2: 435.2118, found: 435.

Elemental Analysis: C, 74%; H, 6%

Synthetic example 3: Synthesis of Intermediate I-3

Intermediate I-2 (50 g, 115 mmol) was dissolved in 0.4 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-3-chlorobenzene (24.2 g, 126 mmol) and tetrakis (triphenylphosphine) palladium 1.15 mmol) were added and stirred. Potassium hydroxide (42.3 g, 288 mmol) saturated with water was added, and the mixture was refluxed by heating at 80 ° C for 7 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-3 (46.4 g, 96%).

HRMS (70 eV, EI +): m / z calcd for C27H18ClN3: 419.1189, found: 419.

Elemental Analysis: C, 77%; H, 4%

Synthetic example 4: Synthesis of intermediate I-4

2-chloro-4,6-diphenylpyrimidine (100 g, 375 mmol) from Shenzhen gre-syn chemical technology (http://www.gre-syn.com/) was reacted in the same manner as in Synthesis Example 1, I-4 (120 g, 93%).

HRMS (70 eV, EI +): m / z calcd for C21H15ClN2: 342.0924, found: 342.

Elemental Analysis: C, 77%; H, 4%

Synthetic example 5: Synthesis of intermediate I-5

Intermediate I-3 (40 g, 95.3 mmol) was reacted in the same manner as in Synthesis Example 2 to obtain Intermediate I-5 (35.6 g, 73%) in a nitrogen atmosphere.

HRMS (70 eV, EI +): m / z calcd for C33H30BN3O2: 511.2431, found: 511.

Elemental Analysis: C, 78%; H, 6%

Synthetic example 6: Synthesis of Intermediate I-6

Intermediate I-6 was synthesized according to the preparation method of the published patent WO2015-137630.

HRMS (70 eV, EI +): m / z calcd for C16H9ClN2S1: 296.0175, found: 511.

Elemental Analysis: C, 65%; H, 3%

Synthetic example 7: Synthesis of Intermediate I-7

3-bromo-9H-carbazole (100 g, 406 mmol) was dissolved in dimethylforamide (DMF) (0.5 L) under a nitrogen atmosphere and the internal temperature was cooled to 0 ° C. Sodium hydride (19.5 g, 813 mmol) was added thereto, stirred for 1 hour, iodomethane (86.5 g, 142 mmol) was added, and the mixture was reacted at room temperature for 10 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-7 (71.7 g, 68%).

HRMS (70 eV, EI +): m / z calcd for C13H10BrN: 258.9997, found: 259.

Elemental Analysis: C, 60%; H, 4%

Synthetic example 8: Synthesis of Intermediate I-8

Bis (pinacolato) diboron (84.0 g, 331 mmol) and (1,1'-bis (diphenylphosphine) diphenylphosphine) were dissolved in 0.8 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (4.50 g, 5.51 mmol) and potassium acetate (81.1 g, 827 mmol) were added and the mixture was refluxed by heating at 150 ° C for 5 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-8 (30 g, 35%).

HRMS (70 eV, EI +): m / z calcd for C19H22BNO2: 307.1744, found: 307.

Elemental Analysis: C, 74%; H, 7%

Synthetic example 9: Synthesis of intermediate I-9

3-Chlorophenylboronic acid (20 g, 128 mmol) and tetrakis (triphenylphosphine) palladium (1.23 g, 1.07 mmol) were dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 2-bromotriphenylene And stirred. Potassium hydroxide (36.8 g, 267 mmol), saturated with water, was added and heated at 80 ° C for 24 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-9 (22.6 g, 63%).

HRMS (70 eV, EI +): m / z calcd for C24H15Cl: 338.0862, found: 338.

Elemental Analysis: C, 85%; H, 5%

Synthetic example 10: Synthesis of intermediate I-10

Bis (pinacolato) diboron (25.4 g, 100 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.3 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.54 g, 0.67 mmol) and potassium acetate (16.4 g, 167 mmol) were added and the mixture was refluxed by heating at 150 ° C for 48 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-10 (18.6 g, 65%).

HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 430.2104, found: 430.

Elemental Analysis: C, 84%; H, 6%

Synthetic example 11: Synthesis of Intermediate I-11

1-bromo-3-iodobenzene (39.4 g, 139 mmol) and tetrakis (triphenylphosphine) palladium (1.34 g, 139 mmol) were dissolved in 0.5 L of tetrahydrofuran (THF) 1.16 mmol) were added and stirred. Potassium hydroxide (40.1 g, 290 mmol), saturated with water, was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-11 (42.6 g, 80%).

HRMS (70 eV, EI +): m / z calcd for C30 H19 Br: 458.0670, found: 458.

Elemental Analysis: C, 78%; H, 4%

Synthetic example 12: Synthesis of intermediate I-12

Intermediate I-11 (40 g, 87.1 mmol) was reacted in the same manner as in Synthesis Example 8 to obtain I-12 (34 g, 77%) in a nitrogen atmosphere.

HRMS (70 eV, EI +): m / z calcd for C36H31BO2: 506.2417, found: 506.

Elemental Analysis: C, 85%; H, 6%

Synthesis of final compound

Synthetic example 13: Synthesis of Compound 1-6

Intermediate I-1 (7.91 g, 23.0 mmol) and bis (dibenzylideneacetone) palladium (o) (0.40 g, 23.0 mmol) were dissolved in 0.1 L of 1,4-dioxane in a nitrogen atmosphere, g, 0.69 mmol), tris-tert butylphosphine (0.70 g, 3.45 mmol) and cesium carbonate (18.7 g, 57.5 mmol) were successively added thereto and heated at 100 ° C for 18 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1-6 (11.3 g, 80%).

HRMS (70 eV, EI +): m / z calcd for C42H28N6: 616.2375, found: 616.

Elemental Analysis: C, 82%; H, 5%

Synthetic example 14: Synthesis of Compound 1-7

Compounds 1-7 (12.0 g, 75%) were obtained in the same manner as in 13, except that I-3 was used instead of the reactant I-1 in Synthesis Example 13.

HRMS (70 eV, EI +): m / z calcd for C48H32N6: 692.2688, found: 692.

Elemental Analysis: C, 83%; H, 5%

Synthetic example 15: Synthesis of Compound 1-18

Intermediate I-4 (7.88 g, 23.0 mmol) and bis (dibenzylideneacetone) palladium (o) (0.40 g, 23.0 mmol) were dissolved in 0.1 L of 1,4-dioxane in a nitrogen atmosphere, g, 0.69 mmol), tris-tert butylphosphine (0.70 g, 3.45 mmol) and cesium carbonate (18.7 g, 57.5 mmol) were successively added thereto and heated at 100 ° C for 18 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1-18 (10.2 g, 72%).

HRMS (70 eV, EI +): m / z calcd for C43H29N5: 615.2423, found: 615.

Elemental Analysis: C, 84%; H, 5%

Synthetic example 16: Synthesis of Compound 1-54

Intermediate I-6 (5.80 g, 19.6 mmol) and bis (dibenzylideneacetone) palladium (o) (0.34 g, 19.6 mmol) were dissolved in 0.1 L of 1,4-dioxane in a nitrogen atmosphere, g, 0.59 mmol), tris-tert butylphosphine (0.60 g, 2.95 mmol) and cesium carbonate (16.0 g, 49.0 mmol) were successively added thereto and refluxed by heating at 100 ° C for 24 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1-54 (9.87 g, 78%).

HRMS (70 eV, EI +): m / z calcd for C43H27N5S: 645.1987, found: 645.

Elemental Analysis: C, 80%; H, 4%

Synthetic example 17: Synthesis of Compound 2-1

3,6-dibromo-9-phenylcarbazole (10 g, 24.9 mmol) purchased from Tokyo Chemical Industry (http://www.tcichemicals.com/) was dissolved in 0.1 L of tetrahydrofuran (THF) 9-phenylcarbazole-3-boronic acid (14.3 g, 49.9 mmol) and tetrakis (triphenylphosphine) palladium (0.58 g, 0.50 mmol) Potassium carbonate (18.3 g, 125 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 9 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Compound 2-1 (16.3 g, 90%).

HRMS (70 eV, EI +): m / z Calcd for C54 H35 N3: 725.2831, found: 725.

Elemental Analysis: C, 89%; H, 5%

Synthetic example 18: Synthesis of Compound 2-6

2,7-dibromo-9-phenylcarbazole (10 g, 24.9 mmol) purchased from Tokyo Chemical Industry (http://www.tcichemicals.com/) was dissolved in 0.1 L of tetrahydrofuran (THF) 9-phenylcarbazole-2-boronic acid (14.3 g, 49.9 mmol) and tetrakis (triphenylphosphine) palladium (0.58 g, 0.50 mmol) Potassium carbonate (18.3 g, 125 mmol) saturated with water was added and heated at 80 ° C for 11 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 2-6 (16.6 g, 92%).

HRMS (70 eV, EI +): m / z Calcd for C54 H35 N3: 725.2831, found: 725.

Elemental Analysis: C, 89%; H, 5%

Synthetic example 19: Synthesis of Compound 2-65

3,6-dibromo-9-phenylcarbazole (10 g, 24.9 mmol) purchased from Tokyo Chemical Industry (http://www.tcichemicals.com/) was dissolved in 0.1 L of tetrahydrofuran (THF) Intermediate I-8 (15.3 g, 49.9 mmol) and tetrakis (triphenylphosphine) palladium (0.58 g, 0.50 mmol) were added and stirred. Potassium carbonate (18.3 g, 125 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 2-65 (13.8 g, 92%).

HRMS (70 eV, EI +): m / z Calcd for C44 H31 N3: 601.2518, found: 601.

Elemental Analysis: C, 88%; H, 5%

Synthetic example 20: Compound HOST1 synthesis

Intermediate 1-12 (20 g, 39.5 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and then a solution of 2- chloro-4,6-diphenyl-1,3,5-triazine (10.6 g, 39.5 mmol) and tetrakis (triphenylphosphine) palladium (0.46 g, 0.4 mmol) were added and stirred. Saturated water-saturated potassium carbonate (13.6 g, 98.8 mmol) was added and the mixture was refluxed by heating at 80 ° C for 23 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain compound HOST1 (17.9 g, 74%).

HRMS (70 eV, EI +): m / z calcd for C45 H29 N3: 611.2361, found: 611.

Elemental Analysis: C, 88%; H, 5%

Synthetic example 21: Compound HOST2 synthesis

3-boronic acid (8.91 g, 31.0 mmol) and tetrakis (triphenylphosphine) were dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 3-bromo-9-phenylcarbazole palladium (0.36 g, 0.31 mmol) were added thereto and stirred. Potassium hydroxide (11.4 g, 77.5 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain compound HOST2 (13.8 g, 92%).

HRMS (70 eV, EI +): m / z Calcd for C36 H24 N2: 484.1939, found: 484.

Elemental Analysis: C, 89%; H, 5%

Fabrication of organic light emitting device

Example One

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 10 minutes, and then the substrate was transferred to a vacuum evaporator. Compound A was vacuum deposited on the ITO substrate using the prepared ITO transparent electrode as an anode to form a hole injection layer having a thickness of 700 Å, Compound B was deposited on the injection layer to a thickness of 50 Å, 1020 A thick to form a hole transport layer. The compound 1-6 obtained in Synthesis Example 13 and the compound 2-1 obtained in Synthesis Example 17 were simultaneously used as a host on the hole transport layer and Tris (2-phenylpyridinato) iridium (III) [Ir (ppy) 3] Was doped to 10 wt%, and a 400 Å thick light emitting layer was formed by vacuum deposition. Here, the compound 1-6 and the compound 2-1 were used in a weight ratio of 1: 1. Subsequently, Compound D and Liq were simultaneously vacuum-deposited on the light emitting layer at a ratio of 1: 1 to form an electron transport layer having a thickness of 300 Å. Liq 15 Å and Al 1200 Å were sequentially vacuum deposited on the electron transport layer to form a cathode, Respectively.

The organic light emitting device has a structure having five organic thin film layers. Specifically, the organic light emitting device has the following structure.

X: X: 10%] (400 Å) / Compound (A) [Compound 1-6: Compound 2-1: Ir (ppy) 3 = X: X: 10% D: Liq (300 Å) / Liq (15 Å) / Al (1200 Å). (X = weight ratio)

Compound A: N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-

Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN),

Compound C: N- (biphenyl-4-yl) -9,9-dimethyl- N- (4- (9-phenyl-9H-carbazol-

Compound D: 8- (4- (4,6-di (naphthalen-2-yl) -1,3,5-triazin- 2- yl) phenyl) quinoline

Example 2

An organic luminescence device was prepared in the same manner as in Example 1, except that the compound 2-6 obtained in Synthesis Example 18 was used instead of the compound 2-1 obtained in Synthesis Example 17.

Example 3

An organic luminescent device was produced in the same manner as in Example 1, except that the compound 2-65 obtained in Synthesis Example 19 was used instead of the compound 2-1 obtained in Synthesis Example 17.

Example 4

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound 1-7 obtained in Synthesis Example 14 was used instead of the compound 1-6 obtained in Synthesis Example 13.

Example 5

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound 1-18 obtained in Synthesis Example 15 was used instead of the compound 1-6 obtained in Synthesis Example 13.

Example 6

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound 1-54 obtained in Synthesis Example 16 was used instead of the compound 1-6 obtained in Synthesis Example 13.

Example 7

Except that the compound 1-7 obtained in Synthesis Example 14 was used instead of the compound 1-6 obtained in Synthesis Example 13 and the compound 2-65 obtained in Synthesis Example 19 was used in place of the compound 2-1 obtained in Synthesis Example 17, The organic light emitting device was manufactured.

Comparative Example One

Except that a single host was used instead of the two-kind host of the compound 1-6 obtained in Synthesis Example 13 and the two kinds of the compound 2-1 obtained in Synthesis Example 17 in Synthesis Example 13, A light emitting device was fabricated.

Comparative Example 2

The same procedure as in Example 1 was repeated except for using the compound 1-6 obtained in Synthetic Example 13 and the compound 2-1 obtained in Synthetic Example 17 instead of the two kinds of the host, A light emitting device was fabricated.

Comparative Example 3

The procedure of Example 1 was repeated except that a single host was used instead of the two-kind host of the compound 1-6 obtained in Synthesis Example 13 and the two kinds of the compound 2-1 obtained in Synthesis Example 17, A light emitting device was fabricated.

Comparative Example 4

Comparative Example 5

The procedure of Example 1 was repeated except that a single host was used instead of the two-kind host of the compound 1-6 obtained in Synthetic Example 13 and the two kinds of the compound 2-1 obtained in Synthetic Example 17, A light emitting device was fabricated.

Comparative Example 6

Comparative Example 7

Comparative Example 8

The same procedure as in Example 1 was carried out except that a single host was used instead of the compound HO- 1 obtained in Synthetic Example 20 instead of the two kinds of the compounds 1-6 obtained in Synthetic Example 13 and 2-1 obtained in Synthetic Example 17, Respectively.

Comparative Example 9

An organic electroluminescent device was prepared in the same manner as in Example 1, except that a single host was used instead of the compound HO- 2 obtained in Synthetic Example 21 instead of the two-kind host of the compound 1-6 obtained in Synthetic Example 13 and the compound 2-1 obtained in Synthetic Example 17 Respectively.

Reference example One

Except that the compound HOST1 was used in place of the compound 1-6 obtained in Synthesis Example 13 and the compound HOST2 obtained in Synthetic Example 21 was used instead of the compound 2-1 obtained in Synthesis Example 17 to prepare an organic light emitting device Respectively.

Reference example 2

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound HOST2 obtained in Synthesis Example 21 was used instead of the compound 2-1 obtained in Synthesis Example 17.

Reference example 3

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound HOST1 obtained in Synthesis Example 20 was used instead of the compound 1-6 obtained in Synthesis Example 13.

evaluation

Emitting efficiency and lifetime characteristics of the organic light-emitting devices according to Examples 1 to 7, Comparative Examples 1 to 9, and Reference Examples 1 to 3 were evaluated.

The specific measurement method is as follows, and the results are shown in Table 1.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Life measurement

The initial luminance (cd / m2) was emitted at 6000 cd / m2 and the decrease in luminance over time was measured, and the time to decrease to 97% of the initial luminance was measured.

The first host Second host The driving voltage (V) color
(EL color) Luminous efficiency
(cd / A) Lifetime T97
(h) Example 1 1-6 2-1 3.5 green 70.0 650 Example 2 1-6 2-6 3.7 green 73.5 600 Example 3 1-6 2-65 3.4 green 79.5 550 Example 4 1-7 2-1 3.6 green 75.0 750 Example 5 1-18 2-1 3.7 green 64.5 600 Example 6 1-54 2-1 3.5 green 68.5 650 Example 7 1-7 2-65 3.4 green 80.0 750 Comparative Example 1 1-6 4.8 green 35.0 10 Comparative Example 2 1-7 5.2 green 30.0 50 Comparative Example 3 1-18 5.0 green 28.5 10 Comparative Example 4 1-54 4.7 green 33.0 10 Comparative Example 5 2-1 4.7 green 40.0 0 Comparative Example 6 2-6 4.9 green 43.5 0 Comparative Example 7 2-65 4.5 green 45.5 0 Comparative Example 8 HOST1 4.0 green 30.1 500 Comparative Example 9 HOST2 4.5 green 20.5 0 Reference Example 1 HOST1 HOST2 4.1 green 50.6 450 Reference Example 2 1-6 HOST2 3.9 green 48.1 350 Reference Example 3 HOST1 2-1 4.0 green 50.0 450

Referring to Table 1, the organic luminescent devices according to Examples 1 to 7 exhibited remarkably improved driving voltage, luminescent efficiency and lifetime characteristics as compared with the organic luminescent devices according to Comparative Examples 1 to 9 and Reference Examples 1 to 3 Can be confirmed. The organic luminescent device according to Examples 1 to 7 of combination of tricarbazole and di ET compound rather than the synergistic effect of the organic luminescent device according to Referential Examples 1 to 3 of the combination of bicarbazole (di HT compound) and mono ET compound remarkably improved the luminescence efficiency and lifetime It can be seen that the characteristics are good. In particular, it is considered that the synergistic effect is generated in the life span and the efficiency as the driving voltage is remarkably improved.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100, 200: Organic light emitting device
105: organic layer
110: anode
120: cathode
130: light emitting layer
140: auxiliary layer

Claims

At least one first compound represented by the following formula 1-I; And
At least one second compound represented by the following formula (II-II) or (II-III)
Wherein the organic photovoltaic device comprises:
[Chemical Formula 1-I]

In the above formula (I-I)
Z ¹ to Z ⁶ are each independently N or CR ^a ,
Z ¹ to Z ³ are each N,
At least two of Z ⁴ to Z ⁶ are N,
R ^a and R ^a1 to R ^a4 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, Lt; / RTI >
L ¹ is a C6 to C30 arylene group which is substituted or unsubstituted with a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group and a C6 to C30 aryl group,
Here, "substituted", except for L ¹ is at least one means that a hydrogen is substituted with deuterium, a halogen group, C1 to C30 alkyl groups, C6 to C30 aryl groups, C2 to C30 heterocyclic group or a cyano group,
[Chemical Formula 2-II] [Chemical Formula 2-III]

In the above Formulas 2-II and 2-III,
L ² and L ³ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group or a combination thereof,
R ⁴ to R ¹¹ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
Means that at least one hydrogen is substituted by deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heterocyclic group, or a cyano group.

delete

The method of claim 1,
R ^a and R ^a1 to R ^a4 are each independently hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, A substituted or unsubstituted phenanthrenyl group, or a substituted or unsubstituted pyridinyl group, each of which is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene group, Composition.

The method of claim 1,
L < ¹ >
A phenylene group substituted or unsubstituted with a C1 to C30 alkyl group or a C6 to C30 aryl group;
A C1 to C30 alkyl group, or a C6 to C30 aryl group;
A terphenylene group substituted or unsubstituted with a C1 to C30 alkyl group or a C6 to C30 aryl group; or
A C1 to C30 alkyl group or a C6 to C30 aryl group,
Compositions for organic optoelectronic devices.

The method of claim 1,
Wherein L < ^{1 >} is one selected from the linking groups listed in the following Group 3:
[Group 3]

In the above group 3, * is a connection point with a neighboring atom.

delete

The method of claim 1,
L ² and L ³ in the above formulas 2-II and 2-III are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, Lt; / RTI &
R ¹ to R ³ each independently represents a methyl group, an ethyl group, a propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, Wherein the organic photovoltaic device is an organic electroluminescent device.

The method of claim 1,
Wherein the second compound is represented by the following formula (II-a) or (II-a):
[Chemical Formula 2-IIa]

[Formula 2-Ilia]

In the above formulas 2-IIa and 2-IIIa,
L ² and L ³ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ³ are each independently a substituted or unsubstituted C6 to C30 aryl group,
R ⁴ to R ¹¹ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
Wherein " substituted " is as defined in claim 1.

The method of claim 1,
A composition for an organic optoelectronic device further comprising a phosphorescent dopant.

The anode and the cathode facing each other, and
At least one organic layer positioned between the anode and the cathode
/ RTI >
Wherein the organic layer comprises the composition for an organic optoelectronic device according to any one of claims 1, 4 to 6, and 8 to 10.

12. The method of claim 11,
Wherein the organic layer includes a light emitting layer,
Wherein the light emitting layer comprises the composition for the organic optoelectronic device.

12. A display device comprising the organic electroluminescent device according to claim 11.