KR101904605B1 - Compound having double spiro structure and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a double spiro compound and an organic light emitting device including the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a double spiro compound and an organic light-

The present application claims the benefit of Korean Patent Application No. 10-2015-0140446 filed on October 6, 2015, the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD The present invention relates to a double spiro compound and an organic light emitting device including the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

Development of new materials for such organic light emitting devices has been continuously required.

Korean Patent Publication No. 2000-0051826

The present invention provides a double spiro compound and an organic light emitting device including the same.

An embodiment of the present disclosure provides a double spiro-type compound represented by the following formula:

[Chemical Formula 1]

In Formula 1,

R1 to R5 are the same or different and each independently represents (L) p-A,

L is a direct bond or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, p is a number of from 0 to 4, and when p is 2 or more, L is the same or different from each other,

A is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; A substituted or unsubstituted amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted arylheteroarylamine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In addition, one embodiment of the present disclosure includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises the double spiro compound of Formula 1, to provide.

The compound described in this specification can be used as a material of an organic layer of an organic light emitting device. The compounds according to at least one embodiment of the present invention can improve the efficiency, lower driving voltage and / or lifetime characteristics in the organic light emitting device. In particular, the compounds described herein can be used as hole injecting, hole transporting, hole injecting and hole transporting, light emitting, electron transporting, or electron injecting materials.

1 shows an organic electronic device 10 according to an embodiment of the present invention.
2 shows an organic electronic device 11 according to another embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention provides a double spiro-type compound represented by the general formula (1).

Illustrative examples of such substituents are set forth below, but are not limited thereto.

및 ------는 연결되는 부위를 의미한다.In the present specification,

And ------ means the connected part.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; And a heterocyclic group, or a substituted or unsubstituted one in which at least two of the above-exemplified substituents are connected to each other. For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be substituted with nitrogen of the amide group by hydrogen, a straight chain, branched chain or cyclic alkyl group of 1 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRR'R ", wherein R, R 'and R" are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl and phenylsilyl groups. Do not.

In the present specification, the boron group may be represented by the formula of -BRR'R ", wherein R, R 'and R" are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group specifically 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, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the alkoxy group is not particularly limited, but preferably has 1 to 40 carbon atoms. According to one embodiment, the number of carbon atoms in the alkoxy group is from 1 to 10. According to another embodiment, the number of carbon atoms of the alkoxy group is from 1 to 6. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an isoamyloxy group and a hexyloxy group.

In the present specification, the number of carbon atoms of the amino group is not particularly limited, but is preferably 1 to 30. Specific examples of the amino group include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9- But are not limited to, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, and a triphenylamine group.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group containing at least two heterocyclic groups may contain a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, the arylheteroarylamine group means an aryl group and an amine group substituted with a heterocyclic group.

In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 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 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group, a fluorenyl group and a triphenylene group.

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

,

,

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, S, Si and Se. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, Benzothiophene group, benzofuranyl group, phenanthroline, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group. However, But is not limited thereto.

In the present specification, the description of the aforementioned heterocyclic group can be applied, except that the heteroaryl group is aromatic.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the arylphosphine group, the aralkyl group, the aralkylamine group, the aralkenyl group, the alkylaryl group, the arylamine group and the arylheteroarylamine group, The description of one aryl group may be applied.

In the present specification, the alkyl group in the alkylthio group, the alkylsulfoxy group, the aralkyl group, the aralkylamine group, the alkylaryl group and the alkylamine group can be applied to the alkyl group described above.

In the present specification, the heteroaryl group in the heteroaryl group, the heteroarylamine group and the arylheteroarylamine group can be applied to the description of the above-mentioned heterocyclic group.

In the present specification, the alkenyl group in the aralkenyl group can be applied to the description of the alkenyl group described above.

In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group.

In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group.

According to one embodiment of the present invention, the formula (1) may be represented by any one of the following formulas (2) to (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Formulas 2 to 6,

L1 to L5 are the same or different from each other and each independently represents a direct bond or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

A1 to A5 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; A substituted or unsubstituted amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted arylheteroarylamine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

t1 to t4 are the same or different from each other and independently an integer of 0 to 4, and when t1 to t4 are each 2 or more, the structures in parentheses are equal to or different from each other.

According to one embodiment of the present invention, L and L1 to L5 are a direct bond or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to one embodiment of the present invention, L and L 1 to L 5 are the same or different and each independently represents a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, A substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted naphthylene group, A substituted or unsubstituted perylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted perylene group,

According to one embodiment of the present invention, L and L1 to L5 are the same or different and each independently substituted or unsubstituted phenylene group.

According to one embodiment of the present invention, L and L1 to L5 are the same or different from each other, and each independently is a phenylene group.

According to one embodiment of the present invention, L and L 1 to L 5 are the same or different and each independently represents a substituted or unsubstituted divalent thiophene group, a substituted or unsubstituted divalent furan group, Substituted or unsubstituted divalent carbazole groups, substituted or unsubstituted divalent benzothiophene groups, substituted or unsubstituted divalent benzofuran groups, substituted or unsubstituted dibenzothiophen groups, substituted or unsubstituted divalent dibenzofurans A substituted or unsubstituted divalent pyridine group, a substituted or unsubstituted divalent bipyridine group, or a substituted or unsubstituted divalent triazine group.

According to one embodiment of the present invention, L and L1 to L5 are the same or different, and each independently is a divalent dibenzothiophene group, a divalent dibenzofurane group, or a divalent carbazole group substituted with a phenyl group .

According to one embodiment of the present disclosure, L and L1 to L5 may be the same or different from each other, and each independently may be any one of the following structures.

The structures include deuterium; A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amine group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; And a heterocyclic group, which may be substituted or unsubstituted.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; A substituted or unsubstituted amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted arylheteroarylamine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represent a substituted or unsubstituted amine group having 6 to 50 carbon atoms.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently an aryl group substituted or unsubstituted amine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted arylamine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, or a fluorenyl group Amine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and are each independently a heteroarylamine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, a fluorenyl group, a dibenzofurane group, A benzothiophene group, or a heteroarylamine group substituted or unsubstituted with a carbazole group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a substituted or unsubstituted phosphine oxide group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a phosphine oxide group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a phenyl group, or a phosphine oxide group substituted with a naphthyl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a substituted or unsubstituted heteroaryl group having 6 to 50 carbon atoms.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted thiophene group, a substituted or unsubstituted furan group, a substituted or unsubstituted benzothiophene A substituted or unsubstituted benzofuran group, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted dibenzofurane group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted benzocarbazole group, a substituted or unsubstituted benzothiophene group, Or a substituted or unsubstituted benzimidazole group, a substituted or unsubstituted phenanthroline, a substituted or unsubstituted pyridine group, a substituted or unsubstituted bipyridine group, a substituted or unsubstituted pyrimidine group, a substituted or unsubstituted pyrimidine group, A substituted triazine group, a substituted or unsubstituted quinolinyl group, or a substituted or unsubstituted quinazoline group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a pyridine group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, or a fluorenyl group Pyridine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a bipyridine group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, or a fluorenyl group Bipyridyl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently a pyrimidine group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, or a fluorenyl group Pyrimidine group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different triazine groups each independently substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, or a fluorenyl group It is triage.

According to one embodiment of the present invention, A and A 1 to A 5 are the same or different from each other, and each independently can be represented by any one of the following structural formulas [A-1] to [A-5].

 [A-1]

[A-2]

[A-3]

[A-4]

[A-5]

In the above structural formulas, R31 to R33 are the same or different from each other, and each independently represents hydrogen, deuterium, an alkyl group, an aryl group or a heterocyclic group.

In one embodiment of the present invention, the formula (1) is any one selected from the following compounds.

The double spiro-type compound according to one embodiment of the present specification can be produced by the following production method. Exemplary examples are described below in the preparation examples, but substituents can be added or removed as needed, and the position of the substituent can be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed.

Also, the present invention provides an organic light emitting device comprising the double spiro compound represented by the above formula (1).

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises the double spiro compound of Formula 1, to provide.

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is understood that it may include other components as well, without departing from the other components unless specifically stated otherwise.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, as a typical example of the organic electronic device of the present invention, the organic light emitting device has a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, . However, the structure of the organic electronic device is not limited thereto and may include a smaller number of organic layers.

In one embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes the double spiro compound.

In one embodiment of the present invention, the organic layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the double spiro compound.

In one embodiment of the present invention, the organic layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the double spiro compound.

In one embodiment of the present invention, the organic layer includes an electron blocking layer, and the electron blocking layer includes the double spiro type compound.

According to an embodiment of the present invention, the organic material layer includes a hole control layer, and the hole control layer includes the double spiro compound represented by the formula (1).

In another embodiment, the organic material layer includes a light emitting layer and an electron transporting layer, and the electron transporting layer includes the double spiro compound of the above formula (1).

In one embodiment of the present invention, the organic light emitting element is a hole injection layer, a hole transport layer, A light emitting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, and an electron blocking layer.

In one embodiment of the present invention, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; And at least one of the organic layers of two or more layers includes the double spiro compound. The light emitting layer may include a double spiro compound. In one embodiment of the present invention, the two or more organic layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports electrons and electrons, and a hole blocking layer.

In one embodiment of the present invention, the organic material layer includes two or more electron transporting layers, and at least one of the two or more electron transporting layers includes the double spiro-type compound. Specifically, in one embodiment of the present specification, the double spiro-type compound may be contained in one of the two or more electron transporting layers, and may be included in each of two or more electron transporting layers.

In addition, in the embodiment of the present specification, when the double spiro-type compound is included in each of the two or more electron transporting layers, the materials other than the above compounds may be the same or different.

In one embodiment of the present invention, the organic layer further includes a hole injection layer or a hole transport layer containing a compound containing an arylamino group, a carbazolyl group or a benzocarbazolyl group in addition to the organic compound layer containing the double spiro compound.

In another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.

When the organic material layer including the double spiro compound of Formula 1 is an electron transporting layer, the electron transporting layer may further include an n-type dopant. As the n-type dopant, those known in the art can be used, and for example, a metal or a metal complex can be used. According to an example, the electron transport layer containing the compound of Formula 1 may further include LiQ.

In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but the present invention is not limited thereto.

1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting diode according to an embodiment of the present invention, and may further include another organic layer.

2 shows a structure in which a first electrode 30, a hole injecting layer 60, a hole transporting layer 70, an electron blocking layer 80, a light emitting layer 40, an electron transporting layer 90, 100 and a second electrode 50 are sequentially laminated on a transparent substrate 100. In this case, 2 is an exemplary structure according to an embodiment of the present invention, and may further include another organic layer.

According to one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer includes a compound represented by the following formula 1-A.

[Chemical Formula 1-A]

In the above formula (1-A)

n1 is an integer of 1 or more,

Ar11 is a substituted or unsubstituted monovalent or more benzofluorene group; A substituted or unsubstituted monovalent or more fluoranthene group; A substituted or unsubstituted monovalent or higher valent phenylene group; Or a substituted or unsubstituted monovalent or more chrysene group,

L11 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Ar11 and Ar12 are the same or different and each independently represents a substituted or unsubstituted aryl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted arylalkyl group; Or a substituted or unsubstituted heteroaryl group or may be bonded to each other to form a substituted or unsubstituted ring,

When n1 is 2 or more, the structures in parentheses two or more are the same or different from each other.

According to one embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes the compound represented by the formula 1-A as a dopant in the light emitting layer.

According to one embodiment of the present disclosure, L11 is a direct bond.

According to one embodiment of the present disclosure, n1 is 2.

In one embodiment of the present invention, Ar11 is a divalent pyylene group substituted or unsubstituted with a deuterium, a methyl group, an ethyl group or a tert-butyl group; Or a divalent cyclic group substituted or unsubstituted with a deuterium, a methyl group, an ethyl group or a tert-butyl group

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and each independently an aryl group substituted or unsubstituted with a silyl group substituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group or an alkyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are aryl groups which are the same or different and are each independently substituted or unsubstituted with a silyl group substituted with an alkyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are aryl groups which are the same or different and are each independently substituted or unsubstituted with trimethylsilyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different from each other and are each independently a phenyl group substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group or a trimethylsilyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and each independently a biphenyl apparatus substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group or a trimethylsilyl group.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and are each independently a terphenyl group substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group or a trimethylsilyl group.

According to one embodiment of the present invention, A12 and Ar13 are the same or different and are each independently a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms.

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and each independently represents a methyl group, an ethyl group, a tert-butyl group, a nitrile group, a silyl group substituted with an alkyl group, Lt; / RTI >

According to one embodiment of the present invention, Ar12 and Ar13 are the same or different and are each independently a dibenzofurane group substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group, a trimethylsilyl group, to be.

According to one embodiment of the present disclosure, the above formula (I-A) is selected from the following compounds.

According to one embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following formula (2-A).

[Chemical Formula 2-A]

In the above formula (2-A)

Ar21 and Ar22 are the same or different and each independently represents a substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group,

G1 to G8 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group.

According to one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound represented by Formula 2-A as a host of the light-emitting layer.

According to one embodiment of the present invention, Ar21 and Ar22 are the same or different and each independently a substituted or unsubstituted polycyclic aryl group.

According to one embodiment of the present invention, Ar21 and Ar22 are the same or different and each independently a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.

According to one embodiment of the present invention, Ar21 and Ar22 are the same or different and each independently a substituted or unsubstituted naphthyl group.

According to one embodiment of the present invention, Ar 21 and Ar 22 are the same or different and each independently a substituted or unsubstituted 1-naphthyl group.

According to one embodiment of the present invention, Ar21 and Ar22 are 1-naphthyl groups.

According to one embodiment of the present invention, G1 to G8 are hydrogen.

According to one embodiment of the present invention, the formula (2-A) may be selected from the following compounds.

According to an embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound represented by the formula 1-A as a dopant of the light emitting layer, .

The organic light-emitting device of the present invention can be produced by materials and methods known in the art, except that one or more of the organic layers include the compound of the present invention, i.e., the double spiro-type compound.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

 The organic light emitting device of the present invention can be produced by materials and methods known in the art, except that one or more of the organic layers include the compound, i.e., the double spiro compound represented by the above formula (1).

For example, the organic light emitting device of the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the double spiro compound of Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present invention, 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 a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode 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 oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The hole-adjusting layer effectively receives holes from the hole-transporting layer and regulates the hole mobility to control the amount of holes transferred to the light-emitting layer. In addition, it can simultaneously serve as an electron barrier to prevent electrons supplied from the light emitting layer from migrating to the hole transporting layer. This can increase the luminous efficiency by maximizing the balance of holes and electrons in the light emitting layer, improve the lifetime of the device through the electron stability of the hole controlling layer, and materials known in the art can be used.

The electron blocking layer is a layer which can prevent the holes injected from the hole injection layer from entering the electron injection layer through the light emitting layer to improve the lifetime and efficiency of the device. If necessary, And may be formed in an appropriate portion between the injection layers.

The light emitting material of the light emitting layer is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Do. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

The organic light emitting device according to the present invention may be of a top emission type, a back emission type, or a both-side emission type, depending on the material used.

In one embodiment of the present invention, the double spiro compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The double spiro compound according to the present invention can act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors and the like.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

< Example >

< Synthetic example  1 > A-1 and A- 2 of  synthesis

(1) Synthesis of A-1

Al (20 g, 64.98 mmol) and CuI (2.48 g, 20 mol%) were added to DMSO (300 ml) and the mixture was heated and stirred at 120 ° C for 48 hours. After the reaction mixture was cooled to room temperature, the reaction mixture was extracted with ethyl acetate and water. After the solvent was removed, the reaction mixture was subjected to column chromatography with hexane to obtain Compound A-1 (15.89 g, yield 80%).

MS [M + H] &lt; ⁺ &gt; = 306.06

(2) Synthesis of A-2

Compound A-2 was synthesized by the same method except for using A2 instead of A1 in the synthesis of A-1 above

MS [M + H] &lt; ⁺ &gt; = 306.06

< Synthetic example  2> Synthesis of B-1, B-2, C-1 and C-2

 (1) Synthesis of B-1

(15 g, 37.75 mmol) was dissolved in THF (250 ml), the temperature was lowered to -78 ° C, and 2.5 M n-BuLi (21.1 ml) was added thereto. After 30 minutes, the above A-1 (11.54 g, 37.75 mmol) was added thereto, and the mixture was stirred for 1 hour. Then, 1N HCl (300 ml) was added thereto, and the mixture was stirred for 30 minutes. Then, the mixture was separated, and the solvent was removed. The residue was recrystallized from ethyl acetate and hexane to obtain Compound B-1 (17.67 g, yield 75%).

MS [M + H] &lt; ⁺ &gt; = 624.20

(2) Synthesis of B-2

Compound B-2 was synthesized by the same method except that A-2 was used instead of A-1 in the synthesis of B-1 above

MS [M + H] &lt; ⁺ &gt; = 624.20

(3) Synthesis of C-1

The above B-1 (15 g, 24.03 mmol) was added to acetic acid (250 ml), 10 ml of trifluoroacetic acid was added dropwise, and the mixture was refluxed with stirring. The temperature was lowered to room temperature and neutralized with water. The filtered solid was recrystallized from ethyl acetate to obtain Compound C-1 (11.65 g, yield 80%).

MS [M + H] &lt; ⁺ &gt; = 606.19

(4) Synthesis of C-2

Compound C-2 was prepared by the same method except for using B-2 instead of B-1 in the synthesis of C-1

MS [M + H] &lt; ⁺ &gt; = 606.19

< Synthetic example  3 > D-1 and D- 2 of  synthesis

(1) Synthesis of D-1

The above C-1 (20 g, 46.1 mmol), bis (pinacolato) diboron (mmol) and potassium acetate (19.1 g, 138 mmol) were mixed in a nitrogen atmosphere, and the mixture was heated to 200 ml with dioxane. Bis (dibenzylidineacetone) palladium (150 mg, 0.92 mmol) and tricyclohexylphosphine (100 mg, 1.84 mmol) were added under reflux and the mixture was heated with stirring for 10 hours. After completion of the reaction, the temperature was lowered to room temperature and then filtered. Water was poured into the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from chloroform to obtain Compound D-1 (20 g, 90%).

MS [M + H] &lt; ⁺ &gt; = 698.32

(2) Synthesis of D-2

Compound D-2 was synthesized by the same method except that C-2 was used instead of C-1 in the synthesis of D-1

MS [M + H] &lt; ⁺ &gt; = 698.32

< Synthetic example  4> E- 1 of  synthesis

Aniline (3.2 g, 33.65 mmol) and sodium-t-butoxide (4.12 g, 42.88 mmol) were added to xylene and the mixture was heated under stirring, (Tri-t-butylphosphine)] palladium (168 mg, 1 mmol%) was added thereto. After the reaction mixture was cooled to room temperature, the reaction mixture was recrystallized from tetrahydrofuran and ethyl acetate to obtain 15.29 g (yield: 70%) of compound E-1.

MS [M + H] &lt; ⁺ &gt; = 663.27

< Manufacturing example  1> Synthesis of Compound 1

(8.26 g, 33.65 mmol) and sodium-t-butoxide (4.4 g, 46.2 mmol) were added to a solution of the above C-1 (20 g, 32.99 mmol) The mixture was heated and stirred under reflux, and [bis (tri-t-butylphosphine)] palladium (336 mg, 2 mmol%) was added thereto. After the reaction mixture was cooled to room temperature, the reaction mixture was recrystallized from tetrahydrofuran and ethyl acetate to obtain Compound 1 (17.48 g, yield 65%).

MS [M + H] &lt; ⁺ &gt; = 815.33

< Manufacturing example  2> Synthesis of Compound 2

Except that 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine was used in place of N-phenyl- (1,1'- To give Compound 2

MS [M + H] &lt; ⁺ &gt; = 855.37

< Manufacturing example  3> Synthesis of Compound 3

Compound 3 was prepared by the same method except that N-phenyl naphthalene-1-amine was used instead of N-phenyl- (1,1'-biphenyl) -4-amine in the synthesis of Compound 1

MS [M + H] &lt; ⁺ &gt; = 789.32

< Manufacturing example  4> Synthesis of Compound 4

C-2 was used instead of C-1 in the synthesis of Compound 1, and N - ([1,1'-biphenyl] -4-yl) - (1,1'-biphenyl) -2-amine, the compound 4 was prepared

MS [M + H] &lt; ⁺ &gt; = 891.37

< Manufacturing example  5> Synthesis of Compound 5

E-1 was used instead of the compound C-1 in the synthesis of the compound 1, and 3-bromo-9-phenyl-9H-carbazole was used in place of N-phenyl- (1,1'-biphenyl) Was synthesized in the same manner as above to give Compound 5

MS [M + H] &lt; ⁺ &gt; = 904.36

< Manufacturing example  6> Synthesis of Compound 6

D-1 (20 g, 28.7 mmol) and 2- (4-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (9.95 g, 28.95 mmol) were placed in THF (300 ml) Potassium carbonate aqueous solution (100 ml) was added, tetrakis triphenylphosphinopalladium (664 mg, 2 mol%) was added, and the mixture was heated and stirred for 10 hours. After the temperature was lowered to room temperature and the reaction was terminated, the layers were separated. Recrystallization from tetrahydrofuran and ethyl acetate gave Compound 6 (16.4 g, 18.7 mmol).

MS [M + H] &lt; ⁺ &gt; = 879.34

< Manufacturing example  7> Synthesis of Compound 7

In the synthesis of the compound 6, 2 - ([1,1'-diphenyl] -4-yl) -4 - (3-chlorophenyl) -6-phenyl-1,3,5-triazine, the compound 7 was prepared

MS [M + H] &lt; ⁺ &gt; = 955.37

< Manufacturing example  8> Synthesis of Compound 8

D-2 was used instead of D-1 in the synthesis of Compound 6, and 4- (4-chlorophenyl) -2 (4-chlorophenyl) -4,6- , 6-diphenylpyrimidine was used to synthesize Compound 8

MS [M + H] &lt; ⁺ &gt; = 878.35

< Manufacturing example  9> Synthesis of Compound 9

(4-chlorophenyl) -2,6-diphenylpyrimidine in place of 4- (4-chlorophenyl) -2,6- -6-phenylpyrimidine, the compound 9 was prepared

MS [M + H] &lt; ⁺ &gt; = 954.38

< Experimental Example  1-1>

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) with a thickness of 1,000 Å was immersed in distilled water and washed with ultrasonic waves. The detergent was a product of Fischer Co. and the distilled water was distilled water secondarily filtered with a filter manufactured by Millipore Co. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On this ITO transparent electrode, hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer.

[LINE]

The following compound 1 (900 Å) was vacuum-deposited on the hole injection layer to form a hole transport layer.

[Compound 1]

Subsequently, HT2 was vacuum deposited on the hole transport layer to a thickness of 100 ANGSTROM to form a hole control layer.

[HT2]

Subsequently, the following host H1 and dopant D1 (25: 1) were vacuum-deposited to a thickness of 300 Å to form a light emitting layer.

[H1]

[D1]

Subsequently, the following E1 (300 ANGSTROM) was sequentially vacuum-deposited by electron injection and transport layer.

 [E1]

Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

< Experimental Example  1-2>

An organic light emitting device was fabricated in the same manner as in Example 1-1, except that Compound 2 was used instead of Compound 1 as the hole transport layer.

< Experimental Example  1-3>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of Compound 1 as the hole transport layer.

< Experimental Example  1-4>

An organic light emitting device was fabricated in the same manner as in Example 1-1, except that Compound 4 was used instead of Compound 1 as the hole transport layer.

< Experimental Example  1-5>

An organic light emitting device was fabricated in the same manner as in Example 1-1, except that Compound 5 was used instead of Compound 1 as the hole transport layer.

< Comparative Example  1-1>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that HT1 was used instead of Compound 1 as the hole transport layer.

[HT1]

The device evaluation results of the organic luminescent devices of Examples 1-1 to 1-5 and Comparative Example 1-1 are shown in Table 1 below.

Experimental Example
50 mA / cm 2 compound
(Hole transport layer) Voltage (V) Current efficiency (cd / A) Comparative Example 1-1 HT1 4.12 5.35 Example 1-1 Compound 1 3.67 5.70 Examples 1-2 Compound 2 3.56 5.75 Example 1-3 Compound 3 3.59 5.88 Examples 1-4 Compound 4 3.66 5.56 Examples 1-5 Compound 5 3.71 5.59

As can be seen from the above Table 1, in the case of the organic light-emitting device manufactured by using the compounds 1 to 5 of the present invention as the hole transporting layer material, the characteristics of the low voltage and the high efficiency are shown compared with the benzidine type material of Comparative Example 1-1 .

< Experimental Example  2-1>

Hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited on the ITO transparent electrode prepared in Experimental Example 1-1 to a thickness of 500 Å to form a hole injection layer. Subsequently, HT1 (900 Å) was vacuum deposited on the hole injection layer to form a hole transport layer, and Compound 4 was vacuum deposited on the hole transport layer to a thickness of 100 Å to form a hole control layer. Subsequently, the host H1 and the dopant D1 compound (25: 1) were vacuum-deposited to a thickness of 300 Å to form a light emitting layer. Then, E1 (300 Å) was sequentially vacuum deposited by electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

< Experimental Example  2-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 2-1 except that Compound 5 was used instead of Compound 4 as the hole control layer.

< Comparative Example  2-1>

An organic light emitting device was fabricated in the same manner as in Experimental Example 2-1, except that HT2 was used instead of Compound 4 as the hole-controlling layer.

[HT2]

The device evaluation results of the organic light emitting devices of Examples 2-1 and 2-2 and Comparative Example 2-1 are shown in Table 2 below.

Experimental Example
50 mA / cm 2 compound
(Hole-adjusting layer) Voltage (V) Current efficiency (cd / A) Comparative Example 2-1 HT2 4.02 5.11 Experimental Example 2-1 Compound 4 3.78 5.45 EXPERIMENTAL EXAMPLE 2-2 Compound 5 3.77 5.55

As can be seen from Table 2, in the case of the organic light-emitting device manufactured by using Compound 4 and 5 of the present invention as the hole-adjusting layer material, the characteristics of low voltage and high efficiency . &Lt; / RTI &gt;

In particular, the double spiro compound represented by formula (1) according to one embodiment of the present invention has a relatively higher triplet energy, thereby improving the device performance.

The spiro-type compound represented by Formula 1 according to one embodiment of the present invention can function as a hole transporting and hole-regulating function in an organic electronic device including an organic light emitting device, and the organic light emitting device according to the present invention can control efficiency, And it shows excellent characteristics in terms of stability.

< Experimental Example  3-1>

Hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited on the ITO transparent electrode prepared in Experimental Example 1-1 to form a hole injection layer. HT1 (900 Å) was vacuum deposited as a hole transport layer thereon, and then HT2 was vacuum deposited on the hole transport layer to a film thickness of 100 Å to form a hole control layer. Subsequently, a host H1 and a dopant D1 compound (25: 1) were vacuum deposited as a light emitting layer to a thickness of 300 Å.

Compound 6 and [LiQ] (Lithiumquinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 350 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode.

< Experimental Example  3-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1, except that Compound 7 was used instead of Compound 6 as the electron transporting layer.

< Experimental Example  3-3>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1, except that Compound 8 was used instead of Compound 6 as the electron transporting layer.

< Experimental Example  3-4>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1, except that Compound 9 was used instead of Compound 6 as the electron transporting layer.

< Experimental Example  3-5>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1 except that Compound 6 was used alone as an electron transporting layer and Compound 6 was used instead of Liq.

< Comparative Example  3-1>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1, except that E1 was used instead of Compound 6 as the electron transporting layer.

< Comparative Example  3-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3-1, except that E1 alone was used instead of Compound 6 and Liq as an electron transporting layer.

The device evaluation results of the organic light emitting devices of Examples 3-1 to 3-5 and Comparative Examples 3-1 and 3-2 are shown in Table 3 below. The driving voltage and the luminous efficiency of the organic light emitting device were measured at a current density of 10 mA / cm ² and a time (T ₉₀ ) of 90% of the initial luminance at a current density of 20 mA / cm ² was measured.

Experimental Example
10mA / ㎠ compound
(Electron transport layer) Voltage (V) Current efficiency
(cd / A) Life span (h)
T ₉₀ at 20 mA / cm ² Comparative Example 3-1 E1 + LiQ 4.11 5.32 90 Comparative Example 3-2 E1 (stand alone) 4.32 5.00 101 Experimental Example 3-1 Compound 6 + LiQ 3.88 5.32 180 Experimental Example 3-2 Compound 7 + LiQ 3.78 5.35 150 Experimental Example 3-3 Compound 8 + LiQ 3.59 5.88 162 Experimental Example 3-4 Compound 9 + LiQ 3.66 5.91 172 Experimental Example 3-5 Compound 6 (alone) 3.91 5.23 169

As shown in Table 3, the organic light emitting device manufactured using the compound of the present invention as an electron transport layer material has excellent thermal stability, and has a deep HOMO level of 5.7 eV or more, high triplet energy (ET), and hole stability And exhibits excellent properties.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. .

10, 11: Organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: Hole injection layer
70: hole transport layer
80: electron blocking layer
90: electron transport layer
100: electron injection layer

Claims (18)

A double spiro-type compound represented by any one of the following formulas (3) to (6):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 3 to 6,
L5 is a direct bond, t5 is 0,
A5 is an aryl group,
L1 to L4 are the same or different from each other and are each independently a direct bond; Or an arylene group, t1 to t4 are each 0 or 1,
A1 to A4 are the same or different and each is a pyrimidine group substituted with at least one of an alkylaryl group and an aryl group; A triazine group substituted by at least one of an alkylaryl group and an aryl group; Or one selected from the following structural formula [A-3].
[A-3]

delete The double spiro-type compound according to claim 1, wherein any one of the above-mentioned formulas (3) to (6) is any one selected from the following compounds:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the double spiro compound of claim 1 or 3, . 5. The organic light emitting device according to claim 4, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic material layer comprises a hole transporting layer, and the hole transporting layer comprises the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic material layer includes a hole injection layer, and the hole injection layer comprises the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic layer includes an electron blocking layer, and the electron blocking layer includes the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic layer includes an electron injection layer or an electron transport layer, and the electron transport layer or the electron injection layer comprises the double spiro compound. [4] The organic light emitting device according to claim 4, wherein the organic layer includes a layer simultaneously injecting holes and transporting holes, and the layer simultaneously injecting holes and transporting holes comprises the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic material layer includes a layer that simultaneously performs electron injection and electron transport, and the layer that simultaneously performs electron injection and electron transport includes the double spiro compound. 5. The organic light emitting device according to claim 4, wherein the organic layer includes a hole adjusting layer, and the hole adjusting layer comprises the double spiro compound. 5. The organic electroluminescent device of claim 4, wherein the organic light emitting device comprises a light emitting layer, a hole injecting layer, and a hole transporting layer. An electron injection layer, an electron transport layer, an electron blocking layer, and a hole control layer. The method of claim 4,
Wherein the organic layer comprises a light-emitting layer, and the light-emitting layer comprises a compound represented by the following Formula 1-A:
[Chemical Formula 1-A]

In the above formula (1-A)
n1 is 2, the structures in parentheses are the same or different from each other,
Ar11 is a divalent pyrene group,
L11 is a direct bond,
Ar12 and Ar13 are the same or different and each independently an aryl group substituted or unsubstituted with a silyl group substituted with an alkyl group. delete The method of claim 4,
Wherein the organic layer includes a light emitting layer, and the light emitting layer comprises a compound represented by the following Formula 2-A:
[Chemical Formula 2-A]

In the above formula (2-A)
Ar21 and Ar22 are each a 1-naphthyl group,
G1 to G8 are each hydrogen. delete 15. The method of claim 14,
Wherein the light emitting layer comprises a compound represented by the following Formula 2-A:
[Chemical Formula 2-A]

In the above formula (2-A)
Ar21 and Ar22 are each a 1-naphthyl group,
G1 to G8 are each hydrogen.

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