Composition, thin film, and organic light emitting device including the same

文档序号：445247 发布日期：2021-12-28 浏览：16次中文

阅读说明：本技术 组合物、薄膜、以及包括组合物和薄膜的有机发光器件 (Composition, thin film, and organic light emitting device including the same ) 是由印守康姜昊锡孙准模李南宪金钟秀金重赫沈明善孙永睦田顺玉许达灏于 2016-09-13 设计创作，主要内容包括：公开组合物、薄膜、以及包括组合物和薄膜的有机发光器件。所述组合物包括给体化合物和受体化合物,其中所述给体化合物和所述受体化合物形成激基复合物。所述激基复合物满足如说明书中所描述的特定的条件。(Disclosed are a composition, a thin film, and an organic light emitting device including the composition and the thin film. The composition includes a donor compound and an acceptor compound, wherein the donor compound and the acceptor compound form an exciplex. The exciplex satisfies specific conditions as described in the specification.)

1. A composition, comprising:

a donor compound and an acceptor compound, wherein,

wherein the donor compound and the acceptor compound form an exciplex,

the exciplex has a maximum emission wavelength in a photoluminescence spectrum of 390 nanometers (nm) or more and 490nm or less,

the decay time of delayed fluorescence in the time-resolved photoluminescence spectrum of the exciplex is 100 nanoseconds (ns) or greater,

the ratio of the delayed fluorescence portion to the total luminescence portion in the time-resolved photoluminescence spectrum of the exciplex is 10% or more,

the exciplex has a photoluminescence stability of 59% or more,

the photoluminescence spectrum and the time-resolved photoluminescence spectrum of the exciplex are each measured at room temperature for a film formed by co-depositing the donor compound and the acceptor compound on a substrate, and

the photoluminescence stability of the exciplex was evaluated according to equation 10:

< equation 10>

Photoluminescence stability (%) ═ (I)₂/I₁)×100

Wherein, in the equation 10,

I₁is an arbitrary unit of intensity of light at a maximum emission wavelength in a photoluminescence spectrum of the film 1, the photoluminescence spectrum of the film 1 being obtained immediately after forming a film by co-depositing the donor compound and the acceptor compound on a substrate, being measured at room temperature in an inert atmosphere in which outside air is shut off, and

I₂is an arbitrary unit of intensity of light at the maximum emission wavelength in the photoluminescence spectrum of the film 2, the photoluminescence spectrum of the film 2 being exposed to I in an inert atmosphere in which the film 1 is shut off from the outside air₁Obtained after 3 hours from the pump laser used in the evaluation of (1), was measured at room temperature in an inert atmosphere in which the outside air was cut off.

2. The composition of claim 1, wherein the maximum emission wavelength is 390nm or more and 440nm or less.

3. The composition of claim 1, wherein

The absolute value of the highest occupied molecular orbital HOMO energy level | HOMO (d) | of the donor compound is 5.78 electron volts (eV) or less,

the absolute value of the lowest unoccupied molecular orbital LUMO level | LUMO (A) | of the acceptor compound is 1.76eV or greater,

HOMO (D) is calculated by using cyclic voltammetry, and

lumo (a) was calculated by using the ultraviolet absorption spectrum measured at room temperature.

4. The composition of claim 1, wherein

An absolute value of a HOMO energy level difference between the acceptor compound and the donor compound | HOMO (A) -HOMO (D) | is 0.037eV or more and 1.1eV or less,

the absolute value of the LUMO level difference between the acceptor compound and the donor compound | LUMO (A) -LUMO (D) | is 0.001eV or more and 1.1eV or less,

HOMO (D) is calculated by using cyclic voltammetry, and

lumo (a) was calculated by using the ultraviolet absorption spectrum measured at room temperature.

5. The composition of claim 1, wherein

The donor compound includes at least one selected from the group consisting of: carbazole-based rings, dibenzofuran-based rings, dibenzothiophene-based rings, indenocarbazole-based rings, indolocarbazole-based rings, benzofurocarbazole-based rings, benzothienocarbazole-based rings, acridine-based rings, and triandolylbenzene-based rings, and

the acceptor compound includes at least one selected from the group consisting of: carbazole-based rings, dibenzofuran-based rings, dibenzothiophene-based rings, indenocarbazole-based rings, indolocarbazole-based rings, benzofurocarbazole-based rings, benzothienocarbazole-based rings, pyridine-based rings, pyrimidine-based rings, and triazine-based rings.

6. The composition of claim 1, wherein

The donor compound does not include an electron withdrawing group, and

the acceptor compound includes at least one electron withdrawing group,

wherein the electron withdrawing group is selected from

-F、-CFH₂、-CF₂H、-CF₃-CN, and-NO₂；

C substituted by at least one member selected from₁-C₆₀Alkyl groups: -F, -CFH₂、-CF₂H、-CF₃-CN, and-NO₂；

Each comprising N as a ring-forming moiety C₁-C₆₀Heteroaryl and monovalent non-aromatic fused polycyclic heterocyclic groups; and

each comprising ═ N —' as a ring-forming moiety and each being substituted with at least one selected from the group consisting of₁-C₆₀Heteroaryl and monovalent non-aromatic fused polycyclic heterocyclic groups: deuterium, -F, -CFH₂、-CF₂H、-CF₃-Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, substituted or unsubstituted C₁-C₆₀Alkyl, substituted or unsubstituted C₂-C₆₀Alkenyl, substituted or unsubstituted C₂-C₆₀Alkynyl, substituted or unsubstituted C₁-C₆₀Alkoxy, substituted or unsubstituted C₃-C₁₀Cycloalkyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkyl, substituted or unsubstituted C₃-C₁₀Cycloalkenyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkenyl, substituted or unsubstituted C₆-C₆₀Aryl, substituted or unsubstituted C₆-C₆₀Aryloxy, substituted or unsubstituted C₆-C₆₀Arylthio, substituted or unsubstituted C₁-C₆₀Heteroaryl, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and substituted or unsubstituted monovalent non-aromatic fused polycyclic groupA heteropolycyclic group.

7. The composition of claim 1, wherein

The donor compound is selected from the group consisting of compounds represented by the formula D-1, and

the acceptor compound is selected from the group consisting of compounds represented by formulas A-1 and A-2:

< formula D-1>

Ar₁-(L₁)_a1-Ar₂

< formula A-1>

Ar₁₁-(L₁₁)_a11-Ar₁₂

< formula A-2>

Wherein, in the formulae D-1, A-2, and 11-14,

Ar₁selected from the group represented by formulas 11 and 12,

Ar₂is selected from

Groups represented by formulas 11 and 12, phenyl, and naphthyl; and

phenyl and naphthyl each substituted with at least one member selected from the group consisting of: deuterium, hydroxy, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl,

Ar₁₁and Ar₁₂Each independently selected from the group represented by formulas 13 and 14,

X₁is N or C (T)₁₄)，X₂Is N or C (T)₁₅)，X₃Is N or C (T)₁₆) Provided that X is₁-X₃At least one of (a) is N,

L₁is selected from

A single bond, a phenylene group, a naphthylene group, a fluorenylene group, a carbazolyl group, a dibenzofuranylene group, and a dibenzothiophenylene group; and

at least one substituted phenylene, naphthylene, fluorenylene, carbazolyl, dibenzofuranylene, and dibenzothiophenylene each selected from the group consisting of: deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

L₁₁-L₁₃Each independently selected from

A single bond, a phenylene group, a pyridylene group, a pyrimidylene group, a pyrazinylene group, a pyridazinylene group, a triazinylene group, a naphthylene group, a fluorenylene group, a carbazolyl group, a dibenzofuranylene group, and a dibenzothiophenylene group; and

at least one substituted phenylene, pyridylene, pyrimidylene, pyrazinylene, pyridazinylene, triazinylene, naphthylene, fluorenylene, carbazolyl, dibenzofuranylene, and dibenzothiophenylene, each selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

a1 and a11-a13 are each independently an integer selected from 0 to 5, and when a1 is 2 or greater, a plurality of L' s₁Same or different from each other, when a11 is 2 or more, a plurality of L₁₁Same or different from each other, when a12 is 2 or more, a plurality of L₁₂Identical to or different from each other when a13 is2 or greater, a plurality of L₁₃Are the same as or different from each other,

CY₁-CY₄each independently selected from a phenyl group, a naphthyl group, a fluorene group, a carbazole group, a benzocarbazole group, an indolocarbazole group, a dibenzofuran group, and a dibenzothiophene group,

A₁is selected from

Single bond, C₁-C₄Alkylene, and C₂-C₄An alkenylene group; and

c each substituted by at least one member selected from the group consisting of₁-C₄Alkylene and C₂-C₄Alkenylene: deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₂₁)(Q₂₂)(Q₂₃)，

A₂Is selected from

Single bond, C₁-C₄Alkylene, and C₂-C₄An alkenylene group; and

c each substituted by at least one member selected from the group consisting of₁-C₄Alkylene and C₂-C₄Alkenylene: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₂₁)(Q₂₂)(Q₂₃)，

R₁、R₁₀And R₂₀Each independently selected from

Hydrogen, deuterium, hydroxy, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl, and C₁-C₂₀An alkoxy group;

each substituted by at least one member selected fromC of (A)₁-C₂₀Alkyl and C₁-C₂₀Alkoxy groups: deuterium, hydroxyl, amino, amidino, hydrazine, hydrazone, carboxylic acid group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl;

phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl;

phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl, each substituted with at least one moiety selected from the group consisting of: deuterium, hydroxy, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl; and

-Si(Q₁)(Q₂)(Q₃)，

T₁₁-T₁₆、R₂、R₃₀and R₄₀Each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, Cyano (CN), nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, and substituted or unsubstituted C₁-C₆₀Alkyl, substituted or unsubstituted C₂-C₆₀Alkenyl, substituted or unsubstituted C₂-C₆₀Alkynyl, substituted or unsubstituted C₁-C₆₀Alkoxy, substituted or unsubstituted C₃-C₁₀Cycloalkyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkyl, substituted or unsubstituted C₃-C₁₀Cycloalkenyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkenyl, substituted or unsubstituted C₆-C₆₀Aryl, substituted or unsubstituted C₆-C₆₀Aryloxy, substituted or unsubstituted C₆-C₆₀Arylthio, substituted or unsubstituted C₁-C₆₀Heteroaryl, substituted or unsubstituted monovalent non-aromatic fused polycyclic radical, substituted or unsubstitutedA monovalent non-aromatic fused heteropolycyclic group of a substituent, and-Si (Q)₁)(Q₂)(Q₃)，

b1-b4 are each independently an integer selected from 0-10, and

said substituted C₁-C₆₀Alkyl, substituted C₂-C₆₀Alkenyl, substituted C₂-C₆₀Alkynyl, substituted C₃-C₁₀Cycloalkyl, substituted C₁-C₁₀Heterocycloalkyl, substituted C₃-C₁₀Cycloalkenyl, substituted C₁-C₁₀Heterocycloalkenyl, substituted C₆-C₆₀Aryl, substituted C₆-C₆₀Aryloxy, substituted C₆-C₆₀Arylthio, substituted C₁-C₆₀At least one of the substituents of the heteroaryl, the substituted monovalent non-aromatic fused polycyclic group, and the substituted monovalent non-aromatic fused heteropolycyclic group is selected from deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, and-Si (Q)₃₁)(Q₃₂)(Q₃₃)，

Wherein Q₁-Q₃、Q₁₁-Q₁₃、Q₂₁-Q₂₃And Q₃₁-Q₃₃Each independently selected from hydrogen, deuterium, C₁-C₆₀Alkyl radical, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical,C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, and a monovalent non-aromatic fused heteropolycyclic group.

8. The composition of claim 7, wherein

Ar₁Selected from the group represented by formulae 11-1 to 11-8 and 12-1 to 12-8,

Ar₂selected from the group represented by the formulae 11-1 to 11-8 and 12-1 to 12-8, phenyl, and naphthyl, and

Ar₁₁and Ar₁₂Each independently selected from the group represented by formulas 13-1 to 13-8 and 14-1 to 14-8:

wherein, in formulae 11-1 to 11-8, 12-1 to 12-8, 13-1 to 13-8, and 14-1 to 14-8,

X₁₁and X₁₃Each independently is C (R)₁₇)(R₁₈)、N(R₁₉) O, or S, in the presence of a catalyst,

X₁₂and X₁₄Each independently is C (R)₃₇)(R₃₈)、N(R₃₉) O, or S, in the presence of a catalyst,

R₁、R₂、A₁and A₂In common with those defined in claim 7,

R₁₁-R₁₉each independently of the other R as defined in claim 7₁₀In the same way, the first and second,

R₂₁-R₂₄each independently of the other R as defined in claim 7₂₀In the same way, the first and second,

R₃₁-R₃₉each independently of the other R as defined in claim 7₃₀In the same way, the first and second,

R₄₁-R₄₄each independently of the other R as defined in claim 7₄₀Are the same as, and

denotes the binding site to the adjacent atom.

9. The composition of claim 8, wherein

A₁Is selected from

Single bond, C₁-C₂Alkylene, and C₂An alkenylene group; and

c each substituted by at least one member selected from the group consisting of₁-C₂Alkylene and C₂Alkenylene: deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₂₁)(Q₂₂)(Q₂₃)，

A₂Is selected from

Single bond, C₁-C₂Alkylene, and C₂An alkenylene group; and

c each substituted by at least one member selected from the group consisting of₁-C₂Alkylene and C₂Alkenylene: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenylNaphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₂₁)(Q₂₂)(Q₂₃) And are and

R₂、R₃₁-R₃₉and R₄₁-R₄₄Each independently selected from

Hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl, and C₁-C₂₀An alkoxy group;

c each substituted by at least one member selected from the group consisting of₁-C₂₀Alkyl and C₁-C₂₀Alkoxy groups: deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl, each substituted with at least one moiety selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃And Q₂₁-Q₂₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical、C₁-C₁₀Alkoxy, phenyl, and naphthyl.

10. The composition of claim 7, wherein

Ar₁Selected from the group represented by formulae 15-1 to 15-17 and 16-1 to 16-8,

Ar₂selected from the group represented by the formulae 15-1 to 15-17 and 16-1 to 16-8, phenyl, and naphthyl, and

Ar₁₁and Ar₁₂Each independently selected from the group represented by formulas 17-1 to 17-3:

wherein, in formulae 15-1 to 15-17, 16-1 to 16-8, and 17-1 to 17-3,

X₁₁and X₁₃Each independently is C (R)₁₇)(R₁₈)、N(R₁₉) O, or S, in the presence of a catalyst,

r 'and R' are each independently selected from hydrogen, deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl,

R₁、R₁₀、R_10a-R_10cand R₂₀Each independently selected from hydrogen, deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁)(Q₂)(Q₃) And are and

R₃₀and R₄₀Each independently selected from

Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl, each substituted with at least one moiety selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl.

11. The composition of claim 7, wherein

i) The donor compound is represented by formula D-1, with the proviso that the donor compound is selected from L in formula D-1₁A compound which is a single bond; or

ii) said donor compound is selected from compounds represented by formulae D-1(1) to D-1 (52):

wherein, in the formulae D-1(1) to D-1(52),

Ar₁and Ar₂In common with those defined in claim 7,

Y₅₁each independently is C (Z)₅₃)(Z₅₄)、N(Z₅₅) O, or S, and

Z₅₁-Z₅₆each independently selected from hydrogen, deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

Wherein Q₁₁-Q₁₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl.

12. The composition of claim 7, wherein

L₁₁-L₁₃Each independently selected from the group represented by formulas 3-1 to 3-56, and i) L in an amount of a11₁₁Ii) a number of L of a12₁₂And iii) a number of L of a13₁₃Each of which is independently selected from the group represented by formulas 3-15 to 3-56:

wherein, in formulae 3-1 to 3-56,

Y₁selected from O, S, C (Z)₃)(Z₄) And N (Z)₅)，

Z₁-Z₅Each independently selected from the group consisting of hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

Wherein Q₁₁-Q₁₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl,

d4 is an integer selected from 0-4,

d3 is an integer selected from 0-3,

d2 is an integer selected from 0-2, and

each of x and x' represents a binding site to an adjacent atom.

13. Such as rightThe composition of claim 7, wherein the composition is prepared from: - (L)₁₁)_a11-*'、*-(L₁₂)_a12-, and- (L)₁₃)_a13The group represented by-' is selected from the group represented by the formulae 4-1 to 4-39:

wherein, in formulae 4-1 to 4-39,

X₂₁is N or C (Z)₂₁)，X₂₂Is N or C (Z)₂₂)，X₂₃Is N or C (Z)₂₃)，X₂₄Is N or C (Z)₂₄)，X₃₁Is N or C (Z)₃₁)，X₃₂Is N or C (Z)₃₂)，X₃₃Is N or C (Z)₃₃)，X₃₄Is N or C (Z)₃₄)，X₄₁Is N or C (Z)₄₁)，X₄₂Is N or C (Z)₄₂)，X₄₃Is N or C (Z)₄₃) And X₄₄Is N or C (Z)₄₄) Provided that X is₂₁-X₂₄Is not N, X₃₁-X₃₄Is not N, and X₄₁-X₄₄Is not N, but is not N,

Z₂₁-Z₂₄、Z₃₁-Z₃₄and Z₄₁-Z₄₄Each independently selected from the group consisting of hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

each of x and x' represents a binding site to an adjacent atom.

14. The composition of claim 1, wherein T is₁₁-T₁₆Each independently selected from

Hydrogen, deuterium, -F, cyano, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H. and-CFH₂；

C each substituted by at least one member selected from the group consisting of₁-C₁₀Alkyl and C₁-C₁₀Alkoxy groups: deuterium, -F, cyano, -CF₃、-CF₂H. and-CFH₂；

Phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

at least one substituted phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl each selected from the group consisting of: deuterium, -F, cyano, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl.

15. The composition of claim 7, wherein

i) The receptor compound is represented by formula a-1, with the proviso that the receptor compound is selected from the group consisting of: wherein Ar in formula A-1₁₁And Ar₁₂Each independently selected from the group represented by formulas 17-1 to 17-3, and Ar₁₁And Ar₁₂At least one selected from the group represented by formulas 17-2 and 17-3;

ii) the receptor compound is represented by formula a-1, with the proviso that the receptor compound is selected from the group consisting of: wherein L in the formula A-1₁₁L selected from the group represented by formulas 3 to 15 and 3 to 28 and having a number of a11₁₁At least one selected from the group represented by formulas 6-1 to 6-4; or

iii) the receptor compound is represented by formula A-2, with the proviso that the receptor compound is selected from the following compounds: wherein X in the formula A-2₁-X₃Are all N:

wherein, in formulae 17-1 to 17-3, 3-15, 3-28, and 6-1 to 6-4,

R₃₀and R₄₀Each independently selected from

Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl, each substituted with at least one moiety selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

Z₁selected from the group consisting of hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

d4 is an integer selected from 0-4,

t1 is an integer selected from 1 and 2,

wherein Q₁-Q₃And Q₁₁-Q₁₃Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl, and

each of x and x' represents a binding site to an adjacent atom.

16. The composition of claim 1 wherein the donor compound is selected from compounds D1-D16 and the acceptor compound is selected from compounds a1-a 11:

17. a film comprising the composition of any one of claims 1-16.

18. An organic light emitting device, comprising:

a first electrode;

a second electrode; and

an organic layer between the first electrode and the second electrode,

wherein the organic layer comprises a film comprising the composition of any one of claims 1-16.

19. The organic light emitting device of claim 18, wherein the exciplex in the composition is a thermally activated delayed fluorescence emitter.

20. An organic light-emitting device according to claim 18 wherein the thin film comprises a composition according to any of claims 1 to 16 and is an emissive layer.

21. The organic light emitting device of claim 20, wherein the light emitted from the emissive layer is blue light, wherein the maximum emission wavelength of the blue light is in the range of 390nm-490nm, the X coordinate of the blue light in CIE color coordinates is in the range of 0.182-0.307, and the Y coordinate of the blue light in CIE color coordinates is in the range of 0.092-0.523.

22. The organic light emitting device of claim 18, wherein the thin film further comprises a fluorescent dopant.

23. An organic light emissive device according to claim 22, wherein

The maximum emission wavelength in the photoluminescence spectrum of the exciplex is less than the maximum emission wavelength in the photoluminescence spectrum of the fluorescent dopant,

the photoluminescence spectrum of the exciplex is a spectrum measured at room temperature for a film formed by co-depositing the donor compound and the acceptor compound on a substrate, and

the photoluminescence spectrum of the fluorescent dopant is a spectrum measured at room temperature for a film formed by depositing the fluorescent dopant on a substrate.

24. The organic light emitting device of claim 23, wherein the fluorescent dopant is selected from compounds represented by formula 501:

< equation 501>

Wherein, in the formula 501,

Ar₅₀₁is selected from

Naphthyl, heptalenyl, fluorenyl, spiro-dibenzofluorenyl, carbazolyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthryl, anthracyl, fluoranthenyl, benzo [9,10 ]]Phenanthryl, pyrenyl,Phenyl, tetracenyl, picenyl, peryleneyl, pentylphenyl, and indenonanthracenyl; and

naphthyl, heptenylene, fluorenyl, spiro-dibenzofluorenyl, carbazolyl, benzofluorenyl, dibenzofluorenyl, phenalkenyl, phenanthrenyl, anthracenyl, fluoranthenyl, benzo [9,10 ] substituted by at least one member selected from the group consisting of]Phenanthryl, pyrenyl,Phenyl, tetracenyl, picenyl, peryleneyl, pentylphenyl, and indenonanthracenyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, and-Si (Q)₅₀₁)(Q₅₀₂)(Q₅₀₃) Wherein Q is₅₀₁-Q₅₀₃Each independently selected from hydrogen and C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₆-C₆₀Aryl, and C₁-C₆₀(ii) a heteroaryl group, wherein,

L₅₀₁-L₅₀₃each independently selected from substituted or unsubstituted C₃-C₁₀Cycloalkylene, substituted or unsubstituted C₁-C₁₀Heterocycloalkylene, substituted or unsubstituted C₃-C₁₀Cycloalkenylene, substituted or unsubstituted C₁-C₁₀Heterocycloalkenylene, substituted or unsubstituted C₆-C₆₀Arylene, substituted or unsubstituted C₁-C₆₀A heteroarylene group, a substituted or unsubstituted divalent non-aromatic fused polycyclic group, and a substituted or unsubstituted divalent non-aromatic fused heteropolycyclic group,

R₅₀₁and R₅₀₂Each independently selected from

Phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, anthracenyl, pyrenyl,A phenyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolinyl group, a carbazolyl group, a triazinyl group, a dibenzofuranyl group, and a dibenzothiophenyl group; and at least one substituted phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracyl, pyrenyl, fluorenyl, or the like, each of which is selected,Phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, triazinyl, dibenzofuranyl, and dibenzothienyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracyl, pyrenyl,Pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, triazinyl, dibenzofuranyl, and dibenzothienyl,

each xd1-xd3 is independently selected from 0, 1, 2, and 3, and

xd4 is selected from 0, 1, 2,3, 4, 5, and 6.

25. The organic light-emitting device of claim 22, wherein the fluorescent dopant comprises at least one compound selected from the compounds FD (1) -FD (5) and FD1-FD 8:

Technical Field

The present disclosure relates to compositions, thin films, and organic light emitting devices.

Background

The organic light emitting device is a self-emission device and has a wide viewing angle, a high contrast ratio, a short response time, and excellent luminance, driving voltage, and response speed characteristics compared to devices in the art and produces a full color image.

A typical OLED includes an anode, a cathode, and an organic layer between the anode and the cathode and including an emissive layer. The hole transport region may be between the anode and the emissive layer, and the electron transport region may be between the emissive layer and the cathode. Holes supplied from the anode may move toward the emission layer through the hole transport region, and electrons supplied from the cathode may move toward the emission layer through the electron transport region. Carriers such as holes and electrons recombine in the emission layer to generate excitons. These excitons transition from an excited state to a ground state, thereby generating light.

Disclosure of Invention

Providing a composition that provides exciplex satisfying specific conditions; a film comprising the composition; and an organic light emitting device including the composition, thus having a low driving voltage, high emission efficiency, high luminance, and a long lifetime.

Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments.

According to an aspect of one embodiment, the composition comprises:

a donor compound and an acceptor compound, wherein,

wherein the donor compound and the acceptor compound form an exciplex,

a maximum emission wavelength (λ) in a Photoluminescence (PL) spectrum of the exciplex_{Maximum of}(Ex)) is about 390 nanometers (nm) or more and about 490nm or less,

decay time (T) of delayed fluorescence in time-resolved photoluminescence (TRPL) spectra of the exciplex_{Attenuation of}(Ex)) is about 100 nanoseconds (ns) or greater,

the exciplex has a ratio of delayed fluorescence moiety to total luminescence moiety in the TRPL spectrum of about 10% or more,

the exciplex has a PL stability of 59% or greater,

the PL spectrum and TRPL spectrum of the exciplex are each a spectrum measured at room temperature for a film formed by co-depositing the donor compound and the acceptor compound on a substrate, and

the PL stability of the exciplex was evaluated according to < equation 10 >:

< equation 10>

PL stability (%) - (I)₂/I₁)×100

Wherein, in the equation 10,

I₁is the maximum emission wavelength (lambda) in the PL spectrum of the film 1_{Maximum of}(Ex)), the PL spectrum of the film 1, obtained immediately after the formation of the film by co-deposition of the donor compound and the acceptor compound on a substrate, is measured at room temperature in an inert atmosphere in which the external air is cut off, and

I₂is the maximum emission in the PL spectrum of the film 2Wavelength of radiation (λ)_{Maximum of}(Ex)), the PL spectrum of the film 2 is exposed to I in an inert atmosphere in which the film 1 is cut off from the outside air₁Obtained after 3 hours from the pump laser (pumping laser light) used in the evaluation of (1), measured at room temperature in an inert atmosphere in which the outside air was cut off.

According to an aspect of another embodiment, a film comprises the composition.

According to an aspect of another embodiment, an organic light emitting device includes a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises a thin film comprising the composition.

Drawings

These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment;

FIGS. 2A to 2E are graphs of photoluminescence spectra of the films measured in evaluation example 1;

FIGS. 3A-3G are graphs of time-resolved photoluminescence (TRPL) spectra of films measured in evaluation example 1; and

FIGS. 4A-4D are graphs of PL spectra measured immediately after formation of each of film D3: A3, TCTA: BmPyPb, CBP: B3PYMPM, and TCTA:3TPYMB ("as prepared"), and three hours after exposure to a laser ("3 hours exposed").

Detailed Description

Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as limited to the descriptions set forth herein. Accordingly, the embodiments are described below to illustrate aspects only by referring to the drawings. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The expression "at least one" of an expression such as "modifies an entire list of elements when preceding or following the list of elements rather than modifying individual elements of the list.

A composition (e.g., mixture) can include a donor compound and an acceptor compound, and the donor compound and the acceptor compound can form an exciplex. For example, the composition (e.g., mixture) can be comprised of a donor compound and an acceptor compound, and the donor compound and the acceptor compound can form an exciplex.

The donor compound may be an electron donor compound in which an electron-donating property is dominant over an electron-accepting property, and the acceptor compound may be an electron acceptor compound in which an electron-accepting property is dominant over an electron-donating property, wherein the donor compound may be a hole-transporting compound and the acceptor compound may be an electron-transporting compound.

The exciplex can be an excited state complex formed between the donor compound and the acceptor compound.

In the composition, the exciplex has a maximum emission wavelength (λ) of Photoluminescence (PL) spectrum_{Maximum of}(Ex)) may be about 390 nanometers (nm) or more and about 490nm or less, in some embodiments about 390nm or more and about 450nm or less, in some embodiments about 390nm or more and about 440nm or less, and in some embodiments, about 390nm or more and about 410nm or less. In this case, the composition may emit blue light. For example, the composition can emit blue light having an X coordinate in CIE color coordinates in the range of about 0.182 to about 0.307 and a Y coordinate in CIE color coordinates in the range of about 0.092 to about 0.523. Therefore, when the composition is used in an electronic device such as an organic light emitting device, the electronic device can emit blue light of high color purity.

In the composition, the decay time (T) of delayed fluorescence in a time-resolved photoluminescence (TRPL) spectrum of the exciplex_{Attenuation of}(Ex)) may be about 100 nanoseconds (ns) or greater, in some embodiments about 150ns or greater, and in some embodiments, about 100ns or greater and about10 milliseconds (ms) or less. The ratio of the delayed fluorescence moiety to the total luminescent moiety in the TRPL spectrum of the exciplex can be about 10% or greater, and in some embodiments about 15% or greater. Therefore, up-conversion (up-conversion) of the exciplex from a triplet state to a singlet state can occur efficiently, and thus high-efficiency delayed fluorescence can be emitted. Therefore, when the composition is used, a high efficiency electronic device such as a high efficiency organic light emitting device can be realized.

The PL spectrum and the TRPL spectrum of the exciplex may each be a spectrum measured at room temperature for a film formed by co-depositing the donor compound and the acceptor compound on a substrate (e.g., a quartz substrate). This can be understood by reference to the following examples and evaluation examples.

T_{Attenuation of}(Ex) can be assessed by using one or more suitable methods using TRPL spectroscopy. E.g. T_{Attenuation of}(Ex) may be evaluated by using the method described in evaluation example 1, but the embodiment is not limited thereto.

The ratio of delayed fluorescence moieties (DF moieties) can be assessed by using one or more suitable methods using TRPL spectroscopy. For example, the ratio of delayed fluorescence part may be evaluated by using the method described in evaluation example 1, but the embodiment is not limited thereto.

The PL stability of the exciplex of the composition may be about 59% or greater, in some embodiments about 60% or greater, and in some embodiments, about 70% or greater. According to one embodiment, the PL stability of the exciplex of the composition may be about 80% or greater, and in some embodiments about 90% or greater. When the exciplex of the composition has PL stability within these ranges, an organic light emitting device employing the composition may have a long lifetime.

The PL stability of the exciplex can be evaluated according to < equation 10 >:

< equation 10>

PL stability (%) - (I)₂/I₁)×100

Wherein, in the equation 10,

I₁may be the maximum emission wavelength (λ) in the PL spectrum of the film 1_{Maximum of}(Ex)), the PL spectrum of the film 1, obtained immediately after the formation of the film by co-deposition of the donor compound and the acceptor compound on a substrate, is measured at room temperature in an inert atmosphere in which the external air is cut off, and

I₂may be the maximum emission wavelength (λ) in the PL spectrum of the film 2_{Maximum of}(Ex)), the PL spectrum of the film 2 is exposed to I in an inert atmosphere in which the film 1 is cut off from the outside air₁Obtained after 3 hours from the pump laser used in the evaluation of (1), was measured at room temperature in an inert atmosphere in which the outside air was cut off.

Embodiments of PL stability evaluation will be described with reference to examples and evaluation examples.

According to one embodiment, the absolute value of the Highest Occupied Molecular Orbital (HOMO) level (| HOMO (d) |) of the donor compound may be about 5.78 electron volts (eV) or less, and in some embodiments about 4.84eV or more and about 5.78eV or less. According to one embodiment, the absolute value of the Lowest Unoccupied Molecular Orbital (LUMO) level (| LUMO (a) |) of the acceptor compound may be about 1.76eV or greater, and in some embodiments about 2.43eV or less and about 1.76eV or greater. Accordingly, exciplex formation efficiency in the composition may be increased, and thus, an electronic device, such as an organic light emitting device, including the composition may have improved efficiency and lifetime.

Homo (d) can be measured by using Cyclic Voltammetry (CV), and lumo (a) can be measured by using UV absorption spectroscopy measured at room temperature. This will be understood with reference to the following examples.

In various embodiments, the absolute value of the HOMO level difference between the acceptor compound and the donor compound (| HOMO (a) -HOMO (d) |) may be about 0.037eV or more and about 1.1eV or less, and in some embodiments about 0.04eV or more and about 0.9eV or less. In various embodiments, the absolute value of the LUMO level difference between the acceptor compound (| LUMO (a) -LUMO (d) |) and the donor compound may be about 0.001eV or more and about 1.1eV or less, and in some embodiments about 0.01eV or more and about 0.9eV or less. Thus, hole transport through the donor compound and electron transport through the acceptor compound can occur efficiently, resulting in efficient formation of an exciplex at the interface between the donor compound and the acceptor compound. Accordingly, electronic devices, such as organic light emitting devices, including the composition may have improved efficiency and lifetime.

The donor compound may include at least one selected from the group consisting of: carbazole-based rings, dibenzofuran-based rings, dibenzothiophene-based rings, indenocarbazole-based rings, indolocarbazole-based rings, benzofurocarbazole-based rings, benzothienocarbazole-based rings, acridine-based rings, and triandolylbenzene-based rings, and

the acceptor compound may include at least one selected from the group consisting of: carbazole-based rings, dibenzofuran-based rings, dibenzothiophene-based rings, indenocarbazole-based rings, indolocarbazole-based rings, benzofurocarbazole-based rings, benzothienocarbazole-based rings, pyridine-based rings, pyrimidine-based rings, and triazine-based rings.

For example, the donor compound may not include an electron withdrawing group, and

the acceptor compound may include at least one electron withdrawing group,

wherein the electron withdrawing group may be selected from

-F、-CFH₂、-CF₂H、-CF₃-CN, and-NO₂；

C substituted by at least one member selected from₁-C₆₀Alkyl groups: -F, -CFH₂、-CF₂H、-CF₃-CN, and-NO₂；

Each comprising N as a ring-forming moiety C₁-C₆₀Heteroaryl and monovalent non-aromatic fused polycyclic heterocyclic groups; and

each comprising ═ N —' as a ring-forming moiety and each being substituted with at least one selected from the group consisting of₁-C₆₀Heteroaryl and monovalent non-aromatic fused polycyclic heterocyclic groups: deuterium, -F, -CFH₂、-CF₂H、-CF₃-Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, substituted or unsubstituted C₁-C₆₀Alkyl, substituted or unsubstituted C₂-C₆₀Alkenyl, substituted or unsubstituted C₂-C₆₀Alkynyl, substituted or unsubstituted C₁-C₆₀Alkoxy, substituted or unsubstituted C₃-C₁₀Cycloalkyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkyl, substituted or unsubstituted C₃-C₁₀Cycloalkenyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkenyl, substituted or unsubstituted C₆-C₆₀Aryl, substituted or unsubstituted C₆-C₆₀Aryloxy, substituted or unsubstituted C₆-C₆₀Arylthio, substituted or unsubstituted C₁-C₆₀A heteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

According to one embodiment, the donor compound may be selected from compounds represented by the formula D-1, and

the acceptor compound may be selected from compounds represented by formulas A-1 and A-2:

< formula D-1>

Ar₁-(L₁)_a1-Ar₂

< formula A-1>

Ar₁₁-(L₁₁)_a11-Ar₁₂

< formula A-2>

Wherein, in the formulae D-1, A-2, and 11-14,

Ar₁may be selected from the group represented by formulas 11 and 12,

Ar₂can be selected from

Groups represented by formulas 11 and 12, phenyl, and naphthyl; and

Ar₁₁and Ar₁₂May be each independently selected from the group represented by formulas 13 and 14,

X₁can be N or C (T)₁₄)，X₂Can be N or C (T)₁₅) And X₃Can be N or C (T)₁₆) Provided that X is₁-X₃At least one of (a) may be N,

L₁can be selected from

A single bond, a phenylene group, a naphthylene group, a fluorenylene group, a carbazolyl group, a dibenzofuranylene group, and a dibenzothiophenylene group; and

phenylene, pyridylene, pyrimidylene, pyridylene each substituted by at least one member selected from the group consisting ofOxazinyl, pyridazinyl, triazinylene, naphthylene, fluorenylene, carbazolyl, dibenzofuranylene, and dibenzothiophenylene: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

a1 and a11-a13 may each independently be an integer selected from 0 to 5, and when a1 is 2 or greater, a plurality of L' s₁May be the same as or different from each other, when a11 is 2 or more, a plurality of L₁₁May be the same as or different from each other, when a12 is 2 or more, a plurality of L₁₂May be the same as or different from each other, when a13 is 2 or more, a plurality of L₁₃May be the same as or different from each other,

A₁can be selected from

Single bond, C₁-C₄Alkylene, and C₂-C₄An alkenylene group; and

A₂Can be selected from

Single bond, C₁-C₄Alkylene, and C₂-C₄An alkenylene group; and

R₁、R₁₀And R₂₀Can be independently selected from

c each substituted by at least one member selected from the group consisting of₁-C₂₀Alkyl and C₁-C₂₀Alkoxy groups: deuterium, hydroxyl, amino, amidino, hydrazine, hydrazone, carboxylic acid group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl;

phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl;

-Si(Q₁)(Q₂)(Q₃)，

T₁₁-T₁₆、R₂、R₃₀and, andR₄₀each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, Cyano (CN), nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, and substituted or unsubstituted C₁-C₆₀Alkyl, substituted or unsubstituted C₂-C₆₀Alkenyl, substituted or unsubstituted C₂-C₆₀Alkynyl, substituted or unsubstituted C₁-C₆₀Alkoxy, substituted or unsubstituted C₃-C₁₀Cycloalkyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkyl, substituted or unsubstituted C₃-C₁₀Cycloalkenyl, substituted or unsubstituted C₁-C₁₀Heterocycloalkenyl, substituted or unsubstituted C₆-C₆₀Aryl, substituted or unsubstituted C₆-C₆₀Aryloxy, substituted or unsubstituted C₆-C₆₀Arylthio, substituted or unsubstituted C₁-C₆₀A heteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group, and-Si (Q)₁)(Q₂)(Q₃)，

b1-b4 may each independently be an integer selected from 0-10, and

said substituted C₁-C₆₀Alkyl, substituted C₂-C₆₀Alkenyl, substituted C₂-C₆₀Alkynyl, substituted C₃-C₁₀Cycloalkyl, substituted C₁-C₁₀Heterocycloalkyl, substituted C₃-C₁₀Cycloalkenyl, substituted C₁-C₁₀Heterocycloalkenyl, substituted C₆-C₆₀Aryl, substituted C₆-C₆₀Aryloxy, substituted C₆-C₆₀Arylthio, substituted C₁-C₆₀At least one substituent of the heteroaryl, substituted monovalent non-aromatic fused polycyclic group, and substituted monovalent non-aromatic fused heteropolycyclic group may be selected from deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereofSalts thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, and-Si (Q)₃₁)(Q₃₂)(Q₃₃)，

Wherein Q₁-Q₃、Q₁₁-Q₁₃、Q₂₁-Q₂₃And Q₃₁-Q₃₃Can be independently selected from hydrogen, deuterium and C₁-C₆₀Alkyl radical, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, and a monovalent non-aromatic fused heteropolycyclic group.

For example, Ar in the formula D-1₁May be selected from the group represented by the formulae 11-1 to 11-8 and 12-1 to 12-8,

ar in the formula D-1₂Can be selected from the group represented by the formulae 11-1 to 11-8 and 12-1 to 12-8, phenyl, and naphthyl, and

ar in the formula A-1₁₁And Ar₁₂May be each independently selected from the group represented by formulae 13-1 to 13-8 and 14-1 to 14-8:

wherein, in formulae 11-1 to 11-8, 12-1 to 12-8, 13-1 to 13-8, and 14-1 to 14-8,

X₁₁and X₁₃May each independently be C (R)₁₇)(R₁₈)、N(R₁₉) O, or S, in the presence of a catalyst,

X₁₂and X₁₄May each independently be C (R)₃₇)(R₃₈)、N(R₃₉) O, or S, in the presence of a catalyst,

R₁、R₂、A₁and A₂May be the same as those defined herein,

R₁₁-R₁₉may be related to R herein₁₀The same as that described above is true for the description,

R₂₁-R₂₄may be related to R herein₂₀The same as that described above is true for the description,

R₃₁-R₃₉may be related to R herein₃₀The same as that described above is true for the description,

R₄₁-R₄₄may be related to R herein₄₀Are the same as described, and

denotes the binding site to the adjacent atom.

In some embodiments, A in formulas 11, 12, 11-1 to 11-8, and 12-1 to 12-8₁Can be selected from

Single bond, C₁-C₂Alkylene, and C₂An alkenylene group; and

A in formulae 13, 14, 13-1 to 13-8, and 14-1 to 14-8₂Can be selected from

Single bond, C₁-C₂Alkylene, and C₂An alkenylene group; and

c each substituted by at least one member selected from the group consisting of₁-C₂Alkylene and C₂Alkenylene: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₂₁)(Q₂₂)(Q₂₃)，

R in formulae 13, 14, 13-1 to 13-8, and 14-1 to 14-8₂、R₃₀-R₃₉And R₄₀-R₄₄Can be independently selected from

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃And Q₂₁-Q₂₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl, but the embodiment is not limited thereto.

According to one embodiment, Ar in formula D-1₁May be selected from the group represented by the formulae 15-1 to 15-17 and 16-1 to 16-8,

ar in the formula D-1₂Can be selected from the group represented by the formulae 15-1 to 15-17 and 16-1 to 16-8, phenyl, and naphthyl, and

ar in the formula A-1₁₁And Ar₁₂May be each independently selected from groups represented by formulae 17-1 to 17-3, but the embodiment is not limited thereto:

wherein, in formulae 15-1 to 15-17, 16-1 to 16-8, and 17-1 to 17-3,

X₁₁and X₁₃May each independently be C (R)₁₇)(R₁₈)、N(R₁₉) O, or S, in the presence of a catalyst,

r 'and R' may each independently be selected from hydrogen, deuterium, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl,

R₁、R₁₀、R₂₀、R₃₀and R₄₀May be the same as those described herein, and

R_10a-R_10cmay be related to R herein₁₀The same is described.

In some embodiments, in formulae 15-1 to 15-17, 16-1 to 16-8, and 17-1 to 17-3,

R₁、R₁₀、R_10a-R_10cand R₂₀Can be independently selected from hydrogen, deuterium and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁)(Q₂)(Q₃)，

R₃₀And R₄₀Can be independently selected from

Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, each substituted with at least one member selected from the group consisting ofDibenzofuranyl, and dibenzothienyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl, but the embodiment is not limited thereto.

In some embodiments of the present invention, the substrate is,

i) the donor compound may be represented by formula D-1, with the proviso that the donor compound may be selected from L in formula D-1₁A compound which is a single bond; or

ii) said donor compound may be selected from compounds represented by formulae D-1(1) to D-1 (52):

wherein, in the formulae D-1(1) to D-1(52),

Ar₁and Ar₂May be the same as those described herein,

Y₅₁may each independently be C (Z)₅₃)(Z₅₄)、N(Z₅₅) O, or S, and

Z₅₁-Z₅₆can be independently selected from hydrogen, deuterium and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

Wherein Q₁₁-Q₁₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, and naphthyl.

In some embodiments, in formulas D-1(1) through D-1(52),

Ar₁can be selected from the group represented by formulas 11 and 12, and

Ar₂can be selected from

Groups represented by formulas 11 and 12, phenyl, and naphthyl; and

According to some embodiments, in formulae D-1(1) to D-1(52),

Ar₁may be selected from the group represented by the formulae 11-1 to 11-8 and 12-1 to 12-8, and

Ar₂groups represented by formulas 11-1 to 11-8 and 12-1 to 12-8, phenyl, and naphthyl may be selected, but the embodiment is not limited thereto.

L in the formulae A-1 and A-2₁₁-L₁₃May each independently be selected from the group represented by formulas 3-1 to 3-56, and i) L in an amount of a11₁₁Ii) a number of L of a12₁₂And iii) a number ofL of a13₁₃May be each independently selected from groups represented by formulae 3-15 to 3-56:

wherein, in formulae 3-1 to 3-56,

Y₁can be selected from O, S, C (Z)₃)(Z₄) And N (Z)₅)，

Z₁-Z₅Each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

Wherein Q₁₁-Q₁₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothienyl,

d4 can be an integer selected from 0-4,

d3 can be an integer selected from 0-3,

d2 can be an integer selected from 0-2, an

Each of x and x' represents a binding site to an adjacent atom.

According to some embodiments, the compounds of formulae a-1 and a-2 are represented by — (L)₁₁)_a11-*'、*-(L₁₂)_a12-, and- (L)₁₃)_a13The group represented by-' may be selected from groups represented by the formulae 4-1 to 4-39:

wherein, in formulae 4-1 to 4-39,

X₂₁can be N or C (Z)₂₁)，X₂₂Can be N or C (Z)₂₂)，X₂₃Can be N or C (Z)₂₃)，X₂₄Can be N or C (Z)₂₄)，X₃₁Can be N or C (Z)₃₁)，X₃₂Can be N or C (Z)₃₂)，X₃₃Can be N or C (Z)₃₃)，X₃₄Can be N or C (Z)₃₄)，X₄₁Can be N or C (Z)₄₁)，X₄₂Can be N or C (Z)₄₂)，X₄₃Can be N or C (Z)₄₃) And X₄₄Can be N or C (Z)₄₄) Provided that X is₂₁-X₂₄At least one of (a) and (b) may not be N, X₃₁-X₃₄At least one of (a) and (b) cannot be N, and X₄₁-X₄₄At least one of (a) may not be N,

Z₂₁-Z₂₄、Z₃₁-Z₃₄and Z₄₁-Z₄₄Each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, cyano-substituted phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and-Si (Q)₁₁)(Q₁₂)(Q₁₃)，

each of x and x' represents a binding site to an adjacent atom.

T in the formula A-2₁₁-T₁₆Can be independently selected from

C each substituted by at least one member selected from the group consisting of₁-C₁₀Alkyl and C₁-C₁₀Alkoxy groups: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, -CF₃、-CF₂H. and-CFH₂；

Phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

phenyl, naphthyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl, each substituted with at least one moiety selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylAcid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H、-CFH₂Phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl; and

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, fluorenyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl.

In some embodiments, T in formula A-2₁₁-T₁₆Can be independently selected from

Hydrogen, deuterium, -F, cyano, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, -CF₃、-CF₂H. and-CFH₂；

C each substituted by at least one member selected from the group consisting of₁-C₁₀Alkyl and C₁-C₁₀Alkoxy groups: deuterium, -F, cyano, -CF₃、-CF₂H. and-CFH₂；

Phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl;

-Si(Q₁)(Q₂)(Q₃)，

wherein Q₁-Q₃Can be independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, phenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, dibenzofuranyl, and dibenzothiophenyl.

In some embodiments of the present invention, the substrate is,

i) the acceptor compound may be represented by formula a-1, with the proviso that the acceptor compound may be selected from the following compounds: wherein Ar in formula A-1₁₁And Ar₁₂May each be independently selected from the group represented by the formulae 17-1 to 17-3, and Ar₁₁And Ar₁₂At least one selected from the group represented by formulas 17-2 and 17-3;

ii) the acceptor compound may be represented by formula a-1, with the proviso that the acceptor compound may be selected from the following compounds: wherein L in the formula A-1₁₁May be selected from the group represented by formulas 3-15 and 3-28, and the number of L is a11₁₁At least one selected from the group represented by formulas 6-1 to 6-4; or

iii) the acceptor compound may be represented by formula A-2, with the proviso that the acceptor compound may be selected from the group consisting of X in formula A-2₁-X₃A compound that may be all N, but the embodiment is not limited thereto.

According to some embodiments, the donor compound may be selected from compounds D1-D16, and the acceptor compound may be selected from compounds a1-a11, but embodiments are not limited thereto:

the composition can be used to form a film. Thus, a film comprising the composition may be provided. In some embodiments, the film can include (e.g., consist of) the composition. In some embodiments, the thin film may include the composition and a fluorescent dopant or the composition and a phosphorescent dopant. In some embodiments, the thin film may be composed of the composition and a fluorescent dopant or the composition and a phosphorescent dopant, but the embodiments are not limited thereto.

The compositions are useful in emissive layers of electronic devices, such as organic light emitting devices. Thus, according to another aspect, there is provided an organic light emitting device comprising: a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode, wherein the organic layer may include a thin film including the composition.

The organic light emitting device may include a thin film including the composition, thereby having a low driving voltage, high efficiency, and a long lifetime. The thin film comprising the composition in the organic light emitting device may be, for example, an emission layer.

Thus, according to an embodiment, the organic light emitting device may include an emission layer including the composition.

The exciplex in the composition included in the emissive layer may have a T of about 100ns or greater (e.g., about 150ns or greater)_{Attenuation of}(Ex), and thus, the exciplex may be, for example, a thermally activated delayed fluorescence emitter (TADF).

According to an embodiment, the emissive layer may comprise (e.g. consist of) the composition.

In some embodiments, in an organic light emitting device whose emission layer includes the composition, light emitted from the emission layer may be blue light, wherein a maximum emission wavelength of the blue light may be in a range of about 390nm to about 490nm, an X coordinate of the blue light in CIE color coordinates may be in a range of about 0.182 to about 0.307, and a Y coordinate of the blue light in CIE color coordinates may be in a range of about 0.092 to about 0.523. Therefore, the organic light emitting device may emit blue light having high color purity.

In various embodiments, the emissive layer may further comprise a fluorescent dopant in addition to the composition. In this case, in the emission layer, the amount of the composition may be greater than the amount of the fluorescent dopant.

In some embodiments, the exciplex has a wavelength of maximum emission (λ) in the PL spectrum of the exciplex_{Maximum of}(Ex)) may be less than a maximum emission wavelength (λ) in a PL spectrum of the fluorescent dopant_{Maximum of}(FD)). Accordingly, energy may be transferred from the composition to the fluorescent dopant, and thus, an emission mechanism in the emission layer may mainly depend on energy transfer of the fluorescent dopant from an excited state to a ground state. In other words, the composition in the emission layer may function as a so-called auxiliary dopant in delaying fluorescence, and thus, the emission color of the fluorescent dopant may determine the emission color of the emission layer. In some embodiments, when the fluorescent dopant is a green dopant, the emission layer may emit green light.

The PL spectrum of the exciplex may be a spectrum measured at room temperature for a film formed by co-depositing the donor compound and the acceptor compound on a substrate, and the PL spectrum of the fluorescent dopant may be a spectrum measured at room temperature for a film formed by depositing the fluorescent dopant on a substrate.

Fig. 1 is a schematic view of an organic light emitting device 10 according to an embodiment. Hereinafter, a structure of an organic light emitting device according to an embodiment and a method of manufacturing the organic light emitting device according to the embodiment will be described with reference to fig. 1. The organic light emitting device 10 includes: a first electrode 11, an organic layer 15, and a second electrode 19, which are sequentially stacked in the stated order.

A substrate may be additionally disposed under the first electrode 11 or over the second electrode 19. Any substrate used in a general organic light emitting device may be used as the substrate, and the substrate may be a glass substrate or a transparent plastic substrate, each of which has excellent mechanical strength, thermal stability, transparency, surface smoothness, easy operability, and water resistance.

The first electrode 11 may be formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. Material for forming the first electrode 11The material may be selected from materials having a high work function to facilitate hole injection. The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. The material for forming the first electrode 11 may be, for example, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin oxide (SnO)₂) And zinc oxide (ZnO). In various embodiments, magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), or magnesium-silver (Mg-Ag) may be used as a material for forming the first electrode 11.

The first electrode 11 may have a single-layer structure or a multi-layer structure including two or more layers. For example, the first electrode 11 may have a three-layer structure of ITO/Ag/ITO, but the structure of the first electrode 11 is not limited thereto.

The organic layer 15 may be disposed on the first electrode 11.

The organic layer 15 may include a hole transport region, an emission layer, and an electron transport region.

The hole transport region may be between the first electrode 11 and the emissive layer.

The hole transport region may include at least one selected from the group consisting of: a hole injection layer, a hole transport layer, an electron blocking layer, and a buffer layer.

The hole transport region may include only a hole injection layer or a hole transport layer. In various embodiments, the hole transport region can have the following structure: a hole injection layer/hole transport layer or a hole injection layer/hole transport layer/electron blocking layer, which are sequentially stacked in the stated order from the first electrode 11.

The hole injection layer may be formed on the first electrode 11 by using one or more suitable methods selected from the group consisting of: vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) deposition.

When the hole injection layer is formed by vacuum deposition, the deposition conditions may vary depending on the material used to form the hole injection layer and the structure and thermal characteristics of the hole injection layer. In some embodiments, the deposition conditions may include a deposition temperature of about 100 ℃ to about 500 ℃, about 10 ℃^-8Torr to about 10^-3Vacuum pressure of the tray, andthe deposition rate of (c). However, the deposition conditions are not limited thereto.

When the hole injection layer is formed using spin coating, coating conditions may vary depending on the material used to form the hole injection layer and the structure and thermal properties of the hole injection layer. For example, the coating speed may be about 2,000 revolutions per minute (rpm) to about 5,000rpm, and the temperature at which the heat treatment to remove the solvent after coating may be about 80 ℃ to about 200 ℃. However, the coating conditions are not limited thereto.

The conditions for forming the hole transport layer and the electron blocking layer may be understood by referring to the conditions for forming the hole injection layer.

The hole transport region may include at least one selected from the group consisting of: m-MTDATA, TDATA, 2-TNATA, NPB, β -NPB, TPD, spiro-NPB, methylated NPB, TAPC, HMTPD, 4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-sulfostyrene) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-sulfostyrene) (Pani/PSS), a compound represented by the following formula 201, and a compound represented by the following formula 202:

< equation 201>

< equation 202>

Wherein Ar in formula 201₁₀₁And Ar₁₀₂Can be independently selected from

Phenylene, pentalenylene, indenylene, naphthylene, azulenylene, heptalenylene, acenaphthylene, fluorenylene, phenalenylene, phenanthrylene, anthrylene, benzo [9,10 ] ene]Phenanthrylene, pyrenylenePhenyl, tetracenyl, picenyl, peryleneyl, and pentylene; and

each of which is at least one substituted phenylene, pentalenylene, indenylene, naphthylene, azulenylene, heptalenylene, acenaphthylene, fluorenylene, phenalenylene, phenanthrylene, anthrylene, benzo [9,10 ] ene]Phenanthrylene, pyrenylenePhenyl, tetracenyl, picenyl, peryleneyl, and pentylene: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, and a monovalent non-aromatic fused heteropolycyclic group.

Xa and xb in formula 201 may each independently be an integer selected from 0 to 5. Alternatively, xa and xb may each independently be an integer selected from 0, 1, and 2. In some embodiments, xa may be 1 and xb may be 0, but embodiments are not limited thereto.

R in formulae 201 and 202₁₀₁-R₁₀₈、R₁₁₁-R₁₁₉And R₁₂₁-R₁₂₄Can be independently selected from

c each substituted by at least one member selected from the group consisting of₁-C₁₀Alkyl and C₁-C₁₀Alkoxy groups: deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, and phosphoric acid group or salt thereof;

phenyl, naphthyl, anthracenyl, fluorenyl, and pyrenyl; and

phenyl, naphthyl, anthracenyl, fluorenyl, and pyrenyl each substituted with at least one group selected from: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₁₀Alkyl, and C₁-C₁₀An alkoxy group,

the embodiments are not limited thereto.

R in formula 201₁₀₉Can be selected from

Phenyl, naphthyl, anthracenyl, and pyridyl; and

phenyl, naphthyl, anthracenyl and pyridinyl, each substituted with at least one substituent selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, anthracenyl, and pyridyl.

In some embodiments, the compound represented by formula 201 may be represented by formula 201A, but embodiments are not limited thereto:

< equation 201A >

Wherein R in formula 201A₁₀₁、R₁₁₁、R₁₁₂And R₁₀₉May be the same as those described herein.

In some embodiments, the compound represented by formula 201 and the compound represented by formula 202 may include compounds HT1-HT20, but embodiments are not limited thereto:

the hole transport region may have a thickness of about-aboutAnd in some embodiments about-aboutWithin the range of (1). When the hole transport region includes at least one of a hole injection layer and a hole transport layer, the hole injection layer may have a thickness of about-aboutAnd in some embodiments about-aboutAnd the thickness of the hole transport layer may be about-aboutAnd in some embodiments about-aboutWithin the range of (1). When the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, excellent hole transport characteristics can be obtained without a significant increase in driving voltage.

The hole transport region may include a charge generation material as well as the above-mentioned materials to improve the conductive properties. The charge generating material may be dispersed uniformly or non-uniformly throughout the hole transport region.

The charge generating material may be, for example, a p-dopant. The p-dopant may be one selected from a quinone derivative, a metal oxide, and a cyano group-containing compound, but the embodiment is not limited thereto. Non-limiting examples of the p-dopant are quinone derivatives such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4-TCNQ); metal oxides such as tungsten oxide or molybdenum oxide; and cyano-containing compounds such as compounds HT-D1 or HP-1, but are not limited thereto:

the hole transport region may include a buffer layer.

In addition, the buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus efficiency of the formed organic light emitting device may be improved.

The hole transport region may further include an electron blocking layer. The electron blocking layer may include, for example, mCP, but the material used therefor is not limited thereto:

an emissive layer can be formed on the hole transport region by using one or more suitable methods, such as vacuum deposition, spin coating, casting, or LB deposition. When the emission layer is formed by vacuum deposition or spin coating, vacuum deposition and coating conditions for the emission layer may be substantially similar to those for forming the hole injection layer, although the conditions may vary depending on the compound used.

When the organic light emitting device 10 is a full-color organic light emitting device, the emission layers may be patterned into a red emission layer, a green emission layer, and a blue emission layer. In some embodiments, the emission layer may have a structure in which a red emission layer, a green emission layer, and/or a blue emission layer are stacked to emit white light, or other various embodiments are possible.

The emissive layer may comprise the above-described composition.

According to an embodiment, the emissive layer may comprise (e.g. consist of) the composition.

In various embodiments, the emissive layer may include the composition and a fluorescent dopant.

The fluorescent dopant may be any suitable fluorescent dopant known in the art.

In some embodiments, the fluorescent dopant may be selected from compounds represented by formula 501:

< equation 501>

Wherein, in the formula 501,

Ar₅₀₁can be selected from

naphthyl, heptenylene, fluorenyl, spiro-dibenzofluorenyl, carbazolyl, benzofluorenyl, dibenzofluorenyl, phenalkenyl, phenanthrenyl, anthracenyl, fluoranthenyl, benzo [9,10 ] substituted by at least one member selected from the group consisting of]Phenanthryl, pyrenyl,Phenyl, tetracenyl, picenyl, peryleneyl, pentylphenyl, and indenonanthracenyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, and-Si (Q)₅₀₁)(Q₅₀₂)(Q₅₀₃) Which isMiddle Q₅₀₁-Q₅₀₃Can be independently selected from hydrogen and C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₆-C₆₀Aryl, and C₁-C₆₀(ii) a heteroaryl group, wherein,

L₅₀₁-L₅₀₃can be independently selected from substituted or unsubstituted C₃-C₁₀Cycloalkylene, substituted or unsubstituted C₁-C₁₀Heterocycloalkylene, substituted or unsubstituted C₃-C₁₀Cycloalkenylene, substituted or unsubstituted C₁-C₁₀Heterocycloalkenylene, substituted or unsubstituted C₆-C₆₀Arylene, substituted or unsubstituted C₁-C₆₀A heteroarylene group, a substituted or unsubstituted divalent non-aromatic fused polycyclic group, and a substituted or unsubstituted divalent non-aromatic fused heteropolycyclic group,

R₅₀₁and R₅₀₂Can be independently selected from

phenyl, naphthyl, fluorenyl, spiro-dibenzofluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracenyl, pyrenyl, substituted by at least one of each,Phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, triazinyl, dibenzofuranyl, and dibenzothienyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracyl, pyrenyl,Pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, triazinyl, dibenzofuranyl, and dibenzothienyl,

each of xd1-xd3 can be independently selected from 0, 1, 2, and 3, and

xd4 may be selected from 0, 1, 2,3, 4, 5, and 6.

In some embodiments, in equation 501,

Ar₅₀₁can be selected from

Naphthyl, heptalenyl, fluorenyl, spiro-dibenzofluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthryl, anthracyl, fluoranthenyl, benzo [9,10 ] b]Phenanthryl, pyrenyl,Phenyl, tetracenyl, picenyl, peryleneyl, pentylphenyl, and indenonanthracenyl; and

naphthyl, heptenylene, fluorenyl, spiro-dibenzofluorenyl, benzofluorenyl, dibenzofluorenyl, phenalkenyl, phenanthrenyl, anthracenyl, fluoranthenyl, benzo [9,10 ] substituted by at least one of each]Phenanthryl, pyrenyl,Phenyl, tetracenyl, picenyl, peryleneyl, pentylphenyl, and indenonanthracenyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracyl, pyrenyl,Pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, isoindolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, and triazinyl,

L₅₀₁-L₅₀₃can be independently selected from

Phenylene, naphthylene, fluorenylene, spiro-dibenzofluorenylene, benzofluorenylene, dibenzofluorenylene, phenanthrylene, anthracylene, pyrenyleneA group selected from the group consisting of pyridyl, pyrazinylene, pyrimidinyl, pyridazinylene, quinolinylene, isoquinolinylene, quinoxalinylene, quinazolinylene, carbazolyl, and triazinylene; and

phenylene, naphthylene, fluorenylene, spiro-dibenzofluorenylene, benzofluorenylene, dibenzofluorenylene, phenanthrenylene, anthracenylene, pyrenylene, each of which is substituted by at least one member selected from the group consisting ofA group, a pyridylene group, a pyrazinylene group, a pyrimidylene group, a pyridazinylene group, a quinolylene group, an isoquinolylene group, a quinoxalylene group, a quinazolinylene group, a carbazolyl group, and a triazinylene group: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracyl, pyrenyl,Pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, isoindolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, and triazinyl,

R₅₀₁and R₅₀₂Can be independently selected from

Phenyl, naphthyl, fluorenyl, spiro-dibenzoenylBenzofluorenyl, dibenzofluorenyl, phenanthrenyl, anthracenyl, pyrenyl,Phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, and triazinyl; and

phenyl, naphthyl, fluorenyl, spiro-dibenzofluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracenyl, pyrenyl, substituted by at least one of each,Phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, and triazinyl: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl, naphthyl, azulenyl, fluorenyl, spiro-dibenzofluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracenyl, pyrenyl,Pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, and triazinyl,

each of xd1-xd3 can be independently 0, 1, or 2, and

xd4 may be 0, 1, 2,3, or 4, but embodiments are not so limited.

According to an embodiment, the fluorescent dopant may include at least one compound selected from compounds FD (1) -FD (5) and FD1-FD8, but the embodiment is not limited thereto:

when the emission layer includes the composition and the fluorescent dopant, the amount of the fluorescent dopant may be selected from a range of about 0.01 parts by weight to about 20 parts by weight based on about 100 parts by weight of the composition, but the embodiment is not limited thereto.

The thickness of the emissive layer may be about-aboutAnd in some embodiments about -aboutWithin the range of (1). When the thickness of the emission layer is within these ranges, excellent light emitting characteristics can be achieved without a significant increase in driving voltage.

An electron transport region may then be formed on the emissive layer.

The electron transport region may include at least one selected from the group consisting of: a hole blocking layer, an electron transport layer, and an electron injection layer.

For example, the electron transport region may have a structure of a hole blocking layer/electron transport layer/electron injection layer or a structure of an electron transport layer/electron injection layer, but the structure of the electron transport region is not limited thereto. The electron transport layer may have a single layer structure or a multi-layer structure including two or more different layers.

The conditions for forming the hole blocking layer, the electron transport layer, and the electron injection layer constituting the electron transport region can be understood by referring to the conditions for forming the hole injection layer.

When the electron transport region includes a hole blocking layer, the hole blocking layer may include, for example, at least one of BCP and Bphen, but may also include other materials:

the hole blocking layer may have a thickness of about-aboutFor example about-aboutWithin the range of (1). When the thickness of the hole blocking layer is within these ranges, the hole blocking layer may have improved hole blocking capability without a significant increase in driving voltage.

The electron transport layer may further include at least one selected from the group consisting of: BCP, BPhen, Alq₃BAlq, TAZ, and NTAZ:

in various embodiments, the electron transport layer may include at least one selected from the compounds ET1, ET2, and ET3, but the embodiments are not limited thereto:

the electron transport layer may have a thickness of about-aboutAnd in some embodiments about-aboutWithin the range of (1). When the thickness of the electron transport layer is within these ranges, excellent electron transport characteristics can be achieved without a significant increase in driving voltage.

Further, the electron transport layer may further include a material including a metal in addition to the above materials.

The metal-containing material may include a Li complex. The Li complex may include, for example, the compounds ET-D1 (lithium 8-quinolinolato, LiQ) or ET-D2:

the electron transport region may include an electron injection layer that facilitates injection of electrons from the second electrode 19.

The electron injection layer may include at least one selected from the group consisting of: LiF, NaCl, CsF, Li₂O, and BaO.

The electron injection layer may have a thickness of about-aboutFor example about-aboutExample (A) ofInside the enclosure. When the thickness of the electron injection layer is within these ranges, excellent electron injection characteristics can be achieved without a significant increase in driving voltage.

The second electrode 19 may be on the organic layer 15. The second electrode 19 may be a cathode. The material for forming the second electrode 19 may be a material having a relatively low work function such as a metal, an alloy, a conductive compound, and a combination thereof. Detailed examples of the material for forming the second electrode 19 may include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). In some embodiments, the transmissive second electrode 19 may be formed using ITO or IZO to manufacture a top emission light emitting device, and such a modification may be possible.

Hereinbefore, the organic light emitting device 10 has been described with reference to fig. 1, but the embodiment is not limited thereto.

The term "C" as used herein₁-C₆₀Alkyl "refers to a straight or branched aliphatic saturated hydrocarbon monovalent radical having 1 to 60 carbon atoms. Detailed examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. The term "C" as used herein₁-C₆₀Alkylene "means having a bond with C₁-C₆₀Alkyl groups are divalent radicals of the same structure.

The term "C" as used herein₁-C₆₀Alkoxy "refers to a group consisting of-OA₁₀₁(wherein A is₁₀₁Is C₁-C₆₀Alkyl) monovalent group. Non-limiting examples thereof include methoxy, ethoxy, and isopropoxy.

The term "C" as used herein₂-C₆₀Alkenyl "is defined by the presence of C₂-C₆₀A group formed by placing at least one carbon-carbon double bond in the middle or at the end of the alkyl group. Detailed examples thereof may include ethenyl, propenyl, and butenyl. The term "C" as used herein₂-C₆₀Alkenylene "means having a group with C₂-C₆₀Divalent radicals of the same structure as the alkenyl radicals.

As herein describedUse of the term "C₂-C₆₀Alkynyl "is intended by the presence of C₂-C₆₀A group formed by placing at least one carbon-carbon triple bond in the middle or at the end of the alkyl group. Detailed examples thereof may include ethynyl and propynyl. The term "C" as used herein₂-C₆₀Alkynylene "means having a bond with C₂-C₆₀Alkynyl groups are divalent radicals of the same structure.

The term "C" as used herein₃-C₁₀Cycloalkyl "refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms. Non-limiting examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. The term "C" as used herein₃-C₁₀Cycloalkylene "means having an alkyl radical with C₃-C₁₀A divalent group of the same structure as the cycloalkyl group.

The term "C" as used herein₁-C₁₀Heterocycloalkyl "refers to a monovalent saturated monocyclic group comprising at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom and 1-10 carbon atoms. Detailed examples thereof may include tetrahydrofuranyl and tetrahydrothienyl. The term "C" as used herein₁-C₁₀Heterocycloalkylene "means having a carbon atom with₁-C₁₀Heterocycloalkyl groups are divalent radicals of the same structure.

The term "C" as used herein₃-C₁₀Cycloalkenyl "refers to a monovalent monocyclic group having 3 to 10 carbon atoms and at least one carbon-carbon double bond in its ring and which is not aromatic. Detailed examples thereof may include cyclopentenyl, cyclohexenyl, and cycloheptenyl groups. The term "C" as used herein₃-C₁₀Cycloalkenyl "means having an alkyl group with C₃-C₁₀And (c) divalent groups having the same structure as the cycloalkenyl groups.

The term "C" as used herein₁-C₁₀Heterocycloalkenyl "refers to a monovalent monocyclic group having at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom, 1 to 10 carbon atoms, and at least one carbon-carbon double bond in its ring. C₁-C₁₀Examples of heterocycloalkenyl groupsMay include 2, 3-dihydrofuranyl and 2, 3-dihydrothienyl. The term "C" as used herein₁-C₁₀Heterocycloalkylene "means having a carbon atom with₁-C₁₀Heterocycloalkyl groups are divalent radicals of the same structure.

The term "C" as used herein₆-C₆₀Aryl "refers to a monovalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms. The term "C" as used herein₆-C₆₀Arylene "refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. C₆-C₆₀Detailed examples of the aryl group may include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, andand (4) a base. When C is present₆-C₆₀Aryl and C₆-C₆₀When the arylene groups each include two or more rings, the rings may be fused to each other.

The term "C" as used herein₁-C₆₀Heteroaryl "refers to a monovalent group having an aromatic system and 1 to 60 carbon atoms as follows: which includes at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom. The term "C" as used herein₁-C₆₀Heteroarylene "refers to a divalent group having a heterocyclic aromatic system and 1 to 60 carbon atoms as follows: which includes at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom. C₁-C₆₀Detailed examples of heteroaryl groups may include pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, and isoquinolinyl groups. When C is present₁-C₆₀Heteroaryl and C₁-C₆₀When the heteroarylenes each include two or more rings, the rings may be fused to each other.

The term "C" as used herein₆-C₆₀Aryloxy "refers to-OA₁₀₂(wherein A is₁₀₂Is C₆-C₆₀Aryl). The term "C" as used herein₆-C₆₀Arylthio "denotes-SA₁₀₃(wherein A is₁₀₃Is C₆-C₆₀Aryl).

The term "monovalent non-aromatic fused polycyclic group" as used herein refers to a monovalent group that is: which has two or more rings fused to each other and has only carbon atoms (for example, the number of carbon atoms may be in the range of 8 to 60) as ring-forming atoms, wherein the molecular structure as a whole is non-aromatic. Non-limiting examples of the monovalent non-aromatic fused polycyclic group include fluorenyl groups. The term "divalent non-aromatic fused polycyclic group" as used herein refers to a divalent group having the same structure as the monovalent non-aromatic fused polycyclic group.

The term "monovalent non-aromatic fused heteropolycyclic group" as used herein refers to a monovalent group that is: having a plurality of rings fused to each other, having a hetero atom selected from N, O, P, and S as a ring-forming atom in addition to a carbon atom (for example, the number of carbon atoms may be in the range of 2 to 60), wherein the molecular structure as a whole is non-aromatic. Non-limiting examples of the monovalent non-aromatic fused heteropolycyclic group include carbazolyl groups. The term "divalent non-aromatic fused heteropolycyclic group" as used herein refers to a divalent group having the same structure as the monovalent non-aromatic fused heteropolycyclic group.

In the present specification, said substituted C₃-C₁₀Cycloalkylene, substituted C₁-C₁₀Heterocycloalkylene, substituted C₃-C₁₀Cycloalkenylene, substituted C₁-C₁₀Heterocycloalkenylene, substituted C₆-C₆₀Arylene, substituted C₁-C₆₀Heteroarylene, substituted divalent non-aromatic fused polycyclic group, substituted divalent non-aromatic fused heteropolycyclic group, substituted C₁-C₆₀Alkyl, substituted C₂-C₆₀Alkenyl, substituted C₂-C₆₀Alkynyl, substituted C₁-C₆₀Alkoxy, substituted C₃-C₁₀Cycloalkyl, substituted C₁-C₁₀Heterocycloalkyl, substituted C₃-C₁₀Cycloalkenyl, substituted C₁-C₁₀Heterocycloalkenyl, substituted C₆-C₆₀Aryl, substituted C₆-C₆₀Aryloxy, substituted C₆-C₆₀Arylthio, substituted C₁-C₆₀At least one of the substituents of the heteroaryl, the substituted monovalent non-aromatic fused polycyclic group, and the substituted monovalent non-aromatic fused heteropolycyclic group may be:

deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, or C₁-C₆₀An alkoxy group;

c each substituted by at least one member selected from the group consisting of₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, or C₁-C₆₀Alkoxy groups: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀Heteroaryl, monovalent non-aromatic fused polycyclic radical, monovalent non-aromatic fused heteropolycyclic radical, -N (Q)₁₁)(Q₁₂)、-Si(Q₁₃)(Q₁₄)(Q₁₅) and-B (Q)₁₆)(Q₁₇)；

C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl, a monovalent non-aromatic fused polycyclic group, or a monovalent non-aromatic fused heteropolycyclic group;

c each substituted by at least one member selected from the group consisting of₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl, a monovalent non-aromatic fused polycyclic group, or a monovalent non-aromatic fused heteropolycyclic group: deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀Heteroaryl, monovalent non-aromatic fused polycyclic radical, monovalent non-aromatic fused heteropolycyclic radical, -N (Q)₂₁)(Q₂₂)、-Si(Q₂₃)(Q₂₄)(Q₂₅) and-B (Q)₂₆)(Q₂₇) (ii) a And

-N(Q₃₁)(Q₃₂)、-Si(Q₃₃)(Q₃₄)(Q₃₅) or-B (Q)₃₆)(Q₃₇，

Wherein Q₁-Q₇、Q₁₁-Q₁₇、Q₂₁-Q₂₇And Q₃₁-Q₃₇Can be each independently hydrogen, C₁-C₆₀Alkyl radical, C₂-C₆₀Alkenyl radical, C₂-C₆₀Alkynyl, C₁-C₆₀Alkoxy radical, C₃-C₁₀Cycloalkyl radical, C₁-C₁₀Heterocycloalkyl radical, C₃-C₁₀Cycloalkenyl radical, C₁-C₁₀Heterocycloalkenyl, C₆-C₆₀Aryl radical, C₆-C₆₀Aryloxy radical, C₆-C₆₀Arylthio group, C₁-C₆₀A heteroaryl group, a monovalent non-aromatic fused polycyclic group, or a monovalent non-aromatic fused heteropolycyclic group.

The term "room temperature" as used herein refers to a temperature of about 25 ℃.

Hereinafter, the organic light emitting device according to the embodiment will be described in detail with reference to synthesis examples and examples, however, the inventive concept is not limited thereto. The expression "use B instead of a" used in describing the synthesis examples means that the amount of B used is equal to the amount of a used, based on molar equivalents.

[ examples ]

Synthesis example 1: synthesis of Compound A1

52mmol of 3, 6-dicyanocarbazole, 52mmol of 9- (3-bromophenyl) -9H-carbazole, 8.8g of CuI, 15.9g of K₂CO₃And 2.5g of 1, 10-phenanthroline to a 250mL two-necked round bottom flask, followed by 150mL of Dimethylformamide (DMF). Subsequently, the composition was stirred at a temperature of 150 ℃ for 28 hours. The resultant was then cooled and MeOH was added thereto to precipitate a solid for filtration. The resulting product was mixed with 1L chloroform, heated, and dissolved. The filtrate obtained by filtration using a celite pad was concentrated under reduced pressure. The obtained product was recrystallized using dichloromethane (MC) and acetone, thereby obtaining 10.9g of Compound A1 (yield: 65.3%).

Calculated values: 458.15, found [ M + H⁺]：459.16

Evaluation example 1: evaluation of PL and TRPL spectra

A quartz substrate washed with chloroform and pure water was prepared. The materials shown in Table 1 are set at 10^-7Vacuum- (co) deposition on the quartz substrate under vacuum of Torr to prepare films D2, A1, D2: A1, A2, D2: A2, D3, A3, D3: A3,D3: A3: TBPe, D3: TBPe, D4, A4, D4: A4, D4: A4: TBPe, D4: TBPe, BmPyPb, TCTA: BmPyPb, CBP: B3PYMPM, or TCTA:3TPYMB, each having a thickness of 50 nm.

[ Table 1]

< Compound FD (5): TBPe >

Subsequently, PL spectra of the prepared films D2, A1, D2: A1, A2, D2: A2, D3, A3, D3: A3, D4, A4, D4: A4, TCTA, BmPyPb, and TCTA: BmPyPb were evaluated at room temperature using the absolute PL Quantaurus-QY (available from Hamamatsu). The results are shown in FIGS. 2A-2E.

In fig. 2A, it was found that the PL spectrum of film D2: a1 was shifted toward a longer wavelength range than those of film D2 and film a 1. In fig. 2B, it was found that the PL spectrum of film D2: a2 was shifted toward a longer wavelength range than those of film D2 and film a 2. In fig. 2C, it was found that the PL spectrum of film D3: A3 was shifted toward a longer wavelength range than those of film D3 and film A3. In fig. 2D, it was found that the PL spectrum of film D4: a4 was shifted toward a longer wavelength range than those of film D4 and film a 4. Thus, it was found that the combinations of the compounds used in the preparation of film D2: A1, film D2: A2, film D3: A3, and film D4: A4 each formed exciplexes.

Furthermore, in FIG. 2A, the lambda of film D2: A1_{Maximum of}Is about 425 nm. In FIG. 2B, lambda of film D2: A2_{Maximum of}Is about465 nm. In FIG. 2C, lambda of film D3: A3_{Maximum of}Is about 430 nm. In FIG. 2D, lambda of film D4: A4_{Maximum of}Is about 470 nm. It was found that the exciplex formed from the compounds D2 and a1, the exciplex formed from the compounds D2 and a2, the exciplex formed from the compounds D3 and A3, and the exciplex formed from the compounds D4 and a4 each emitted blue light.

Subsequently, PL spectra of films D2, a1, D2: a1, a2, D2: a2, D3: A3, D3: A3: TBPe, D3: TBPe, D4: a4, D4: a4: TBPe, D4: TBPe, and TCTA: BmPyPb were evaluated at room temperature by using TRPL measurement system FluoTime 300 (manufactured by PicoQuant), and pump laser PLS340 (manufactured by PicoQuant, excitation wavelength 340nm, spectral width 20 nm). Then, the wavelengths of the main peaks in the PL spectrum were measured, and the number of photons emitted at the wavelengths of the main peaks of each of the films was repeatedly measured over time by time-dependent single photon counting (TCSPC) according to the photon pulse (pulse width: 500 picoseconds) applied to the film by PLs340, thereby obtaining a TRPL curve that can be used for a sufficient fit. Based on the results obtained therefrom, two or more exponential decay functions were proposed for the fitting to obtain decay times T of T for each of the films D2: A1, D2: A2, D3: A3, D3: A3: TBPe, D4: A4, D4: A4: TBPe, and TCTA: BmPy Pb_{Attenuation of}(Ex). Function for fitting and<equation 1>And taking the decay time T having the maximum value among the values of each of the exponential decay functions used for fitting_{Attenuation of}As decay time T_{Attenuation of}(Ex). Using the remaining decay time T_{Attenuation of}The values determine the lifetime of a typical fluorescence to be attenuated. Here, the same measurement is repeated again in a dark state (i.e., a state in which a pump signal incident on a predetermined film is blocked) during the same measurement time as that for obtaining the TRPL curve, thereby obtaining a background signal curve or baseline that can be used as a baseline for fitting.

Subsequently, for the integral value of the time-dependent intensity of all emissions, the measurement will be determined as the decay time T_{Attenuation of}(Ex) exponential decay curve (═ change in intensity over time), and therefore, calculationThe ratio of the integrated value with time, thereby evaluating the ratio of delayed fluorescence to the total light-emitting portions.

< equation 1>

In the diagrams of films D2: A1, D2: A2, D3: A3, D3: A3: TBPe, D4: A4, D4: A4: TBPe, and TCTA: BmPyPb in FIGS. 3A-3G, T_{Attenuation of}(Ex) and the ratio of delayed fluorescence moiety to the total light-emitting moiety are shown in table 2:

[ Table 2]

Thus, it was found that i) the exciplex formed from compounds D2 and a1, ii) the exciplex formed from compounds D2 and a2, iii) the exciplex formed from compounds D3 and A3, iv) the combination of the exciplex formed from compounds D3 and A3 and TBPe, v) the exciplex formed from compounds D4 and a4, and vi) the combination of the exciplex formed from compounds D4 and a4 and TBPe had a T of about 100ns or more (e.g., 150ns or more)_{Attenuation of}(Ex) and a ratio of delayed fluorescence moieties to total luminescence moieties of about 10% or more (e.g., 15% or more).

On the other hand, the ratio of the delayed fluorescence part to the whole light-emitting part in the film TCTA: BmPyPb was about 4%. Thus, the delayed fluorescence due to exciplex in the film TCTA BmPyPb was found to contribute to the overall fluorescence to a relatively small extent.

Evaluation example 2: evaluation of HOMO and LUMO energy levels

The HOMO and LUMO energy levels of compounds D1, a1, D2, a2, D3, A3, D4, and a4 were evaluated according to the methods shown in table 3. The results are shown in Table 4.

[ Table 3]

[ Table 4]

Referring to table 4, compounds D1, a1, D2, a2, D3, A3, D4, and a4 were found to have suitable electrical properties for forming exciplexes that can emit delayed fluorescence.

Evaluation example 3: evaluation of Photoluminescence (PL) stability

The PL spectra of the films were evaluated at room temperature in an argon atmosphere with the outside air cut off, using a He-Cd laser (available from Kimmon Koha co., Ltd, excitation wavelength 325nm) immediately after the films D3: A3, TCTA: BmPyPb, CBP: B3PYMPM, and TCTA:3TPYMB were formed. Measuring the intensity I of light of the maximum emission wavelength in the PL spectrum for each of the films₁(arbitrary unit). The results are shown in Table 5.

Subsequently, the films D3: A3, TCTA: BmPyPb, CBP: B3PYMPM, and TCTA:3TPYMB were each exposed to an argon atmosphere in which the outside air was shut off₁The pump laser He — Cd laser (available from Kimmon Koha co., Ltd, excitation wavelength 325nm) used in the evaluation of (1) was irradiated for 3 hours. Then, the PL spectra of the respective films obtained after the above three-hour exposure were evaluated at room temperature using a He — Cd laser (available from Kimmon Koha co., Ltd, excitation wavelength 325 nm). Then, the intensity I of light at the maximum emission wavelength in the PL spectrum was measured for each of the films₂(arbitrary unit). The results are shown in Table 5.

The PL-spectra measured immediately after formation of each of films D3: A3, TCTA: BmPyPb, CBP: B3PYMPM and TCTA:3TPYMB (shown as prepared) and after three hours of exposure to the laser (shown as 3 hours of exposure) are shown in FIGS. 4A-4D.

From I measured as above₁And I₂By using (I)₂/I₁) X 100 (%) PL stability of each film was calculated. The results are shown in Table 5.

[ Table 5]

Referring to Table 5, it was found that film D3: A3 had higher PL stability than films TCTA: BmPyPb, CBP: B3PYMPM, and TCTA:3 TPYMB.

Example (b): fabrication of Organic Light Emitting Devices (OLEDs)

As an anode, a glass substrate having an ITO electrode thereon was cut into dimensions of 50 millimeters (mm) × 50mm × 0.5 mm. The glass substrate was then sonicated in acetone, isopropanol, and pure water for about 15 minutes in each solvent and cleaned by exposure to ultraviolet light and ozone for 30 minutes.

Co-depositing compounds HT3 and TCNPQ (wherein the concentration of TCNPQ is about 3 weight percent) on the anode to form a catalyst having a chemical composition of aboutA hole injection layer of the thickness of (1). Compound HT3 was then deposited on the hole injection layer to form a hole injection layer having a thickness of aboutA hole transport layer of the thickness of (1).

Then co-depositing compound D2 and compound A2 on the hole transport layer at a volume ratio of about 3:7 to form a layer having a thickness of aboutThe thickness of the emission layer of (1).

Co-depositing compound ET16 and LiQ on the emissive layer at a weight ratio of about 5:5 to form a layer having a thickness of aboutElectron transport layer of thickness (b). Subsequently, LiQ is deposited on the electron transport layer to form a layer having a thickness of aboutElectron injection layer of (3). Forming a layer having a thickness of about A MgAg electrode of thickness (wherein the amount of Ag is about 10 wt%). The compound HT13 was deposited on a MgAg electrode to form a thin film having a thickness of aboutThereby completing the fabrication of the organic light emitting device. The donor compounds, acceptor compounds, and/or fluorescent dopants used in the formation of the emission layers of the fabricated OLEDs 1 to 3 and a and B and the volume ratios thereof are shown in table 6.

[ Table 6]

Evaluation example 4

The manufactured OLEDs 1 to 3 and a and B were measured for driving voltage, brightness, power, color coordinate, roll-off, and lifetime (T-off) by using a Keithley 2400 current voltmeter and luminance meter (Minolta Cs-1000A)₉₅). The results are shown in Table 7. In Table 7, T₉₅Life data representing the time taken for the luminance (at 9000 nits) to reach 95% relative to 100% of the initial luminance was evaluated. Roll-off device<Equation 20>And (3) calculating:

< equation 20>

Roll-off {1- (efficiency (at 9000 nits)/maximum emission efficiency) } × 100%

[ Table 7]

Referring to table 7, it was found that OLED 1 had a low driving voltage, high efficiency, low roll-off, and long life span compared to OLED a, and that OLEDs 2 and 3 had a low driving voltage, high efficiency, low roll-off, and long life span compared to OLED B.

It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within various embodiments should typically be considered as available for other similar features or aspects in other embodiments.

Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.

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