KR102548911B1 - Organic Light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

Description

Organic light emitting device {Organic Light emitting device}

The present invention relates to an organic light emitting device having high luminous efficiency and excellent lifespan.

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 light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, 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 light emitting 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 when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Meanwhile, in recent years, an organic light emitting device using a solution process, particularly an inkjet process, instead of a conventional deposition process has been developed to reduce process costs. In the early days, an attempt was made to develop an organic light emitting device by coating all organic light emitting device layers with a solution process, but the current technology has limitations, so only HIL, HTL, and EML in the form of a regular structure are carried out as a solution process, and the subsequent process is the existing deposition process A hybrid process that utilizes is being studied.

Accordingly, the present invention provides a novel organic light emitting device material that can be used in an organic light emitting device and can be used in a solution process at the same time.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device having high luminous efficiency and excellent lifespan.

In order to solve the above problems, the present invention provides the following organic light emitting device.

The organic light emitting device according to the present invention,

anode; hole injection layer; hole transport layer; light emitting layer; electron transport layer; and a cathode;

The hole injection layer includes a compound represented by Formula 1 below,

The hole transport layer includes a copolymer including repeating units represented by Chemical Formulas 2 and 3 below:

[Formula 1]

In Formula 1,

L and L ₁ to L ₄ are each independently a substituted or unsubstituted C _6-60 arylene;

Ar ₁ is -Ar ₁₁ -(E ₁ )e ₁ ;

Ar ₂ is -Ar ₁₂ -(E ₂ )e ₂ ;

Ar ₁₁ and Ar ₁₂ are each independently C _6-60 aryl; Or a C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

E ₁ , E ₂ and R ₁ to R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 Aryl, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

Y ₁ to Y ₄ are each independently hydrogen or -XA, provided that at least two of Y ₁ to Y ₄ are -XA;

X is O or S;

A is a functional group crosslinkable by heat or light,

e1 and e2 are each an integer from 0 to 5;

n1 and n4 are each an integer from 0 to 4;

n2 and n3 are each an integer from 0 to 3;

[Formula 2]

In Formula 2,

L ₁₁ and L ₁₂ are each independently a single bond; A substituted or unsubstituted C _1-60 alkylene; Substituted or unsubstituted C _1-60 oxyalkylene; Substituted or unsubstituted C _7-60 Aralkylene; or a substituted or unsubstituted C _6-60 arylene;

Z ₁ , R ₃₁ and R ₃₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or A C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

Y ₁₁ and Y ₁₂ are each independently -X'-A';

X' is a single bond, O, or S;

A' is a functional group crosslinkable by heat or light,

a1 and a2 are each an integer from 0 to 3;

b1 is an integer from 0 to 4;

n is a real number from 1 to 9;

[Formula 3]

In Formula 3,

Q is a substituted or unsubstituted C _6-60 arylene;

Ar ₃ is -Ar ₁₃ -(E ₃ )e ₃ ;

Ar ₄ is -Ar ₁₄ -(E ₄ )e ₄ ;

Ar ₁₃ and Ar ₁₄ are each independently C _6-60 aryl; Or a C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

E ₃ , E ₄ , Z ₂ , R ₃₃ and R ₃₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

e3 and e4 are each an integer from 0 to 5;

a3, a4 and b2 are each an integer from 0 to 4;

m is a real number from 1 to 9;

n+m is 10,

When a1 to a4, b1, b2, and e1 to e4 are 2 or more, structures in parentheses of two or more are the same as or different from each other.

The above-described organic light emitting device includes the compound represented by Chemical Formula 1 as a material for the hole injection layer and at the same time includes a copolymer including repeating units represented by Chemical Formulas 2 and 3 as a material for the hole transport layer. While the injection layer and the hole transport layer can be manufactured by a solution process, they can have high luminous efficiency and long lifespan characteristics.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7. it is depicted
2 is composed of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 8 and a cathode 7 An example of an organic light emitting device is shown.

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.

Definition of Terms

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

and

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more 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 number of carbon atoms of the carbonyl group is not particularly limited, but 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 an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 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 silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.

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

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary 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, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are 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 number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heteroaryl include a thiophene group, a furan group, a pyrrole 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 triazine group, an acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, a phenothiazinyl group and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the above-described heteroaryl may be applied to the heteroaryl among heteroarylamines. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of heteroaryl described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that it is formed by combining two substituents.

hole injection layer and hole transport layer

The present invention, an anode; cathode; a light emitting layer between the anode and cathode; a hole injection layer and a hole transport layer between the anode and the light emitting layer; And an organic light emitting device comprising an electron transport layer between the cathode and the light emitting layer, wherein the hole injection layer of the organic light emitting device is positioned adjacent to the anode and includes the compound represented by Formula 1, wherein the hole transport layer is It is characterized in that it comprises a copolymer including repeating units represented by Chemical Formulas 2 and 3 while being positioned adjacent to the light emitting layer.

When materials used in the conventional vacuum deposition process are used in a solution process to form multiple layers of an organic light emitting device, these materials have very low solubility in solvents or poor resistance to solvents, so that interlayer materials are mixed There has been a problem that the performance of the organic light emitting device is degraded.

However, the compound used in the hole injection layer and the copolymer used in the hole transport layer according to the present invention have excellent resistance to the solvent used in the solution process, and thus interlayer mixing can be prevented during the manufacture of an organic light emitting device by a solution process. can In addition, the compound used in the hole injection layer and the copolymer used in the hole transport layer have amine moieties similar to each other, so that energy levels between layers are effectively aligned, and thus hole movement between the hole injection layer and the hole transport layer can be increased. Accordingly, an organic light emitting device employing them exhibits high efficiency and increased lifetime.

Preferably, the compound represented by Chemical Formula 1 and the copolymer including repeating units represented by Chemical Formulas 2 and 3 have the same amine moiety in each molecule. At this time, 'the amine moiety in each molecule is the same' means that L and Q in Formulas 1 and 3 are the same, Ar ₁₁ and Ar ₁₃ are the same, and Ar ₁₂ and Ar ₁₄ are the same as each other. means In this case, hole hopping between the hole injection layer and the hole transport layer is increased, and thus the lifespan of the organic light emitting device may be further improved.

(Compound represented by Formula 1)

As the compound represented by Formula 1 contains oxygen (O) or sulfur (S) atoms in its molecule, it can form a completely cured and stable thin film by heat treatment or UV treatment. In addition, it has high affinity with solvents, has solvent selectivity (orthogonality), and has excellent resistance to solvents used in solution processes.

Preferably, in Formula 1, L is Formula 1-A or 1-B:

[Formula 1-A]

[Formula 1-B]

In Formulas 1-A and 1-B,

R ₁₁ to R ₁₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N, O And C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of S,

m1 to m3 are each an integer of 0 to 4;

When m1 to m3 are 2 or more, respectively, two or more structures in parentheses are the same as or different from each other.

More preferably, L is biphenyldiyl, most preferably, biphenyl-4,4'-diyl.

Preferably, L ₁ to L ₄ are each independently unsubstituted or halogen; C _1-10 alkyl; C _1-10 alkoxy; or C _6-20 arylene substituted with C _6-10 aryloxy.

More preferably, L ₁ to L ₄ are each independently unsubstituted or halogen; C _1-10 alkyl; C _1-10 alkoxy; or benzene substituted with C _6-10 aryloxy, or unsubstituted, or halogen; C _1-10 alkyl; C _1-10 alkoxy; or naphthyl substituted with C _6-10 aryloxy.

Preferably, Ar ₁₁ and Ar ₁₂ are each independently phenyl or biphenylyl, and E ₁ and E ₂ are hydrogen. At this time, more preferably, Ar ₁ and Ar ₂ are the same as each other.

Preferably, A is any one selected from the group consisting of:

From above,

T ₁ is hydrogen; or a substituted or unsubstituted C _1-6 alkyl;

T ₂ to T ₄ are each independently a substituted or unsubstituted C _1-6 alkyl.

Preferably, Formula 1 is represented by any one of Formulas 1-1 to 1-4 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

R ₁ to R ₄ , n1 to n4, Ar ₁ , Ar ₂ and L are as defined in Formula 1 of claim 1,

X ₁ to X ₄ are each independently O or S;

A ₁ to A ₄ are each independently a functional group crosslinkable by heat or light;

R ₂₁ to R ₂₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N , C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of O and S,

p1 and p2 are each an integer from 0 to 5,

p3 and p4 are each an integer from 0 to 4;

p5 and p6 are each an integer from 0 to 7;

When p1 to p6 are 2 or more, respectively, two or more structures in parentheses are the same as or different from each other.

More preferably, in Formulas 1-1 to 1-4,

R ₁ and R ₄ are each independently hydrogen or phenyl;

R ₂ and R ₃ are hydrogen;

R ₂₁ to R ₂₆ are each independently hydrogen, fluoro, methyl, tert-butyl, 2-ethylhexyl, methoxy, 2-ethoxyethoxy, or phenoxy;

p1 to p6 are integers of 0 to 2, respectively.

An example of the compound represented by Formula 1 is any one selected from the group consisting of:

Meanwhile, the compound represented by Chemical Formula 1 can be prepared by the same method as in Reaction Scheme 1 below.

[Scheme 1]

In Scheme 1, the definitions except for X" are as defined above, and X" is halogen, preferably bromo or chloro. Reaction Scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Meanwhile, the hole injection layer further includes a p-doping material in addition to the compound represented by Chemical Formula 1. The p-doped material means a material that allows the host material to have p-semiconductor characteristics. The p semiconductor property refers to a property of injecting or transporting holes at the highest occupied molecular orbital (HOMO) energy level, that is, a property of a material having high hole conductivity.

Preferably, the p-doping material may be any one of the following compounds A to H.

[Compound A]

[Compound B]

[Compound C]

[Compound D]

[Compound E]

[Compound F]

[Compound G]

[Compound H]

Preferably, the content of the p-doping material is 0% to 50% by weight compared to the compound represented by Formula 1.

(Copolymers containing repeating units represented by Formulas 2 and 3)

Copolymers containing repeating units represented by Chemical Formulas 2 and 3 have block or random copolymer forms, and are curable polymers that form stable thin films completely cured by heat treatment or UV treatment. In addition, it has excellent resistance to solvents used in solution processing due to its high molecular weight.

In the repeating unit represented by Formula 2, A' is any one selected from the group consisting of:

From above,

T ₅ is hydrogen; or a substituted or unsubstituted C _1-6 alkyl;

T ₆ to T ₈ are each independently a substituted or unsubstituted C _1-6 alkyl.

Preferably, Formula 2 is represented by any one of Formulas 2-1 to 2-3 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

Z ₁ , R ₃₁ , R ₃₂ , a1, a2, b1 and n are as defined in Formula 2 of claim 1,

X' ₁ and X' ₂ are each independently a single bond, O, or S;

A' ₁ and A' ₂ are each independently a functional group crosslinkable by heat or light;

R ₅₁ and R ₅₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N , C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of O and S,

d1 and d2 are each an integer from 1 to 10;

q1 and q2 are each an integer from 0 to 4;

When q1 and q2 are 2 or more, respectively, two or more structures in parentheses are the same as or different from each other.

Preferably, in Formulas 2-1 to 2-3,

Z ₁ is hydrogen or C _1-10 alkyl;

X' ₁ and X' ₂ are each independently a single bond or O;

R ₃₁ , R ₃₂ , R ₅₁ and R ₅₂ are hydrogen;

b1 is 0 or 2;

d1 and d2 are 1;

a1, a2, q1 and q2 are 0 or 1.

For example, the repeating unit represented by Chemical Formula 2 is any one selected from the group consisting of:

From above,

Z ₁ is hydrogen, methyl, propyl, heptyl, or hexyl.

In the repeating unit represented by Formula 3, Q is Formula 3-A or 3-B:

[Formula 3-A]

[Formula 3-B]

In Formulas 3-A and 3-B,

R ₄₁ to R ₄₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N, O And C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of S,

c1 to c3 are each an integer from 0 to 4;

When c1 to c3 are 2 or more, respectively, two or more structures in parentheses are the same as or different from each other.

Preferably, in Formulas 3-A and 3-B, R ₄₁ to R ₄₃ are each independently hydrogen or methyl, and c1 to c3 are 0 or 2, respectively.

More preferably, Q is phenylene or biphenyldiyl unsubstituted or substituted with one or more methyls, most preferably 1,4-phenylene, biphenyl-4,4'-diyl, or 2 ,2',5,5'-tetramethylbiphenyl-4,4'-diyl.

Preferably, Ar ₁₃ and Ar ₁₄ are each independently phenyl or biphenylyl, E ₃ and E ₄ are each independently hydrogen, C _1-10 alkyl, or C _1-10 alkoxy, and e3 and e4 are Each is 0, 1, 2, or 3. At this time, more preferably, Ar ₃ and Ar ₄ are the same as each other.

More preferably, Ar ₁₃ and Ar ₁₄ are each independently phenyl or biphenylyl, and E ₃ and E ₄ are each independently hydrogen, methyl, propyl, tert-butyl, pentyl, 4,4-dimethyl-2 -pentyl, or methoxy, and e3 and e4 are each 0, 1, 2, or 3;

Preferably, Z ₁ and Z ₂ are identical to each other, more preferably, Z ₁ and Z ₂ are hydrogen or C _1-10 alkyl, and are identical to each other. Also, preferably, b1 and b2 are equal to each other, and more preferably, b1 and b2 are equal to 0 or 2.

For example, the repeating unit represented by Chemical Formula 3 is any one selected from the group consisting of:

From above,

Z ₂ is hydrogen, methyl, propyl, pentyl, or hexyl.

Preferably, the copolymer including the repeating units represented by Chemical Formulas 2 and 3 has a number average molecular weight (Mn) of 50,000 g/mol to 300,000 g/mol. In the case of having such a number average molecular weight, it is possible to prevent interlayer migration of materials by forming a stable thin film structure after curing while exhibiting appropriate solubility in a solution process.

On the other hand, in Formulas 2 and 3, n and m mean the mole fraction in the copolymer when the total number of moles of the copolymer is 10, respectively, and the copolymer including the repeating unit represented by Formulas 2 and 3 The repeating unit (n) represented by Chemical Formula 2 and the repeating unit (m) represented by Chemical Formula 3 are included in a molar ratio of 1:9 to 9:1. This molar ratio can be adjusted by adjusting the reaction molar ratio of the monomers represented by Chemical Formulas 4 to 6 described later.

More preferably, the copolymer including the repeating units represented by Chemical Formulas 2 and 3 contains the repeating unit (n) represented by Chemical Formula 2 and the repeating unit (m) represented by Chemical Formula 3 in a ratio of 1:9 to 4 :6 in a molar ratio. In other words, the copolymer including the repeating units represented by Chemical Formulas 2 and 3 contains 60 mol% to 90 mol%, more preferably 70 mol% to 90 mol% of the repeating units represented by Chemical Formula 3, Preferably it contains 80 mol% to 90 mol%. In this case, since the ratio of the amine moiety in the copolymer is high, hole migration can effectively occur between the hole injection layer and the hole transport layer having the same amine moiety.

Meanwhile, in the copolymer including the repeating units represented by Chemical Formulas 2 and 3, for example, when Z ₁ and Z ₂ are identical to each other and b1 and b2 are identical to each other, monomer compounds represented by Chemical Formulas 4 to 6 are prepared. It can be prepared by copolymerization:

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, the description of each substituent is the same as defined above, and this reaction is a Suzuki coupling reaction, and the substituent for the reaction can be changed as known in the art. The manufacturing method may be more specific in examples to be described later. In addition, n in Formula 2 and m in Formula 3 can be adjusted by adjusting the reaction molar ratio of the monomers represented by Formulas 4 to 6.

(coating composition)

Meanwhile, the hole injection layer and the hole transport layer described above may be formed by a solution process. Specifically, the hole injection layer is prepared using a coating composition including the compound represented by Formula 1 and a solvent, and the hole transport layer is prepared using a coating composition including the above-described copolymer and a solvent.

The solvent that can be used at this time is not particularly limited as long as it is a solvent capable of dissolving or dispersing the above-mentioned compounds and copolymers, respectively. For example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloro chlorine-based solvents such as roethane, chlorobenzene, and o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents, such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. alcohol and its derivatives; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide-based solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; benzoate solvents such as butyl benzoate and methyl-2-methoxy benzoate; tetralin; and solvents such as 3-phenoxy-toluene. In addition, the above-mentioned solvent may be used alone or in combination of two or more solvents.

In addition, each coating composition may further include one or two or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, oxide, such as bis-3,5,5-trimethylhexanoyl peroxide, lauryl peroxide, benzoyl peroxide, or the like, or azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile. There is an azo type, but is not limited thereto.

As the photopolymerization initiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxyethoxy ) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1- Phenyl propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) acetophenone-based or ketal-based photopolymerization initiators such as oxime; benzoin ether-based photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin ethyl ether; benzophenone-based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoyl phenyl ether; thioxanthone-based photopolymerization initiators such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; and ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, Other photopolymerization initiators such as, but not limited to, bis(2,4-dimethoxy benzoyl)-2,4,4-trimethyl pentylphosphine oxide.

In addition, those having a photopolymerization accelerating effect may be used alone or in combination with the photopolymerization initiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, 4,4'-dimethylaminobenzophenone, etc. Not limited.

The hole injection layer is formed by coating a coating composition containing the compound represented by Chemical Formula 1 on an anode by a solution process, and then heat-treating or light-treating the coated coating composition. In addition, the hole transport layer is formed by coating the coating composition containing the above-described copolymer on the hole injection layer formed previously by a solution process, and then heat-treating or light-treating the coated coating composition.

Here, the solution process means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited to these.

In addition, the heat treatment temperature is preferably 150 to 230 ℃. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen. In addition, a process of evaporating a solvent may be further included between the coating step and the heat treatment or light treatment.

Each of the hole injection layer and the hole transport layer formed by the above method has a stable thin film structure because a plurality of polymers included in the coating composition can be completely cured after crosslinking through the heat treatment or light irradiation step. Therefore, even if the hole transport layer is formed on the hole injection layer or another layer is formed on the hole transport layer through a solution process, it is possible to prevent it from being dissolved by the solvent used or decomposed due to morphological influence. . Accordingly, it is possible to form a plurality of layers through a solution process, and the lifespan characteristics of the organic light emitting diode may be improved by increasing the stability of the formed layers.

Meanwhile, the rest of the organic light emitting device except for the hole injection layer and the hole transport layer described above are not particularly limited as long as they can be used in the organic light emitting device, and each component will be described below.

anode and cathode

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode material 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); combinations of metals and oxides such as ZnO:Al or SNO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

light emitting layer

The light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

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, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer that receives electrons from a cathode or an electron injection layer and transports electrons to an electron control layer.

As the electron transport material, a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include NaF, CsF, LiF, KF, MgF ₂ , CaF ₂ such as alkali halides; 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 transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer for injecting electrons from the electrode.

As an electron injection material, it has the ability to transport electrons, has an excellent electron injection effect from a cathode, a light emitting layer or a light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , compounds having excellent thin film forming ability are preferred.

Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, 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-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 .

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7. it is depicted In this structure, the compound represented by Chemical Formula 1 may be included in the hole blocking layer and the compound represented by Chemical Formula 3 may be included in the electron transport layer, respectively.

2 is composed of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 8 and a cathode 7 An example of an organic light emitting device is shown. The compound represented by Chemical Formula 1 may be included in the hole blocking layer and the compound represented by Chemical Formula 3 may be included in the electron transport layer, respectively.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

[ manufacturing example ]

manufacturing example 1: preparation of compound 28

1) Preparation of Intermediate 28-1

In a 250 ml round flask, 4-(2-bromo-9-(p-tolyl)-9H-fluoren-9-yl)phenol 15 g (35.1 mmol, 1.0 eq), potassium carbonate 14.6 g (105.3 mmol, 3 eq) ), 334.3 mg (1.76 mmol, 0.05 eq) of copper iodide, and 4.4 g (35.1 mmol, 1.0 eq) of 1-butylimidazole were dissolved in 175 ml of toluene. After installing a reflux device, the mixture was heated to 120° C. and the reaction proceeded with stirring. After the reaction was completed, the reaction was stopped with saturated NaHCO ₃ aqueous solution and worked up with water and ethyl acetate. The organic layer was separated, dried over MgSO ₄ and filtered. Thereafter, the solvent is removed using a rotary vacuum evaporator. The obtained crude material was purified by column chromatography to obtain an intermediate compound 28-1.

2) Preparation of Compound 28

In a 250 ml round flask, 10.0 g (18.89 mmol, 2.05 eq) of intermediate 28-1, 3.10 g (9.21 mmol, 1.0 g) of N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine eq), 3.10 g (32.24 mmol, 3.5 eq) of NaOtBu, and 235.1 mg (0.46 mmol, 0.05 eq) of Pd (PtBu ₃ ) ₂ were dissolved in 120 ml of toluene, followed by stirring to react under a nitrogen atmosphere. After the reaction was completed, work-up was performed with water and ethyl acetate, and the organic layer was separated, dried, and filtered. After that, the solvent was removed using a rotary vacuum evaporator. The obtained crude material was purified by column chromatography and the solvent was removed to obtain Compound 28 as a white solid.

1H NMR (500 MHz): δ 7.90-7.87 (m, 4H), 7.56-7.53 (m, 6H), 7.48-7.30 (m, 16H), 7.27 (s, 2H), 7.25-7.22 (d, 4H) , 7.20-7.15 (m, 18H), 7.14-7.12 (d, 4H), 2.88 (s, 8H), 2.19 (s, 6H)

manufacturing example 2: preparation of compound 2

Compound 2 was prepared in the same manner as in Preparation Example 1, except that Intermediate Compound 2-1 was used instead of Intermediate Compound 28-1 in Preparation Example 1.

1H NMR (500 MHz): δ 7.91-7.88 (m, 4H), 7.69-7.67 (d, 4H), 7.62-7.55 (m, 6H), 7.42-7.00 (m, 34H), 6.92-6.87 (m, 6H), 6.74-6.73 (m, 2H), 5.73 (d, 2H), 5.27 (d, 2H), 5.10 (s, 4H), 2.15 (s, 6H), 2.13 (s, 6H)

manufacturing example 3: preparation of compound 18

Compound 18 was prepared in the same manner as in Preparation Example 1, except that Intermediate Compound 18-1 was used instead of Intermediate Compound 28-1 in Preparation Example 1.

1H NMR (500 MHz): δ 8.11-8.08 (m, 4H), 7.78-7.60 (m, 10H), 7.54-7.05 (m, 38H), 6.89-6.85 (m, 4H), 6.74-6.73 (m, 2H), 5.70 (d, 2H), 5.26 (d, 2H), 3.78 (s, 6H)

manufacturing example 4: preparation of compound 33

Compound 33 was prepared in the same manner as in Preparation Example 1, except that Intermediate Compound 33-1 was used instead of Intermediate Compound 28-1 in Preparation Example 1.

1H NMR (500 MHz): δ 8.21-8.20 (d, 2H), 7.91-7.88 (m, 4H), 7.80-7.74 (m, 6H), 7.61-7.04 (m, 46H), 7.02-7.00 (m, 4H), 2.90 (s, 8H)

manufacturing example 5: Preparation of Copolymer 1

1.0 g (2.007 mmol, 1.0 eq) of P1, 1.3896 g (1.706 mmol, 0.85 eq) of N1, 159.01 mg (0.301 mmol, 0.15 eq) of F1, and 51.284 mg (0.1 mmol, 0.05 eq) of catalyst were added to 25 ml RBF. Then, it was dissolved in 20 ml of THF (0.1 M), purged with nitrogen, and stirred at 80 degrees. After 10 minutes, 5 ml (3.0 eq) of Et ₄ NOH aqueous solution (35 wt. % in H2O) was slowly added and the reaction proceeded ovenight. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.05 eq) and a small amount of phenylboronic acid were dissolved in 3 ml of THF, added thereto, and stirred. Next, a small amount of sodium diethyldithiocarbonate trihydrate was added and stirred under reflux. Thereafter, the mixture was washed twice each with an aqueous hydrochloric acid solution and an aqueous ammonia solution and three times with water, and the organic layer was separated, and the separated organic layer was dropped into methanol to precipitate and the obtained solid was dried. The dried solid was dissolved in toluene and passed through an alumina-silica layer. Then, the crude was dissolved in toluene and added dropwise to MeOH, and the obtained solid was dried to obtain the copolymer 1 in the title. The sum is 10).

The prepared copolymer 1 had a number average molecular weight of 68,000 g/mol and a weight average molecular weight of 108,000 g/mol. At this time, the molecular weight was measured by GPC using PC Standard using an Agilent 1200 series.

manufacturing example 6: Preparation of Copolymer 2

Copolymer 2 was prepared in the same manner as in Preparation Example 5, except that P2, N2, and F2 were used instead of P1, N1, and F1 in Preparation Example 5.

The prepared copolymer 2 had a number average molecular weight of 76,000 g/mol and a weight average molecular weight of 136,800 g/mol. At this time, the molecular weight was measured by GPC using PC Standard using an Agilent 1200 series.

manufacturing example 7: Preparation of copolymer 3

Copolymer 3 was prepared in the same manner as in Preparation Example 5, except that P2, N3, and F3 were used instead of P1, N1, and F1 in Preparation Example 5.

The prepared copolymer 3 had a number average molecular weight of 67,900 g/mol and a weight average molecular weight of 118,800 g/mol. At this time, the molecular weight was measured by GPC using PC Standard using an Agilent 1200 series.

manufacturing example 8: Preparation of copolymer 4

Copolymer 4 was prepared in the same manner as in Preparation Example 5, except that P3, N3, and F2 were used instead of P1, N1, and F1 in Preparation Example 5.

The prepared copolymer 4 had a number average molecular weight of 88,900 g/mol and a weight average molecular weight of 177,800 g/mol. At this time, the molecular weight was measured by GPC using PC Standard using an Agilent 1200 series.

Comparative Manufacturing Example 1: Preparation of Copolymer A

Copolymer A was prepared in the same manner as in Preparation Example 5, except that P2, N4, and F2 were used instead of P1, N1, and F1 in Preparation Example 5.

The prepared copolymer A had a number average molecular weight of 76,800 g/mol and a weight average molecular weight of 114,500 g/mol. At this time, the molecular weight was measured by GPC using PC Standard using an Agilent 1200 series.

Example One

A glass substrate on which indium tin oxide (ITO) was deposited with a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water washing was completed, the substrate was ultrasonically washed with solvents such as isopropyl alcohol and acetone for 30 minutes each, dried, and transported to a glove box.

On the ITO transparent electrode thus prepared, compound 18 and compound D prepared in Preparation Example 3 were mixed at a weight ratio of 8:2 and a solution dissolved in cyclohexanone was spin-coated to form a film with a thickness of 400 Å, which was heated at 220 degrees for 30 minutes under a nitrogen atmosphere. The hole injection layer was formed by heating. Thereafter, copolymer 1 prepared in Preparation Example 5 was dissolved in toluene, spin-coated on the hole injection layer to form a film of 200 Å, and heated at 170 degrees for 1 hour under a nitrogen atmosphere to form a hole transport layer.

Thereafter, the following compound Alq3 was dissolved in toluene to form a film of 200 Å, and heated at 160 degrees for 30 minutes under a nitrogen atmosphere to form a light emitting layer. A compound LiF was vacuum thermally deposited on the light emitting layer to form an electron transport layer having a thickness of 350 Å, and Al was vacuum thermally deposited on the electron transport layer to form a cathode.

Thereafter, sealing was performed by bonding the sealing glass and the glass substrate to the glass using a photocurable epoxy resin to produce an organic EL element having a multilayer structure. Subsequent operations were performed in the air at room temperature (25 degrees).

[Compound D]

[Alq3]

Example 2 to 4; comparative example 1 and comparative example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that compounds or copolymers listed in Table 1 were used as materials for the hole injection layer and the hole transport layer in Example 1.

Specific structures of materials used in Examples and Comparative Examples are as follows.

[Compound A]

[Compound F]

[Compound X]

Experimental example : Device characteristic evaluation

When a current was applied to the organic light emitting device prepared in Examples 1 to 4, Comparative Example 1 and Comparative Example 2, driving voltage, current efficiency, quantum efficiency (QE), and luminance lifetime at a current density of 10 mA/cm ² was measured and the results are shown in Table 1 below. T90 means the time required for the luminance to decrease from the initial luminance to 90%.

hole injection layer hole transport layer drive voltage
(V) current efficiency
(cd/A) QE
(%) luminance
(cd/m ² ) T90
(hr) Example 1 compound 18
compound D copolymer 1 4.52 6.35 6.87 634.92 181.9 Example 2 compound 2 compound D copolymer 2 4.74 6.57 7.10 657.49 191.7 Example 3 compound 33
compound F copolymer 3 4.96 6.75 7.30 674.97 170.1 Example 4 Compound 28 Compound F copolymer 4 5.12 6.81 7.42 681.15 191.4 Comparative Example 1 compound 2
compound D Copolymer A - 3.66 4.23 366.12 98.5 Comparative Example 2 compound X
compound A copolymer 2 - 3.77 4.32 376.81 94.4

Referring to Table 1, the organic light emitting device according to the present invention in which the compound of the hole injection layer and the copolymer of the hole transport layer have the same amine moiety is compared to the organic light emitting device of Comparative Example 1 which does not have the same amine moiety. , it can be seen that it exhibits excellent characteristics in terms of efficiency, luminance and lifetime. In addition, in the organic light emitting device according to the present invention, even though the material of the hole injection layer and the material of the hole transport layer have the same amine moiety, the compound represented by Formula 1 of the present invention is not used as the hole injection layer material. Compared to the organic light emitting diode of Example 2, it can be seen that it exhibits excellent characteristics in terms of efficiency, luminance, and lifetime.

1: substrate 2: anode
3: hole injection layer 4: hole transport layer
5: light emitting layer 6: electron transport layer
7: cathode 8: electron injection layer

Claims (18)

anode; hole injection layer; hole transport layer; light emitting layer; electron transport layer; and a cathode;
The hole injection layer includes a compound represented by Formula 1 below,
The hole transport layer includes a copolymer including repeating units represented by Chemical Formulas 2 and 3,
Organic Light-Emitting Elements:
[Formula 1]

In Formula 1,
L and L ₁ to L ₄ are each independently a substituted or unsubstituted C _6-60 arylene;
Ar ₁ is -Ar ₁₁ -(E ₁ )e ₁ ;
Ar ₂ is -Ar ₁₂ -(E ₂ )e ₂ ;
Ar ₁₁ and Ar ₁₂ are each independently C _6-60 aryl; Or a C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
E ₁ , E ₂ and R ₁ to R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 Aryl, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
Y ₁ to Y ₄ are each independently hydrogen or -XA, provided that at least two of Y ₁ to Y ₄ are -XA;
X is O or S;
A is a functional group crosslinkable by heat or light,
e1 and e2 are each an integer from 0 to 5;
n1 and n4 are each an integer from 0 to 4;
n2 and n3 are each an integer from 0 to 3;
[Formula 2]

In Formula 2,
L ₁₁ and L ₁₂ are each independently a single bond; A substituted or unsubstituted C _1-60 alkylene; Substituted or unsubstituted C _1-60 oxyalkylene; Substituted or unsubstituted C _7-60 Aralkylene; or a substituted or unsubstituted C _6-60 arylene;
Z ₁ , R ₃₁ and R ₃₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or A C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
Y ₁₁ and Y ₁₂ are each independently -X'-A';
X' is a single bond, O, or S;
A' is a functional group crosslinkable by heat or light,
a1 and a2 are each an integer from 0 to 3;
b1 is an integer from 0 to 4;
n is a real number from 1 to 9;
[Formula 3]

In Formula 3,
Q is a substituted or unsubstituted C _6-60 arylene;
Ar ₃ is -Ar ₁₃ -(E ₃ )e ₃ ;
Ar ₄ is -Ar ₁₄ -(E ₄ )e ₄ ;
Ar ₁₃ and Ar ₁₄ are each independently C _6-60 aryl; Or a C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
E ₃ , E ₄ , Z ₂ , R ₃₃ and R ₃₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
e3 and e4 are each an integer from 0 to 5;
a3, a4 and b2 are each an integer from 0 to 4;
m is a real number from 1 to 9;
n+m is 10,
L and Q are equal to each other.
According to claim 1,
Ar ₁₁ and Ar ₁₃ are the same as each other;
Ar ₁₂ and Ar ₁₄ are identical to each other;
organic light emitting device.
According to claim 1,
L is Formula 1-A or 1-B,
Organic Light-Emitting Elements:
[Formula 1-A]

[Formula 1-B]

In Formulas 1-A and 1-B,
R ₁₁ to R ₁₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N, O And C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of S,
m1 to m3 are integers of 0 to 4, respectively.
According to claim 1,
L ₁ to L ₄ are each independently unsubstituted or halogen; C _1-10 alkyl; C _1-10 alkoxy; or C _6-20 arylene substituted with C _6-10 aryloxy;
organic light emitting device.
According to claim 1,
Ar ₁₁ and Ar ₁₂ are each independently phenyl or biphenylyl;
E ₁ and E ₂ are hydrogen;
organic light emitting device.
According to claim 1,
A is any one selected from the group consisting of
Organic Light-Emitting Elements:

From above,
T ₁ is hydrogen; or a substituted or unsubstituted C _1-6 alkyl;
T ₂ to T ₄ are each independently a substituted or unsubstituted C _1-6 alkyl.
According to claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-4,
Organic Light-Emitting Elements:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
R ₁ to R ₄ , n1 to n4, Ar ₁ , Ar ₂ and L are as defined in Formula 1 of claim 1,
X ₁ to X ₄ are each independently O or S;
A ₁ to A ₄ are each independently a functional group crosslinkable by heat or light;
R ₂₁ to R ₂₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N , C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of O and S,
p1 and p2 are each an integer from 0 to 5,
p3 and p4 are each an integer from 0 to 4;
p5 and p6 are each an integer from 0 to 7.
According to claim 7,
R ₁ and R ₄ are each independently hydrogen or phenyl;
R ₂ and R ₃ are hydrogen;
R ₂₁ to R ₂₆ are each independently hydrogen, fluoro, methyl, tert-butyl, 2-ethylhexyl, methoxy, 2-ethoxyethoxy, or phenoxy;
p1 to p6 are each an integer from 0 to 2,
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

According to claim 1,
The hole injection layer further comprises a p doping material,
organic light emitting device.
According to claim 1,
A 'is any one selected from the group consisting of
Organic Light-Emitting Elements:

From above,
T ₅ is hydrogen; or a substituted or unsubstituted C _1-6 alkyl;
T ₆ to T ₈ are each independently a substituted or unsubstituted C _1-6 alkyl.
According to claim 1,
Formula 2 is represented by any one of the following Formulas 2-1 to 2-3,
Organic Light-Emitting Elements:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,
Z ₁ , R ₃₁ , R ₃₂ , a1, a2, b1 and n are as defined in Formula 2 of claim 1,
X' ₁ and X' ₂ are each independently a single bond, O, or S;
A' ₁ and A' ₂ are each independently a functional group crosslinkable by heat or light;
R ₅₁ and R ₅₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N , C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of O and S,
d1 and d2 are each an integer from 1 to 10;
q1 and q2 are each an integer from 0 to 4.
According to claim 1,
The repeating unit represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:

From above,
Z ₁ is hydrogen, methyl, propyl, heptyl, or hexyl.
According to claim 1,
Q is Formula 3-A or 3-B,
Organic Light-Emitting Elements:
[Formula 3-A]

[Formula 3-B]

In Formulas 3-A and 3-B,
R ₄₁ to R ₄₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _6-60 aryl, or N, O And C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of S,
c1 to c3 are integers of 0 to 4, respectively.
According to claim 1,
Ar ₁₃ and Ar ₁₄ are each independently phenyl or biphenylyl;
E ₃ and E ₄ are each independently hydrogen, C _1-10 alkyl, or C _1-10 alkoxy;
e3 and e4 are each 0, 1, 2, or 3;
organic light emitting device.
According to claim 1,
The repeating unit represented by Formula 3 is any one selected from the group consisting of
Organic Light-Emitting Elements:

From above,
Z ₂ is hydrogen, methyl, propyl, pentyl, or hexyl.
According to claim 1,
Copolymers containing repeating units represented by Formulas 2 and 3 have a number average molecular weight (Mn) of 50,000 g/mol to 300,000 g/mol,
organic light emitting device.
According to claim 1,
The copolymer containing repeating units represented by Formulas 2 and 3 contains 60 mol% to 90 mol% of repeating units represented by Formula 3,
organic light emitting device.

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