KR20230081837A - Spiro compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a novel spiro compound and an organic light emitting device including the same. The spiro compound according to the present invention contains indole at a specific position centered on 9,9'-spirobifluorene. It has a polycyclic heterocyclic structure in which a multicyclic skeleton in which indole or benzofuran is fused is used as a mother core and at least one substituent other than hydrogen is introduced, and can be used as an organic material layer material of an organic light emitting device.

Description

Spiro compound and an organic light emitting device including the same {SPIRO COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to a spiro compound having a novel structure and an organic light emitting device including the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electronic device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer between the anode. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic electronic device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and the injected holes and electrons meet to form excitons, and these excitons form the bottom again. It will light up when falling. Such an organic electronic device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.

Materials used as organic layers in organic electronic devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. In addition, the light emitting material can be classified into a high molecular weight type and a low molecular weight type according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. can In addition, light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color.

In particular, several studies are being conducted on organic materials inserted into a hole transport layer or a buffer layer for excellent lifespan characteristics of organic electronic devices. A hole injection layer material having high uniformity and low crystallinity upon formation is required.

It delays penetration and diffusion of metal oxide from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, and has stable characteristics against Joule heating generated during device operation, that is, high glass transition temperature. It is necessary to develop a hole injection layer material having In addition, it has been reported that the low glass transition temperature of the material for the hole transport layer greatly affects the lifetime of the device according to the property that the uniformity of the surface of the thin film collapses during device operation. In addition, since the deposition method is the mainstream in the formation of OLED devices, there is a need for a material with strong heat resistance that can withstand such a deposition method for a long time.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. Therefore, color purity increases and energy transfer A host/dopant system may be used as a light emitting material in order to increase luminous efficiency. The principle is that when a small amount of a dopant having a smaller energy band gap than the host forming the light emitting layer is mixed into the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

In order to fully exhibit the excellent characteristics of the above-mentioned organic electronic device, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. are supported by stable and efficient materials. Although this should be preceded, stable and efficient organic material layer materials for organic electric devices have not yet been sufficiently developed, and therefore, development of new materials is continuously required.

KR 10-2011-0100762 A KR 10-2011-0068330 A

An object of the present invention is to provide a spiro compound having a novel structure that can be used as a material for an organic layer of an organic light emitting device.

In addition, an object of the present invention is to provide an organic light emitting device including the spiro compound as an organic material layer material.

The present invention relates to a spiro compound having a novel structure and an organic light emitting device including the same. It has a polycyclic heterocyclic structure having a multicyclic skeleton in which indole or benzofuran is fused as a mother core and introducing at least one substituent other than hydrogen, and can be used as an organic material layer material of an organic light emitting device.

The present invention provides a spiro compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is N-Ar or O;

Ar is C6-C60 aryl or C2-C60 heteroaryl;

R ¹ and R ² are each independently C1-C60 alkyl, C1-C60 alkoxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C2-C60 alkenyl, C2-C60 alkynyl, C6-C60 aryl, C2 -C60 heteroaryl, C6-C60 aryloxy or -L ¹ -Ar ¹ ;

L ¹ is C6-C60 arylene or C2-C60 heteroarylene;

Ar ¹ is C6-C60 aryl or C2-C60 heteroaryl;

aryl and heteroaryl of Ar above, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl and aryloxy of R ¹ and R ² , arylene and heteroarylene of L ¹ , Ar Aryl and heteroaryl of ¹ are C1-C60 Alkyl, HaloC1-C60 Alkyl, Deuterium, Halogen, Cyano, C3-C60 Cycloalkyl, C2-C60 Heterocycloalkyl, C1-C60 Alkoxy, HaloC1-C60 Alkoxy, C6 -C60 Aryl, C6-C60 Aryloxy, C6-C60 ArylC1-C60 Alkyl, C1-C60 AlkylC6-C60 Aryl, C2-C60 Heteroaryl, -P(=O)R ^a R ^b , -SiR ^c R ^d R ^e , may be further substituted with one or more selected from the group consisting of nitro and hydroxy;

R ^a and R ^b are each independently C1-C60 alkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl or C2-C60 heteroaryl;

R ^c to R ^e are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C2-C60 heteroaryl;

a is an integer from 0 to 4, b is an integer from 0 to 2, provided that a and b are not 0 at the same time;

The heteroaryl, heterocycloalkyl and heteroarylene include one or more heteroatoms selected from N, O, S and Se.

In addition, the present invention provides an organic light emitting device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein at least one layer of the organic material layer includes the spiro compound represented by Chemical Formula 1. do.

The spiro compound according to the present invention has a multi-ring skeleton in which indole or benzofuran is fused at a specific position centered on 9,9'-spirobifluorene as a mother nucleus. It has a polycyclic heterocyclic structure in which at least one substituent other than hydrogen is introduced, and can be used as an organic material layer material of an organic light emitting device. The spiro compound may serve as a light emitting material, a hole injection material, a hole transport material, a light emitting material, an electron transport material, or an electron injection material in an organic light emitting device.

Due to its structural specificity, the spiro compound according to the present invention can be employed as an organic material layer material such as a light emitting material, a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material. It has mobility, so it has high efficiency and low driving voltage at the same time, and life characteristics can also be surprisingly improved.

That is, the spiro compound according to the present invention has excellent electron mobility due to its structural specificity, thereby improving the current characteristics of the device and strengthening the driving voltage, thereby inducing an increase in power efficiency to manufacture an organic light emitting device with improved power consumption. .

The present invention is detailed below, but unless there is another definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and in the following description Descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter of the invention will be omitted.

Throughout this specification, unless the context requires otherwise, the terms "comprise" and "comprising" include a given step or component, or group of steps or components, but any other step or component, or It is to be understood that steps or groups of components are not excluded.

In this specification, “substituent”, “radical”, “group”, “moiety”, and “fragment” may be used interchangeably.

In the present specification, “C _A -C _B ” means “a number of carbon atoms greater than or equal to A and less than or equal to B”.

In the present specification, "alkyl", "alkoxy" and other substituents including "alkyl" moieties include both straight-chain and branched forms.

In the present specification, "alkyl" includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl may be 1 to 60, specifically 1 to 30, more specifically, 1 to 20, preferably 1 to 10.

In the present specification, "alkenyl" includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of alkenyl may be 2 to 60, specifically 2 to 30, more specifically, 2 to 20, preferably 2 to 10.

In the present specification, "alkynyl" includes straight or branched chains having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of alkynyl may be 2 to 60, specifically 2 to 30, more specifically, 2 to 20, preferably 2 to 10.

In the present specification, "cycloalkyl" includes monocyclic or polycyclic groups having 3 to 60 carbon atoms, and may be further substituted with other substituents. Here, polycyclic means a group in which cycloalkyl is directly connected or condensed with another ring group. Here, the other ring group may be cycloalkyl, but other types of ring groups such as heterocycloalkyl, aryl, heterocyclic, etc. may also be used. Cycloalkyl may have 3 to 60 carbon atoms, specifically 3 to 30, and more specifically 5 to 20 carbon atoms.

In the present specification, "heterocycloalkyl" includes at least one selected from N, O, S, and Se as a heteroatom, and includes monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may be further substituted by other substituents. can Here, polycyclic means a group in which heterocycloalkyl is directly linked or condensed with another ring group. Here, the other ring group may be heterocycloalkyl, but other types of ring groups such as cycloalkyl, aryl, heterocyclic, etc. may also be used. Heterocycloalkyl may have 2 to 60, specifically 2 to 30, and more specifically 3 to 20 carbon atoms.

In the present specification, "aryl" is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted with other substituents. Here, the polycyclic means a group in which aryl is directly linked or condensed with another ring group. Here, the other ring group may be aryl, but may also be other types of ring groups, such as cycloalkyl, heterocycloalkyl, heterocyclic, and the like. The number of carbon atoms of aryl may be 6 to 60, specifically 6 to 30, and more specifically 6 to 20. Specific examples of aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, Fluorenyl, indenyl, acenaphthylenyl, fluorenyl, etc., or condensed rings thereof, but are not limited thereto.

In the present specification, "heterocyclic group" includes at least one selected from N, O, S, and Se as a hetero atom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by another substituent. can Heteroaryl is included in the scope of a heterocyclic group and is a heteroaromatic ring group. Here, the polycyclic means a group in which a heterocyclic group is directly connected or condensed with another cyclic group. Here, the other ring group may be a heterocyclic group, but may also be another type of ring group, such as cycloalkyl, heterocycloalkyl, aryl, and the like. The number of carbon atoms in the heterocyclic group may be 2 to 60, specifically 2 to 30, and more specifically 3 to 20. Specific examples of the heterocyclic group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Furazanil, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranil, thiopyranil, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, iso Quinolyl, quinazolinyl, isoquinazolinyl, naphthyridyl, acridinyl, phenanthridinyl, imidazopyridinyl, diazanaphthalenyl, triazinden, indolyl, indolizinyl, benzothiazolyl, Benzoxazolyl, benzoimidazolyl, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl, etc., or condensed rings thereof, but limited thereto it is not going to be

As used herein, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, and Se as an aromatic ring skeletal atom, and the remaining aromatic ring skeletal atoms being carbon. 6-membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, the heteroaryl in the present invention includes a form in which one or more heteroaryls are connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. Monocyclic heteroaryl of; Benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, quinolyl, iso polycyclic heteroaryls such as quinolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, and benzocarbazolyl; and the like, but are not limited thereto.

The present invention relates to a spiro compound and an organic light emitting device including the same, and more particularly, the spiro compound according to the present invention may be represented by Formula 1 below:

[Formula 1]

In Formula 1,

X is N-Ar or O;

Ar is C6-C60 aryl or C2-C60 heteroaryl;

R ¹ and R ² are each independently C1-C60 alkyl, C1-C60 alkoxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C2-C60 alkenyl, C2-C60 alkynyl, C6-C60 aryl, C2 -C60 heteroaryl, C6-C60 aryloxy or -L ¹ -Ar ¹ ;

L ¹ is C6-C60 arylene or C2-C60 heteroarylene;

Ar ¹ is C6-C60 aryl or C2-C60 heteroaryl;

aryl and heteroaryl of Ar above, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl and aryloxy of R ¹ and R ² , arylene and heteroarylene of L ¹ , Ar Aryl and heteroaryl of ¹ are C1-C60 Alkyl, HaloC1-C60 Alkyl, Deuterium, Halogen, Cyano, C3-C60 Cycloalkyl, C2-C60 Heterocycloalkyl, C1-C60 Alkoxy, HaloC1-C60 Alkoxy, C6 -C60 Aryl, C6-C60 Aryloxy, C6-C60 ArylC1-C60 Alkyl, C1-C60 AlkylC6-C60 Aryl, C2-C60 Heteroaryl, -P(=O)R ^a R ^b , -SiR ^c R ^d R ^e , may be further substituted with one or more selected from the group consisting of nitro and hydroxy;

R ^a and R ^b are each independently C1-C60 alkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl or C2-C60 heteroaryl;

R ^c to R ^e are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C2-C60 heteroaryl;

a is an integer from 0 to 4, b is an integer from 0 to 2, provided that a and b are not 0 at the same time;

The heteroaryl, heterocycloalkyl and heteroarylene include one or more heteroatoms selected from N, O, S and Se.

Specifically, the spiro compound of Chemical Formula 1 is a multi-ring skeleton in which indole or benzofuran is fused at a specific position centered on 9,9'-spirobifluorene. It has a polycyclic heterocyclic structure in which at least one substituent other than hydrogen is introduced, and can be usefully used as an organic material layer material of an organic light emitting device.

The spiro compound of Chemical Formula 1 can lower driving voltage, improve luminous efficiency and color purity, and exhibit surprisingly improved lifespan characteristics when employed as an organic material layer of an organic light emitting device, particularly a hole transport material of an organic light emitting device, due to the above structural characteristics. there is.

In one embodiment, Ar is C6-C30 aryl or C2-C30 heteroaryl; R ¹ and R ² are each independently C1-C30 alkyl, C6-C30 aryl, C2-C30 heteroaryl or -L ¹ -Ar ¹ ; L ¹ is C6-C30 arylene or C2-C30 heteroarylene; Ar ¹ is C6-C30 aryl or C2-C30 heteroaryl; Aryl and heteroaryl of Ar, alkyl, aryl and heteroaryl of R ¹ and R ² , arylene and heteroarylene of L ¹ , aryl and heteroaryl of Ar ¹ are C1-C30 alkyl, haloC1-C30 alkyl, Deuterium, halogen, cyano, C1-C30 alkoxy, haloC1-C30 alkoxy, C6-C30 aryl, C6-C30 aryloxy, C6-C30 arylC1-C30 alkyl, C1-C30 alkylC6-C30 aryl, C2-C30 may be further substituted with one or more selected from the group consisting of heteroaryl, -P(=0)R ^a R ^b , -SiR ^c R ^d R ^e , nitro and hydroxy; R ^a and R ^b are each independently C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl; R ^c is C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl; R ^d and R ^e are each independently hydrogen, C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl; a and b are each independently an integer of 0 to 2, provided that 1≤a+b≤4 may be satisfied.

In one embodiment, in order to implement more improved device characteristics of the spiro compound, the a+b may be an integer of 1 or 2.

In one embodiment, the a+b may be an integer of 1.

In one embodiment, a may be an integer of 1 and b may be an integer of 0.

In one embodiment, a may be an integer of 0 and b may be an integer of 1.

In one embodiment, the spiro compound may be represented by Formula 2 or 3:

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

X is N-Ar or O;

Ar is C6-C20 aryl;

R ¹ and R ² are each independently C1-C20 alkyl, C6-C20 aryl, C2-C20 heteroaryl or -L ¹ -Ar ¹ ;

L ¹ is C6-C20 arylene or C2-C20 heteroarylene;

Ar ¹ is C6-C20 aryl or C2-C20 heteroaryl;

Aryl of Ar, alkyl, aryl and heteroaryl of R ¹ and R ² , arylene and heteroarylene of L ¹ , aryl and heteroaryl of Ar ¹ are C1-C20alkyl, haloC1-C20alkyl, deuterium, halogen , cyano, C1-C20 alkoxy, haloC1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C6-C20 arylC1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C2-C20 heteroaryl, -P(=0)R ^a R ^b , -SiR ^c R ^d R ^e , may be further substituted with one or more selected from the group consisting of nitro and hydroxy;

R ^a and R ^b are each independently C6-C20 aryl or C2-C20 heteroaryl;

R ^c is C1-C20 alkyl, C6-C20 aryl or C2-C20 heteroaryl;

R ^d and R ^e are each independently hydrogen, C1-C20 alkyl, C6-C20 aryl or C2-C20 heteroaryl;

a and b are each independently an integer of 1 or 2;

In one embodiment, the spiro compound may be represented by any one of Formulas 4 to 8:

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 4 to 8,

X is N-Ar or O;

Ar is C6-C20 aryl;

R ¹ and R ² are each independently C1-C20 alkyl, C6-C20 aryl, C2-C20 heteroaryl or -L ¹ -Ar ¹ , and the alkyl, aryl and heteroaryl of R ¹ and R ² are C1-C20 Alkyl, HaloC1-C20 Alkyl, Deuterium, Halogen, C1-C20 Alkoxy, HaloC1-C20 Alkoxy, C6-C20 Aryl, C6-C20 Aryloxy, C6-C20 ArylC1-C20 Alkyl, C1-C20 AlkylC6-C20 may be further substituted with one or more selected from the group consisting of aryl, C2-C20 heteroaryl, and -P(=O)R ^a R ^b ;

L ¹ is C6-C20 arylene or C2-C20 heteroarylene;

Ar ¹ is C6-C20 aryl or C2-C20 heteroaryl, and the aryl and heteroaryl of Ar ¹ are C1-C20 alkyl, haloC1-C20 alkyl, deuterium, halogen, C6-C20 aryl, C6-C20 arylC1- may be further substituted with one or more selected from the group consisting of C20 alkyl, C1-C20 alkylC6-C20 aryl, and C2-C20 heteroaryl;

R ^a and R ^b are each independently C6-C20 aryl or C2-C20 heteroaryl.

In one embodiment, X is N-Ar; Ar may be C6-C12 aryl, specifically phenyl, naphthyl or biphenyl.

In one embodiment, the R ¹ and R ² are each independently C1-C10 alkyl, or may be selected from the following structure, but is not limited thereto:

From above,

X ¹ is NR ^X1 , O or S;

Y ¹ is CR ^Y1 R ^Y2 , O or S;

R ^X1 is C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;

R ^Y1 and R ^Y2 are each independently C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;

R ³¹ , R ³² and R ³³ independently represent hydrogen, C6-C20 aryl, C3-C20 heteroaryl or -P(=0)R ^Z1 R ^Z2 ;

R ^Z1 and R ^Z2 are each independently C6-C20 aryl or C3-C20 heteroaryl;

R ³⁴ and R ³⁵ are each independently C1-C20 alkyl or C6-C20 aryl;

Aryl and heteroaryl of R ³¹ , R ³² and R ³³ may be further substituted with one or more selected from the group consisting of C1-C20 alkyl and C6-C20 aryl.

In one embodiment, the R ¹ and R ² may each independently be C1-C7alkyl, specifically methyl, ethyl, propyl or butyl.

In one embodiment, R ¹ and R ² may each independently be selected from the following structures.

From above,

X ₁ is NR ^X1 , O or S;

R ^X1 is C1-C10 alkyl or C6-C12 aryl;

R ³¹ , R ³² and R ³³ independently represent hydrogen, C6-C12 aryl, C3-C12 heteroaryl or -P(=0)R ^Z1 R ^Z2 ;

R ^Z1 and R ^Z2 are each independently C6-C12 aryl;

R ³⁴ and R ³⁵ are each independently C1-C10 alkyl or C6-C12 aryl;

Aryl and heteroaryl of R ³¹ , R ³² and R ³³ may be further substituted with one or more selected from the group consisting of C1-C10 alkyl and C6-C12 aryl.

In one embodiment, the spiro compound may be selected from the following, but is not limited thereto.

The spiro compound according to an embodiment of the present invention may be used in an organic material layer of an organic light emitting device due to its structural specificity, and may be specifically used as a material for forming a hole transport layer in the organic material layer.

In addition, the aforementioned compounds can be prepared based on Preparation Examples/Examples described below. In Preparation Examples/Examples to be described later, representative examples are described, but, if necessary, substituents may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. Changing the type or position of the substituents at the remaining positions, if necessary, can be performed by those skilled in the art using techniques known in the art.

In addition, the present invention provides an organic light emitting device including the spiro compound of Chemical Formula 1.

Specifically, the organic light emitting device according to the present invention includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer includes the spiro compound of Chemical Formula 1 above.

However, structures of organic light emitting devices known in the art may also be applied to the present invention. The scope of the present invention is not limited by such a laminated structure.

The organic light emitting device according to the present invention may be manufactured with materials and methods known in the art, except for including the spiro compound of Chemical Formula 1 in at least one of the organic material layers.

The spiro compound of Chemical Formula 1 alone may constitute one or more layers of the organic material layer of the organic light emitting device. However, if necessary, the organic material layer may be formed by mixing with other materials.

The spiro compound of Chemical Formula 1 may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and the like in an organic light emitting device. The spiro compound may be used as a material for one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As an example, the spiro compound may be used as a material for a hole injection and transport layer of an organic light emitting device. As an example, the spiro compound may be used as a material for an electron injection and transport layer of an organic light emitting device. As another example, the spiro compound may be used as a material for a light emitting layer of an organic light emitting device. As another example, the spiro compound may be used as a host material for a phosphorescent emission layer of an organic light emitting device. Preferably, the spiro compound may be used as a hole transport layer material of an organic light emitting device.

In the organic light emitting device according to the present invention, materials other than the spiro compound are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present invention, and may be replaced with materials known in the art. can

As the anode material, materials having a relatively large work function may be used. Specific examples include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc. Metal oxides such as oxide (IZO), combinations of metals and oxides such as ZnO:Al or SnO2:Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiol Ofene] (PEDT), conductive polymers such as polypyrrole and polyaniline may be used, but are not limited thereto. In addition, the anode layer may be formed of only one type of the above materials or may be formed of a mixture of a plurality of materials, and a multilayer structure composed of a plurality of layers of the same composition or different compositions may be formed.

Materials with a relatively low work function may be used as the anode material, and specific examples include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof , a multi-layer structure material such as LiF/Al or LiO/Al may be used.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as CuPc (copper phthalocyanine) disclosed in U.S. Patent No. 4,356,429 or a document [Advanced Material, 6, p.677 (1994)] , such as TCTA (tris(4-carbazoyl-9-ylphenyl)amine), m-MTDATA (4,4',4"-tris(3-Methylphenylphenylamino)triphenylamine), m- MTDAPB (1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene), soluble conductive polymer Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid) or PEDOT:PSS (poly(3,4-ethylenedioxythiophene) -poly(styrnesulfonate)), Pani/CSA (Polyaniline/Camphor sulfonic acid), or PANI/PSS (Polyaniline/Poly(4-styrene-sulfonate)) may be used.

As the hole transport material, the spiro compound according to an embodiment of the present invention may be used alone or in combination with known hole transport materials.

Specifically, the hole transport material includes a spiro compound according to an embodiment of the present invention, but may be used with pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc., and low molecular or high molecular materials may be used together. may be As a specific example, NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidine), NPD (N, N'-bis (naphthalen-1-yl) -N, N'-bis(phenyl)-2,2'-dimethylbenzidine), mCP (1,3-Bis(N-carbazolyl)benzene), TPD (N,N'-Bis(3-methylphenyl)-N,N'- diphenylbenzidine), TTB (N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4-diamine), TTP (N1,N4-diphenyl-N1,N4- dim-tolylbenzene-1,4-diamine), ETPD (N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl )biphenyl]-4,4'-diamine), VNPB (N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine), ONPB (N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), OTPD (N4,N4 small molecule hole transporters such as '-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine); There are polymer hole transport materials such as PVK (poly-N-vinylcarbazole), polyaniline, and (phenylmenyl) polysilane.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone. Metal complexes of derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, etc. may be used, and high molecular materials as well as low molecular materials may be used. As specific examples, TSPO1 (diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide), TPBI (1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene); Alq ₃ (tris(8-hydroxyquinolinato)aluminum); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2-(4-biphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadizole), TAZ (3-(4-biphenyl)-4-phenyl-5-(4- tert-butyl-phenyl)-1,2,4-triazole), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene) azole compounds such as; tris(phenylquinoxaline) (TPQ); TmPyPB (3,3'-[5'-[3-(3-Pyridinyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bispyridine) etc. may, but is not limited thereto.

As an electron injection material, for example, LIF or Liq (lithium quinolate) is typically used in the art, but is not limited thereto.

A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In addition, a fluorescent material can be used as a light emitting material, but it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

The light emitting layer may be formed by a method such as a vacuum deposition method, a spin coating method, a cast method, an LB method, etc. of a light emitting material. In general, it can be selected from almost the same range of conditions as the formation of the hole injection layer. In addition, a known compound can be used as a host or dopant for the light emitting layer material.

Also, for example, as a material for the light emitting layer, as a fluorescent dopant, IDE102 or IDE105 from Idemitsu, BD-331 or BD-142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -Dimesityl trisene-6,12-diamine) can be used, and as the phosphorescent dopant, green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine)iridium), blue dopant F2Irpic (iridium(III) bis[ 4,6-difluorophenyl)-pyridinato-N,C2']picolinate), UDC's red phosphorescent dopant RD61, etc. may be co-evaporated (doped).

The phosphorescent dopant is a compound capable of emitting light from triplet excitons, and is not particularly limited as long as it emits light from triplet excitons. A specific example may be a metal complex including one or more metals selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re, and may be a porphyrin metal complex or an ortho metallized metal complex.

The porphyrin metal complex may be specifically a porphyrin platinum complex.

The ortho metallized metal complex is a 2-phenylpyridine (ppy) derivative, a 7,8-benzoquinoline derivative, a 2-(2-thienyl)pyridine (2-(2-thienyl)pyridine, tp) derivative , 2-(1-naphthyl)pyridine (2-(1-naphthyl)pyridine, npy) derivatives, 2-phenylquinoline (2-phenylquinoline, pq) derivatives, etc. may be included as a ligand. At this time, these derivatives may have a substituent as needed. As an auxiliary ligand, it may further have ligands other than the above ligands, such as acetylacetonato (acac) and picric acid. Specific examples include bisthienylpyridine acetylacetonate iridium, bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III) (bis(2- benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III), Ir(btp) ₂ (acac)), bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III) ( bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III), Ir(bt) ₂ (acac)), bis(1-phenylisoquinoline)(acetylacetonato)iridium(III) (bis(1-phenylisoquinoline)( acetylacetonato)Iridium(III), Ir(piq) ₂ (acac)), tris(1-phenylisoquinoline)iridium(III) (tris(1-phenylisoquinoline)iridium(III), Ir(piq) ₃ ), tris( 2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III), Ir (ppy) ₃ ), tris (2-biphenylpyridine) iridium (tris (2-biphenylpyridine) iridium), tris (3 - Biphenylpyridine) iridium (tris (3-biphenylpyridine) iridium), tris (4-biphenylpyridine) iridium (tris (4-biphenylpyridine) iridium), and the like, but are not limited thereto.

In addition, when used with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) may be additionally laminated by vacuum deposition or spin coating to prevent diffusion of triplet excitons or holes into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but can be selected and used arbitrarily from known ones used as hole blocking materials. For example, it may be an oxadiazole derivative or a triazole derivative or a phenanthroline derivative, specifically Balq (bis(8-hydroxy-2-methylquinolinato)-aluminum biphenoxide), phenanthrolines type compounds (: BCP (vasocuproin) from UDC), etc. can be used.

Hereinafter, the present invention will be described in more detail through examples, but these are only for exemplifying the present invention and are not intended to limit the scope of the present invention.

[Example 1] Preparation of compound 1-1

Preparation of compound a-1

To a reaction flask cooled to -78°C, 25.0 g (63.2 mmol) of 1-bromo-9,9'-spirobifluorene and 350 mL of diethyl ether were added, followed by 28.5 mL of n-butyllithium (2.5 M in hexane). (71.3 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 30 minutes, warmed to room temperature and then re-cooled to -78 °C. 8.54 g (82.2 mmol) of trimethylborate was then rapidly added to the mixture. After the temperature was raised to -10°C, 50 mL of 2N hydrochloric acid was added to the mixture to terminate the reaction, and the organic layer was washed with water, dried using sodium sulfate (Na ₂ SO ₄ ), and concentrated. The residue was washed with 150 mL of n-hexane, filtered, and vacuum dried to obtain 22.3 g (61.9 mmol) of intermediate compound a-1. Yield: 98%.

Preparation of compound a-2

In a reaction flask, 22.3 g (61.9 mmol) of intermediate compound a-1, 17.0 g (68.1 mmol) of 3-bromo-[1,1'-biphenyl] -4-ol, and 4.95 g (123.8 mmol) of sodium hydroxide were added to the reaction flask. , 310 mL of tetrahydrofuran and 155 mL of water were added dropwise. Thereafter, 4.29 g (3.7 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ ) was added dropwise and stirred at 80°C for 18 hours. After completion of the reaction, extraction was performed with 150 mL of methylene chloride and 100 mL of water, and the organic layer was dried over sodium sulfate and concentrated. Then, the residue was separated by column chromatography and recrystallized to obtain 26.7 g (55.1 mmol) of intermediate compound a-2. Yield: 89%.

Preparation of compound 1-1

In a reaction flask, 26.7 g (55.1 mmol) of intermediate compound a-2, 0.62 g (2.8 mmol) of palladium acetate (Pd(OAc) ₂ ), 0.34 g (2.8 mmol) of 3-nitropyridine, t-butyl peroxybenzoate 21.4g (110.2mmol), 92mL of hexafluorobenzene, and 55mL of N,N'-dimethylimidazolidinone were added, followed by reflux stirring at 90°C for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with 150 mL of ethyl acetate and 100 mL of water. After drying and concentrating the organic layer with sodium sulfate, the residue was separated by column chromatography and recrystallized to obtain 17.3 g (35.8 mmol) of the target compound Com 1-1. Yield: 65%.

[Example 2] Preparation of compound 1-52

Preparation of compound b-2

30.0 g (92.8 mmol) of 4-(2-bromophenyl)dibenzofuran and 300 mL of tetrahydrofuran were added to the reaction flask, and the mixture was cooled to -78°C. Then, 35.3 mL of n-butyllithium (2.5 M in hexane) was slowly added dropwise. After stirring for 1 hour, 17.6 g (97.5 mmol) of fluoren-9-one was dissolved in 200 mL of tetrahydrofuran and added dropwise. After raising the temperature to room temperature and stirring overnight, ice water was added and extraction was performed with dichloromethane. The organic layer was extracted with water, dried over sodium sulfate, and concentrated. The residue was mixed with 100 mL of hydrochloric acid and 1100 mL of acetic acid and stirred under reflux at 100 °C overnight without further purification. After completion of the reaction, the precipitated solid was filtered, washed with 100 mL of water and 300 mL of ethanol, and recrystallized from n-heptane to obtain 23.0 g (56.6 mmol) of intermediate compound b-2. Yield: 61%.

Preparation of compound b-3

23.0 g (56.6 mmol) of intermediate compound b-1, 6.6 g (56.6 mmol) of tetramethylethylenediamine, and 100 mL of tetrahydrofuran were added dropwise to the reaction flask. Thereafter, 56.6 mL of n-butyllithium (2.5 M in hexane) was slowly added dropwise at 0° C., and the mixture was heated to room temperature and stirred for 4 hours. Thereafter, the reaction mixture was cooled to -78°C, and 17.8 g (164.1 mmol) of chlorotrimethylsilane was added thereto, followed by slowly raising the temperature to room temperature and stirring overnight. After completion of the reaction, the reaction mixture was filtered through silica and concentrated. The residue was dissolved in 100 mL of dichloromethane, and 6.4 mL (67.9 mmol) of boron tribromide was added dropwise and stirred overnight. After completion of the reaction, ice water was added to the reaction mixture, and the organic layer was separated and extracted with ethyl acetate. The extracted organic layer was dried over magnesium sulfate and concentrated. After separation by column chromatography, 13.0 g (28.9 mmol) of intermediate compound b-3 was obtained. Yield: 51%.

Preparation of compounds 1-52

13.0g (28.9mmol) of intermediate compound b-3, 15.0g (31.8mmol) of bromobenzene, 8.0g (57.7mmol) of potassium carbonate, 128mL of tetrahydrofuran, and 64mL of water were added dropwise to the reaction flask. Thereafter, 2.0 g (1.7 mmol) of tetrakis(triphenylphosphine)palladium(0) was added dropwise and stirred under reflux at 80°C for 16 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with 150 mL of ethyl acetate and 200 mL of water, and the organic layer was dried over magnesium sulfate and concentrated. The concentrated organic layer was purified by column chromatography and recrystallized with n-heptane to obtain 12.8 g (26.6 mmol) of the target compound Com 1-52. Yield: 92%.

[Example 3] Preparation of compound 2-1

Preparation of 3-chloro-4-nitro-1,1'-biphenyl

Under an argon atmosphere, 16.7 g (87.0 mmol) of 2,4-dichloro-1-nitrobenzene, 21.3 g (104.4 mmol) of iodobenzene, 24.0 g (174.0 mmol) of potassium carbonate, and 73 mL of toluene were added dropwise to the reaction flask. After that, 1.8g (7.0mmol) of 18-crown-6 and 1.6g (1.7mmol) of tris(dibenzylideneacetone)dipalladium (0) were added dropwise and stirred under reflux at 115°C for 18 hours. After completion of the reaction, it was cooled to room temperature, and the reaction mixture was extracted with 150 mL of ethyl acetate and 250 mL of water. The extracted organic layer was concentrated by drying over sodium sulfate, and the residue was separated by column chromatography to obtain 15.8 g (67.6 mmol) of 3-chloro-4-nitro-1,1'-biphenyl. Yield: 78%.

Preparation of compound c-1

Intermediate compound a-1 22.1g (61.5mmol), 3-chloro-4-nitro-1,1'-biphenyl 15.8g (67.6mmol), sodium carbonate 19.5g (184.4mmol), 1,4-dioxane 100mL , 0.36 g (0.31 mmol) of tetrakis (triphenylphosphine) palladium (0) was added dropwise to a reaction flask containing 50 mL of water, stirred at room temperature for 30 minutes, and then stirred under reflux at 100 ° C. for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with 150 mL of water and 300 mL of dichloromethane, and the organic layer was concentrated to dryness with sodium sulfate. The concentrated organic layer was purified by column chromatography to obtain 20.1 g (39.3 mmol) of intermediate compound c-1. Yield: 58%.

Preparation of compound c-2

20.1 g (39.3 mmol) of intermediate compound c-1 and 32.5 g (195.7 mmol) of triethylphosphite were added to the reaction flask, and 195 mL of cumene was added dropwise, followed by reflux stirring at 155 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and purified by column chromatography to obtain 13.4g (27.9mmol) of intermediate compound c-2. Yield: 71%.

Preparation of compound 2-1

After adding 13.4 g (27.9 mmol) of intermediate compound c-2, 4.81 g (30.6 mmol) of bromobenzene, 4.68 g (41.7 mmol) of potassium t-butoxide, and 140 mL of xylene to a reaction flask under an argon atmosphere, palladium ( II) Acetate 0.125g (0.56mmol) and tri-t-butylphosphine 0.563g (2.8mmol) were added dropwise and stirred under reflux at 120°C for 24 hours. After completion of the reaction, it was cooled to room temperature, crystallized by adding 150 mL of methanol, and the solid filtered under reduced pressure was purified by column chromatography to obtain 13.7 g (24.6 mmol) of the target compound Com 2-1. Yield: 88%.

[Example 4] Preparation of compound 2-25

Preparation of compound d-1

Except for using 2-(3-chloro-4-nitrophenyl)dibenzo[b,d]furan 25g (77.2mmol) instead of 3-chloro-4-nitro-1,1'-biphenyl, 25.2 g (41.7 mmol) of intermediate compound d-1 was obtained by reacting in the same manner as in the synthesis method of intermediate compound c-1 of Example 3. Yield: 54%.

Preparation of compound d-2

Except for using 25.2 g (41.7 mmol) of intermediate compound d-1 instead of intermediate compound c-1, the reaction was performed in the same manner as in the synthesis method of intermediate compound c-2 in Example 3 to obtain 17.4 g (30.5 g) of intermediate compound d-2. mmol) was obtained. Yield: 73%.

Preparation of compounds 2-25

Except for using 17.4 g (30.5 mmol) of intermediate compound d-2 instead of intermediate compound c-2, the reaction was performed in the same manner as in the synthesis method of compound 2-1 in Example 3 to obtain 17.2 g (26.5 mmol) of the target compound Com 2-25 was obtained. Yield: 87%.

[Example 5] Preparation of compound 2-68

Preparation of compound e-1

In a reaction flask, 35.0 g (95.7 mmol) of 3-chloro-9,9'-spirobifluoren-2-amine, 29.8 g (105.2 mmol) of 1-brovo-2-iodobenzene, sodium-t-butoxide 18.4 g (191.3 mmol), 4.4 g (7.7 mmol) of XantPhos, and 0.4 g (1.9 mmol) of palladium acetate were dissolved in 640 mL of 1,4-dioxane and stirred under reflux for 3 hours. After completion of the reaction, the solvent was removed under reduced pressure, extracted with 300 mL of ethyl acetate and 450 mL of water, and the organic layer was dried over magnesium sulfate, and the solvent was partially concentrated. Thereafter, while stirring the reaction mixture under reflux, n-hexane was added, crystals were dropped, cooled, and filtered. The residue was purified by column chromatography to obtain 30.9 g (59.3 mmol) of the intermediate compound e-1. Yield: 62%.

Preparation of compound e-2

30.9 g (59.3 mmol) of the intermediate compound e-1, 0.3 g (0.593 mmol) of bis (tri-t-butylphosphine) palladium (0), and 16.4 g (118.7 mmol) of potassium carbonate were added dropwise to the reaction flask, followed by diethylacetate. It was dissolved in 300 mL of amide and stirred under reflux for 3 hours. After completion of the reaction, water was poured into the reaction mixture, and crystals were precipitated by filtration. The filtered solid was completely dissolved in 400 mL of 1,2-dichlorobenzene, extracted with water, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 9.4 g (21.4 mmol) of the intermediate compound e-2. Yield: 36%.

Preparation of compound e-3

9.4 g (21.4 mmol) of the intermediate compound e-2, 3.7 g (23.5 mmol) of bromobenzene, 4.1 g (4.3 mmol) of sodium t-butoxide, and 142 mL of xylene were added dropwise to the reaction flask. Thereafter, 0.346 g (1.7 mmol) of tri-t-butylphosphine and 0.391 g (0.427 mmol) of tris (dibenzylidene acetone) dipalladium (0) were added dropwise and stirred at 120 ° C. for 18 hours under reflux. After completion of the reaction, the mixture was cooled to room temperature, extracted with 150 mL of ethyl acetate and 200 mL of water, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 9.6 g (18.6 mmol) of the intermediate compound e-3. Yield: 87%.

Preparation of compound 2-68

In a reaction flask, 9.6 g (18.6 mmol) of intermediate compound e-3, 4.3 g (20.5 mmol) of dibenzo[b,d]furan-2-ylboronic acid, 5.1 g (37.2 mmol) of potassium carbonate, 62 mL of tetrahydrofuran , 31 mL of water was added dropwise. Thereafter, 1.3 g (1.1 mmol) of tetrakis(triphenylphosphine)palladium(0) was added dropwise and stirred under reflux at 80°C for 18 hours. After completion of the reaction, the reaction mixture was extracted with 150 mL of ethyl acetate and 250 mL of water, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 9.4 g (14.5 mmol) of the target compound Com 2-68 after recrystallization. Yield: 78%.

Compounds 1-1 to 1-83 and 2-1 to 2-83 in Table 1 were prepared using the methods of the above examples.

[Table 1]

¹ H NMR and MS values of the prepared compounds 1-1 to 1-83 and 2-1 to 2-83 are shown in Table 2 below.

[Table 2]

[Example 6] Preparation and evaluation of organic light emitting device

An organic light emitting device was manufactured according to a conventional method using the compounds obtained in Examples as hole transport layers, respectively.

First, an ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) is applied on the ITO layer (anode) formed on the glass substrate. was vacuum deposited to form a hole injection layer having a thickness of 10 nm, and then a hole transport layer having a thickness of 20 nm was formed by vacuum depositing the spiro compound prepared in Example of the present invention.

Subsequently, BD-331 (Idemitsu Co.) was used as a light emitting dopant, AND (9,10-Bis(2-naphthyl)anthracene) was used as a host material, and the doping concentration was fixed at 4% to form a layer on the hole transport layer. A light emitting layer was deposited with a thickness of 30 nm.

Subsequently, Alq3 (tris-(8-hydroxyquinoline)aluminum) was vacuum deposited to a thickness of 40 nm as an electron transport layer on the light emitting layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, followed by Al to a thickness of 150 nm, and Al/LiF was used as a cathode to fabricate an organic light emitting device.

[Comparative Examples 1 to 3]

An organic light emitting diode was manufactured in the same manner as in Example 6, except that Comparative Compound A, Comparative Compound B, or Comparative Compound C was used instead of the spiro compound of the present invention as a hole transport material.

A forward bias DC voltage was applied to each organic light emitting device manufactured by Example 6 and Comparative Examples 1 to 3 of the present invention, and electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch, 300 cd / m ² At the standard luminance, T95 life was measured through life measurement equipment manufactured by McScience. T95 means the time taken for the luminance of the light emitting device to reach 95% of the initial luminance.

It can be seen that the spiro compounds developed in the present invention, as hole transport materials, can improve power consumption by inducing an increase in power efficiency by lowering the driving voltage along with better light emission characteristics than conventional hole transport materials, and also life characteristics. It can be seen that there is also a significant increase in

Therefore, the spiro compound of the present invention can be used as a material for forming an organic layer such as a hole transport material to produce an organic light emitting device exhibiting low driving voltage, excellent color purity, high luminous efficiency, and long lifespan. In addition, it is obvious that the same effect can be obtained even when the spiro compounds of the present invention are used in other organic material layers of an organic light emitting device, for example, a light emitting layer, a hole injection layer, an electron injection layer, and an electron transport layer.

That is, the spiro compound according to the present invention has excellent electron mobility due to its structural specificity, thereby improving the current characteristics of the device and strengthening the driving voltage, thereby inducing an increase in power efficiency to manufacture an organic light emitting device with improved power consumption. .

Claims (8)

A spiro compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X is N-Ar or O;
Ar is C6-C60 aryl or C2-C60 heteroaryl;
R ¹ and R ² are each independently C1-C60 alkyl, C1-C60 alkoxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C2-C60 alkenyl, C2-C60 alkynyl, C6-C60 aryl, C2 -C60 heteroaryl, C6-C60 aryloxy or -L ¹ -Ar ¹ ;
L ¹ is C6-C60 arylene or C2-C60 heteroarylene;
Ar ¹ is C6-C60 aryl or C2-C60 heteroaryl;
aryl and heteroaryl of Ar above, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl and aryloxy of R ¹ and R ² , arylene and heteroarylene of L ¹ , Ar Aryl and heteroaryl of ¹ are C1-C60 Alkyl, HaloC1-C60 Alkyl, Deuterium, Halogen, Cyano, C3-C60 Cycloalkyl, C2-C60 Heterocycloalkyl, C1-C60 Alkoxy, HaloC1-C60 Alkoxy, C6 -C60 Aryl, C6-C60 Aryloxy, C6-C60 ArylC1-C60 Alkyl, C1-C60 AlkylC6-C60 Aryl, C2-C60 Heteroaryl, -P(=O)R ^a R ^b , -SiR ^c R ^d R ^e , may be further substituted with one or more selected from the group consisting of nitro and hydroxy;
R ^a and R ^b are each independently C1-C60 alkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C3-C60 cycloalkyl, C2-C60 heterocycloalkyl, C6-C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl or C2-C60 heteroaryl;
R ^c to R ^e are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C2-C60 heteroaryl;
a is an integer from 0 to 4, b is an integer from 0 to 2, provided that a and b are not 0 at the same time;
The heteroaryl, heterocycloalkyl and heteroarylene include one or more heteroatoms selected from N, O, S and Se. According to claim 1,
Ar is C6-C30 aryl or C2-C30 heteroaryl;
R ¹ and R ² are each independently C1-C30 alkyl, C6-C30 aryl, C2-C30 heteroaryl or -L ¹ -Ar ¹ ;
L ¹ is C6-C30 arylene or C2-C30 heteroarylene;
Ar ¹ is C6-C30 aryl or C2-C30 heteroaryl;
Aryl and heteroaryl of Ar, alkyl, aryl and heteroaryl of R ¹ and R ² , arylene and heteroarylene of L ¹ , aryl and heteroaryl of Ar ¹ are C1-C30 alkyl, haloC1-C30 alkyl, Deuterium, halogen, cyano, C1-C30 alkoxy, haloC1-C30 alkoxy, C6-C30 aryl, C6-C30 aryloxy, C6-C30 arylC1-C30 alkyl, C1-C30 alkylC6-C30 aryl, C2-C30 may be further substituted with one or more selected from the group consisting of heteroaryl, -P(=0)R ^a R ^b , -SiR ^c R ^d R ^e , nitro and hydroxy;
R ^a and R ^b are each independently C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl;
R ^c is C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl;
R ^d and R ^e are each independently hydrogen, C1-C30 alkyl, C6-C30 aryl or C2-C30 heteroaryl;
a and b are each independently an integer of 0 to 2, provided that 1≤a+b≤4 is satisfied, a spiro compound According to claim 2,
The spiro compound is a spiro compound represented by Formula 2 or 3 below:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
X is N-Ar or O;
Ar is C6-C20 aryl;
R ¹ and R ² are each independently C1-C20 alkyl, C6-C20 aryl, C2-C20 heteroaryl or -L ¹ -Ar ¹ ;
L ¹ is C6-C20 arylene or C2-C20 heteroarylene;
Ar ¹ is C6-C20 aryl or C2-C20 heteroaryl;
Aryl of Ar, alkyl, aryl and heteroaryl of R ¹ and R ² , arylene and heteroarylene of L ¹ , aryl and heteroaryl of Ar ¹ are C1-C20alkyl, haloC1-C20alkyl, deuterium, halogen , cyano, C1-C20 alkoxy, haloC1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C6-C20 arylC1-C20 alkyl, C1-C20 alkyl C6-C20 aryl, C2-C20 heteroaryl, -P(=0)R ^a R ^b , -SiR ^c R ^d R ^e , may be further substituted with one or more selected from the group consisting of nitro and hydroxy;
R ^a and R ^b are each independently C6-C20 aryl or C2-C20 heteroaryl;
R ^c is C1-C20 alkyl, C6-C20 aryl or C2-C20 heteroaryl;
R ^d and R ^e are each independently hydrogen, C1-C20 alkyl, C6-C20 aryl or C2-C20 heteroaryl;
a and b are each independently an integer of 1 or 2; According to claim 2,
The spiro compound is a spiro compound represented by any one of Formulas 4 to 8:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 4 to 8,
X is N-Ar or O;
Ar is C6-C20 aryl;
R ¹ and R ² are each independently C1-C20 alkyl, C6-C20 aryl, C2-C20 heteroaryl or -L ¹ -Ar ¹ , and the alkyl, aryl and heteroaryl of R ¹ and R ² are C1-C20 Alkyl, HaloC1-C20 Alkyl, Deuterium, Halogen, C1-C20 Alkoxy, HaloC1-C20 Alkoxy, C6-C20 Aryl, C6-C20 Aryloxy, C6-C20 ArylC1-C20 Alkyl, C1-C20 AlkylC6-C20 may be further substituted with one or more selected from the group consisting of aryl, C2-C20 heteroaryl, and -P(=O)R ^a R ^b ;
L ¹ is C6-C20 arylene or C2-C20 heteroarylene;
Ar ¹ is C6-C20 aryl or C2-C20 heteroaryl, and the aryl and heteroaryl of Ar ¹ are C1-C20 alkyl, haloC1-C20 alkyl, deuterium, halogen, C6-C20 aryl, C6-C20 arylC1- may be further substituted with one or more selected from the group consisting of C20 alkyl, C1-C20 alkylC6-C20 aryl, and C2-C20 heteroaryl;
R ^a and R ^b are each independently C6-C20 aryl or C2-C20 heteroaryl. According to claim 2,
Wherein R ¹ and R ² are each independently C1-C10 alkyl, or a spiro compound selected from the following structures.

From above,
X ₁ is NR ^X1 , O or S;
Y ₁ is CR ^Y1 R ^Y2 , O or S;
R ^X1 is C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;
R ^Y1 and R ^Y2 are each independently C1-C20 alkyl, C6-C20 aryl or C3-C20 heteroaryl;
R ³¹ , R ³² and R ³³ independently represent hydrogen, C6-C20 aryl, C3-C20 heteroaryl or -P(=0)R ^Z1 R ^Z2 ;
R ^Z1 and R ^Z2 are each independently C6-C20 aryl or C3-C20 heteroaryl;
R ³⁴ and R ³⁵ are each independently C1-C20 alkyl or C6-C20 aryl;
Aryl and heteroaryl of R ³¹ , R ³² and R ³³ may be further substituted with one or more selected from the group consisting of C1-C20 alkyl and C6-C20 aryl. According to claim 1,
Wherein the spiro compound is selected from:

An organic light emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer including the spiro compound according to any one of claims 1 to 6. . According to claim 7,
The organic material layer is at least one layer selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, an organic light emitting device.