KR102421843B1 - Compound including pyrimidine, and organic light emitting diode having the same - Google Patents

Abstract

The present invention relates to a compound for an organic light emitting diode, an organic light emitting diode using the same, and an electronic device including the organic light emitting diode. , long lifespan and high color purity can be achieved.

Description

A compound containing pyrimidine and an organic light emitting diode containing the same

The present invention relates to a compound for an organic light emitting diode, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting diode using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer therebetween. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting diode, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. can be made with

A material used as an organic layer in an organic light emitting diode may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to a function. In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. have. In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

2. Description of the Related Art An organic light emitting diode (OLED) is a self-emission type device and is used in a display or lighting. Recently, organic light emitting diodes are being applied to display panels, and compared to the existing liquid crystal displays, the viewing angle is wide and the contrast is excellent, the response time is fast, the luminance, driving voltage and response speed characteristics are excellent, and the advantages of being able to multicolor are available. Have.

These organic light emitting diodes are driven by DC, and when a DC voltage is applied between the anode and the cathode, holes injected from the anode move to the emission layer via the hole injection/transport layer, and electrons injected from the cathode pass through the electron injection/transport layer. move to the light emitting layer. Holes and electrons reaching the emission layer generate excitons in an excited state through recombination, and the excitons change to a ground state and emit light of a specific wavelength.

When excitons are formed, 25% of singlet states and 75% of triplet states are formed according to the quantum spin statistical law. Light-emitting materials can be largely divided into fluorescent materials and phosphorescent materials. In the case of fluorescent materials, since they emit light using only a singlet state, theoretically, quantum efficiency is very low. Therefore, in order to improve the efficiency of the light emitting layer or the efficiency of the organic light emitting diode, triplet excitons should be utilized as much as possible.

Therefore, in the case of a phosphorescent material including a heavy metal such as iridium (Ir) or platinum (Pt), triplet excitons can be converted into light, and thus a highly efficient organic light emitting diode device can be manufactured. However, the cost of iridium (Ir) or platinum (Pt) is expensive and the supply of materials is limited, and especially in the case of blue phosphorescent materials, the problem of device lifetime must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan.

Therefore, it is necessary to develop a light emitting material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer.

Accordingly, as a result of research to provide a light emitting material of a new design, the present inventors have derived the present invention through the three-dimensional structure of HOMO and LUMO by appropriately combining donor and acceptor molecules based on pyrimidine.

An object of the present invention is to provide an organic material having improved efficiency and improved lifespan, and an organic light emitting diode containing the same. In addition, it is intended to improve the color purity and lifespan characteristics of blue, green, and red light emitting materials applicable to displays.

In one aspect, the present invention provides a compound represented by the following formula.

<Formula 1>

In another aspect, the present invention provides an organic light emitting diode using the compound represented by the above formula, and an electronic device thereof.

By using the compound according to the present invention, there is an effect of achieving a high glass transition temperature and high molecular stability, high luminous efficiency, long lifespan, and high color purity.

1 is a cross-sectional view showing an organic light emitting diode according to an embodiment of the present invention.
2 shows a chemical formula according to an aspect of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

In order to describe the present embodiments, it should be noted that in adding reference numerals to components in each drawing, the same components are given the same reference numerals as much as possible even though they are indicated in different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted. In the drawings referenced below, no scale ratio applies.

In describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms.

When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is between each component. It should be understood that elements may be “connected,” “coupled,” or “connected.”

Also, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” another component, but also when another component is in between. It should be understood that cases may be included. Conversely, it should be understood that when an element is said to be "on top of" another part, it means that there is no other part in the middle.

Terms used in this specification and the appended claims are as follows, unless otherwise stated, without departing from the spirit of the present invention.

As used herein, the term "halo" or "halogen" includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has 1 to 60 carbons linked by a single bond, and is a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted means a radical of saturated aliphatic functional groups including cycloalkyl groups, cycloalkyl-substituted alkyl groups. In addition, it may be used including “alkenyl” or “alkynyl” below.

The term "alkenyl" or "alkynyl" as used in this application has a double bond or a triple bond instead of a single bond in the "alkyl", respectively, unless otherwise specified, and includes a straight or branched chain group, 2 It has a carbon number of to 60, but is not limited thereto.

As used herein, the term "cycloalkyl" refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present application, the aryl group or the arylene group includes a single ring type, a ring aggregate, a fused multiple ring-based compound, and the like. For example, the aryl group may include a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, or a substituted fluorenyl group, and the arylene group may include a fluorenylene group, a substituted fluorenylene group. group may be included.

Since the aryl group in the present application includes a ring aggregate, the aryl group includes biphenyl and terphenyl in which a single aromatic benzene ring is connected by a single bond.

As used herein, the term "fused multiple ring system" means a fused ring type sharing at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. These fused multiple ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "heterocyclic group" used in the present application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, the number of carbon atoms each containing one or more heteroatoms It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Se, unless otherwise specified, and the heterocyclic group includes a monocyclic group, a ring aggregate, a fused multiple ring system, etc. including a heteroatom. it means.

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" used in this application, "substitution" means hydrogen, deuterium, C ₁ -C ₉ alkyl group, C ₃ -C ₃₀ cycloalkyl group, C ₆ - C ₃₀ Aryl group, C ₈ -C ₃₀ Alkylaryl group, C ₈ -C ₃₀ Arylalkyl group, C ₂ -C ₃₀ Heteroaryl group, aryloxy group, arylamine, fused arylamine group, phosphine Or it means substituted with one or more substituents selected from the group consisting of a phosphine oxide group, a thiol group, a sulfoxide or a sulfone group, but is not limited to these substituents.

In this application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituents in the present application may be described as 'the name of the functional group reflecting the valence', but it is described as 'the name of the parent compound' You may.

Hereinafter, a stacked structure of an organic light emitting diode including the compound of the present invention will be described with reference to FIG. 1 .

Referring to FIG. 1 , referring to FIG. 1 , the organic light emitting diode is disposed between the anode 10 and the cathode 70 , the light emitting layer 40 disposed between these two electrodes, and the anode 10 and the light emitting layer 40 . and a hole conductive layer 20 and an electron conductive layer 50 disposed between the light emitting layer 40 and the cathode 70 .

The hole conductive layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. In addition, the electron conductive layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating electron injection.

In addition, a first exciton blocking layer (not shown) may be disposed between the emission layer 40 and the hole transport layer 25 . Also, a second exciton blocking layer (not shown) may be disposed between the emission layer 40 and the electron transport layer 55 . Also, the present invention is not limited thereto, and the electron transport layer 55 may serve as the second exciton blocking layer, or the hole transport layer 25 may serve as the first electron blocking layer.

When a forward bias is applied to the organic light emitting diode, holes flow into the light emitting layer 40 from the anode 10 , and electrons flow into the light emitting layer 40 from the cathode 70 . Electrons and holes introduced into the emission layer 40 combine to form excitons, and light is emitted as the excitons transition to a ground state.

The light emitting layer 40 may be made of a single light emitting material, and may include a light emitting host material and a light emitting dopant material. When the light emitting layer 40 includes a light emitting host material and a light emitting dopant material, electrons and holes introduced into the light emitting layer 40 combine in the light emitting host material to form excitons, and then the excitons are transferred to the light emitting dopant material to form a base state can be transferred. The light emitting layer 40 including the light emitting host material and the light emitting dopant material may be a phosphorescent light emitting layer or a fluorescent light emitting layer, for example, a delayed fluorescent light emitting layer.

Any one of the compounds according to the present invention may be used for any one of the organic layers 20, 40, and 50 of the organic light emitting diode. Specifically, the compound may be used as any one of a hole injection material, a hole transport material, an exciton blocking material, a light emitting host material, a light emitting dopant material, an electron injection material, and an electron transport material.

In detail, the organic material may be used as a light emitting dopant material, and in this case, the light emitting layer 40 may be a delayed fluorescent light emitting layer.

In addition, the organic material may be used as a sensor for a general fluorescent dopant. In this case, the light emitting layer may be a light emitting layer composed of a delayed fluorescent host and a fluorescent dopant.

In addition, when the organic material binds an acceptor (electron withdrawing group) to the 1st position of the triazole and connects a donor (electron donor) to the 2nd and 5th positions, effective HOMO-LUMO separation is achieved. Therefore, charge transfer absorption and emission form are formed in the molecular structure, and a difference between singlet energy and triplet energy, that is, narrow ΔEst, may be exhibited. Accordingly, the organic material can improve the quantum efficiency and lifespan of the organic light emitting diode.

In addition, the host of the emission layer 40, in addition to the compound according to the present invention, mCP (N,N-dicarbazolyl-3,5-benzene), TSPO1 (diphenylphosphine oxide-4-(triphenylsilyl)phenyl), DPEPO (bis[2- (diphenylphosphino)phenyl]ether oxide), BSB (4,4 ′-bistriphenylsilanyl-biphenyl), UGH3 (m-bis- (triphenylsilyl)benzene), SimCP(3,5-di(N-carbazolyl)tetraphenylsilane), SimCP2 ( bis(3,5-di(9H-carbazol-9-yl)phenyl)diphenylsilane), CzSi(9-(4-tertbutylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole), SiCa(Diphenyldi(4) -(9-carbazoly)phenyl)silane), DCPPO((3,5-di(9H-carbazole-9-yl)phenyl)diphenylphosphine oxide), DFCz (2,8-di(9Hcarbazol-9-yl)dibenzo[ b,d]furan), DBT1(2,8-di(9H-carbazol-9-yl)dibenzo[b,d]thiophene), 26mCPy (2,6-bis(N-carbazolyl)pyridine), or any of these It may be a mixture of two or more.

In addition, the host is Alq3, CBP (4,4'-N,N'-dicarbazole-biphenyl), 9,10-di (naphthalen-2-yl) anthracene, TPBI (1,3,5-tris ( N-phenylbenzimidazol-2-yl)benzene (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN (3-tert-butyl-9,10-di(naphth- 2-day) anthracene).

The anode 10 may be a conductive metal oxide, metal, metal alloy, or carbon material. Conductive metal oxides include indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), fluorine doped tin oxide (FTO), SnO ₂ , ZnO, or a combination thereof. Suitable metals or metal alloys as anode 10 may be Au and CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

The hole injection layer 23 and/or the hole transport layer 25 is a layer having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, from the anode 10 to the light emitting layer 40 It functions to increase the injection or transport efficiency of holes. In addition, the electron injection layer 53 and/or the electron transport layer 55 are layers having a LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40 , and the light emitting layer 40 in the cathode 70 . ) to increase the injection or transport efficiency of electrons.

The hole injection layer 23 or the hole transport layer 25 may include a material commonly used as a hole transport material, and one layer may include different hole transport material layers.

The hole transport material is, for example, mCP (N,N-dicarbazolyl-3,5-benzene); PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate); NPD (N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine); N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl (TPD); N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl; N,N,N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl; N,N,N'N'-tetraphenyl-4,4'-diaminobiphenyl; porphyrin compound derivatives such as copper(II)1,10,15,20-tetraphenyl-21H,23H-porphyrin; TAPC(1,1-Bis[4-[N,N'-Di(ptolyl)Amino]Phenyl]Cyclohexane); triarylamine derivatives such as N,N,N-tri(p-tolyl)amine, 4,4′,4′-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine; carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; phthalocyanine derivatives such as metal-free phthalocyanine and copper phthalocyanine; starburst amine derivatives; enamine stilbene derivatives; derivatives of aromatic tertiary amines and styryl amine compounds; and polysilane. Such a hole transport material may serve as the first exciton blocking layer.

The second exciton blocking layer serves to prevent triplet excitons or holes from diffusing in the cathode 70 direction, and may be arbitrarily selected from known hole blocking materials. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, etc. can be used.

The electron transport layer 55 is, in addition to the compound according to the present invention, TSPO1 (diphenylphosphine oxide-4-(triphenylsilyl)phenyl), TPBi(1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene), Tris (8-quinolinolate) aluminum (Alq3), 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF-6P), COTs (Octasubstituted cyclooctatetraene), Bphen (4,7-diphenyl) -1,10-phenanthroline (4,7-diphenyl-1,10-phenanthroline).

The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate). The cathode 70 is a conductive film having a lower work function than the anode 10, for example, aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, silver, lead, metals such as cesium, or these It can be formed using a combination of two or more types of

The anode 10 and the cathode 70 may be formed using a sputtering method, a vapor deposition method, or an ion beam deposition method. The hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the exciton blocking layer, the electron transport layer 55, and the electron injection layer 53 are independent of each other by a deposition method or a coating method, for example, spraying. , spin coating, dipping, printing, doctor blading, or electrophoresis. The scope of the present invention is not limited by this forming method.

The organic light emitting diode may be disposed on a substrate (not shown). The substrate may be disposed under the anode 10 or disposed above the cathode 70 . In other words, the anode 10 may be formed before the cathode 70 or the cathode 70 may be formed before the anode 10 on the substrate.

The substrate may be a light-transmitting substrate as a flat member, and in this case, the substrate may include glass; ceramic materials; It may be made of a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP), and the like. However, the present invention is not limited thereto, and the substrate may be a metal substrate capable of reflecting light.

The organic light emitting diode according to FIG. 1 may further include a protective layer (not shown) and an encapsulation layer (not shown). The protective layer may be disposed on the capping layer, and the encapsulation layer may be disposed on the capping layer, and may be formed to cover side portions of at least one of the anode, the cathode, and the organic layer to protect the anode, the cathode, and the organic layer.

The protective layer may provide a planarized surface so that the encapsulation layer is uniformly formed, and may serve to protect the first electrode, the second electrode, and the organic layer during the manufacturing process of the encapsulation layer.

The encapsulation layer may serve to prevent the penetration of external oxygen and moisture into the organic light emitting diode.

The organic light emitting diode according to an embodiment of the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

Another embodiment of the present invention may include a display device including the organic light emitting diode of the present invention described above, and an electronic device including a controller for controlling the display device.

Hereinafter, the compound according to an aspect of the present invention will be described.

The compound according to one aspect of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1,

A ¹ and A ² are each independently an atom capable of a divalent bond, preferably O or S,

R ₁ and R ₂ are each independently a substituted or unsubstituted C ₄ -C ₃₀ alkyl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₃₀ aryl group, A substituted or unsubstituted C ₆ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylamine, a substituted or unsubstituted It may be a fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide or sulfone group,

R′, R” and R ₃ to R ₁₈ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, substituted or unsubstituted a C ₅ to C ₃₀ aryl group, a substituted or unsubstituted C ₅ to C ₃₀ alkylaryl group, a substituted or unsubstituted C ₆ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₃ -C ₃₀ Heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylamine, substituted or unsubstituted fused arylamine group, substituted or unsubstituted phosphine or phosphine oxide group, substituted or unsubstituted A thiol group, a substituted or unsubstituted sulfoxide or sulfone group, or adjacent groups may be bonded to each other to form a ring.

In the compound, pyrimidine, which is one of heteroaryl groups having an acceptor property in the center, was selectively used. Pyrimidine has a stronger acceptor property than pyridine, which is a similar heteroaryl group in the form of a six-membered ring in which a nitrogen atom is included in the 1st and 3rd positions of the ring, but has relatively weak acceptor properties compared to triazines in which three nitrogens are substituted. have Therefore, it can be applied to light emitting devices in the deep blue to red region depending on the characteristics of the substituents introduced at the 4th and 6th positions of the pyrimidine.

When a compound having a bulky structure, for example, dibenzofuran and dibenzothiophene, is introduced at the 4th and 6th positions of the pyrimidine, the bond between the substituent and the pyrimidine secures twisting characteristics to suppress the substituent and the inhibitor. The scepters will not be coplanar.

Meanwhile, the compound of Formula 1 may be one of the following compounds P-1 to P-128, but is not limited thereto.

In another embodiment of the present invention, the present invention provides a first electrode; a second electrode; and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes the compound represented by Formula 1 alone or in combination.

The organic layer includes at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. That is, at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport auxiliary layer, or an electron injection layer included in the organic layer may include the compound represented by Formula 1.

Preferably, the organic layer includes the light emitting layer. That is, the compound may be included in the light emitting layer or the electron transport layer.

The organic layer includes two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode.

Another aspect of the present invention is to provide an electronic device including a display device including an organic light emitting diode including the compound represented by Chemical Formula 1 and a controller for driving the display device.

In an embodiment of the present invention, the compound of Formula 1 may be included alone, the compound may be included in a combination of two or more different types, or the compound may be included in a combination of two or more other compounds.

Hereinafter, a synthesis example of the compound represented by Formula 1 and a manufacturing example of an organic light emitting diode according to the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

< Synthesis example >

The final product represented by Formula 1 according to the present invention may be synthesized from Sub A as shown in Scheme 1 below, but is not limited thereto.

<P- 1> of Synthesis example

(1) Synthesis of 2-chloro-4,6-bis(dibenzo[ b,d ]furan-4-yl)-5-methylpyrimidine

10 g (50.65 mmol) of 2,4,6-trichloro-5-methylpyrimidine and 20.40 g (96.23 mmol) of dibenzo[ b,d ]furan-4-yl boronic acid, tetrakis(triphenylphosphine) ) Palladium (0) 1.76 g (1.52 mmol) is dissolved using 300 ml of tetrahydrofuran. Then, 100 ml of a 2 M potassium carbonate solution was added and stirred under reflux for 24 hours. After the reaction, extraction with methylene chloride and purification by column chromatography using a mixed solvent of methylene chloride / hexane resulted in 17.2 g (72% yield) of 2-chloro-4,6-bis(dibenzo[ b,d ]furan-4 -yl)-5-methylpyrimidine was obtained.

2-chloro-4,6-bis(dibenzo[ b,d ]furan-4-yl)-5-methylpyrimidine: mass spectrometry (FD+) m/z 460

(2) Synthesis of <P-1>

2-chloro-4,6-bis(dibenzo[ b,d ]furan-4-yl)-5-methylpyrimidine 5 g (10.85 mmol) and phenylboronic acid 1.45 g (11.93 mmol), tetrakis Dissolve 0.38 g (0.33 mmol) of (triphenylphosphine)palladium (0) using 150 ml of tetrahydrofuran. After that, 50 ml of a 2 M potassium carbonate solution was added and stirred under reflux for 24 hours. After the reaction, extraction was performed with methylene chloride, followed by purification by column chromatography with a mixed solvent of methylene chloride/hexane, and finally, 4.7 g of a pure white solid was obtained through sublimation purification.

<P-1>: Yield 86%, mass spectrometry (FD+) m/z 502, elemental analysis theoretical value C ₃₅ H ₂₂ N ₂ O ₂ : C,83.65%, H,4.41%, N,5.57%, O,6.37 %. Measured value: C,83.62%, H,4.47%, N,5.60%, O,6.31%

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.28 (d, 2H), 7.89 (d, 4H), 7.66 (d, 4H), 7.51 (t, 2H), 7.41 (m, 3H), 7.38 (t) , 4H), 7.32 (t, 2H), 2.34 (s, 3H)

<P- 4> of Synthesis example

2,4,6-trichloro-5-methylpyrimidine 2 g (10.13 mmol) and dibenzo[ b,d ]furan-4-yl boronic acid 7.52 g (35.45 mmol), bis(triphenylphosphine) Dissolve 0.36 g (0.51 mmol) of palladium (2) dichloride using 105 ml of dioxane. After that, 35 ml of a 2 M potassium carbonate solution was added and stirred under reflux for 24 hours. After the reaction, extraction was performed with methylene chloride, followed by purification by column chromatography with a mixed solvent of methylene chloride/hexane, and finally, 5.7 g of a pure white solid was obtained through sublimation purification.

<P-4>: Yield 95%, mass spectrometry (FD+) m/z 592, elemental analysis theoretical value C ₄₁ H ₂₄ N ₂ O ₃ : C,83.09%, H,4.08%, N,4.73%, O,8.10 %. Measured value: C,83.01%, H,4.07%, N,4.74%, O,8.18%

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.89 (d, 3H), 7.85 (d, 3H), 7.81 (d, 1H), 7.66 (d, 3H), 7.62 (d, 2H), 7.38 (t) , 6H), 7.32 (m, 3H), 2.34 (s, 3H)

<P- 80> of Synthesis example

(1) Synthesis of 2-chloro-4,6-bis(dibenzo[ b,d ]furan-1-yl)-5-methylpyrimidine

10 g (50.65 mmol) of 2,4,6-trichloro-5-methylpyrimidine and 20.40 g (96.23 mmol) of dibenzo[ b,d ]furan-1-yl boronic acid, tetrakis(triphenylphosphine) ) Palladium (0) 1.76 g (1.52 mmol) is dissolved using 300 ml of tetrahydrofuran. Then, 100 ml of a 2 M potassium carbonate solution was added and stirred under reflux for 24 hours. After the reaction, extraction was performed with methylene chloride, and as a result of purification by column chromatography with a mixed solvent of methylene chloride/hexane, 15.2 g (65% yield) of 2-chloro-4,6-bis(dibenzo[ b,d ]furan- 1-yl)-5-methylpyrimidine was obtained.

2-Chloro-4,6-bis(dibenzo[ b,d ]furan-1-yl)-5-methylpyrimidine: mass spectrometry (FD+) m/z 460

(2) Synthesis of <P-80>

2-chloro-4,6-bis(dibenzo[ b,d ]furan-1-yl)-5-methylpyrimidine 5 g (10.85 mmol) and phenylboronic acid 1.45 g (11.93 mmol), tetrakis Dissolve 0.38 g (0.33 mmol) of (triphenylphosphine)palladium (0) using 150 ml of tetrahydrofuran. After that, 50 ml of a 2 M potassium carbonate solution was added and stirred under reflux for 24 hours. After the reaction, the mixture was extracted with methylene chloride, purified by column chromatography with a methylene chloride/hexane mixed solvent, and finally, 4.2 g of a pure white solid was obtained through sublimation purification.

<P-80>: Yield 77%, mass spectrometry (FD+) m/z 502, elemental analysis theoretical value C ₃₅ H ₂₂ N ₂ O ₂ : C,83.65%, H,4.41%, N,5.57%, O,6.37 %. Measured value: C,83.63%, H,4.46%, N,5.56%, O,6.35%

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.28 (d, 2H), 7.89 (d, 2H), 7.75 (d, 2H), 7.66 (d, 2H), 7.62 (d, 2H), 7.51 (t) , 2H), 7.44 (t, 2H), 7.41 (t, 1H), 7.38 (t, 4H), 2.34 (s, 3H)

<P- 96> of Synthesis example

(1) Synthesis of 2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-5-methylpyrimidine

10 g (50.65 mmol) of 2,4,6-trichloro-5-methylpyrimidine and 9.66 g (45.58 mmol) of dibenzo[ b,d ]furan-4-yl boronic acid, tetrakis(triphenylphosphine) ) Palladium (0) 1.76 g (1.52 mmol) is dissolved using 210 ml of tetrahydrofuran. After that, 70 ml of a 2 M potassium carbonate solution was added, and the mixture was stirred under reflux for 24 hours. After the reaction, extraction with methylene chloride and purification by column chromatography with a mixed solvent of methylene chloride/hexane resulted in 8.7 g (52% yield) of 2,4-dichloro-6-(dibenzo[b,d]furan-4- Day)-5-methylpyrimidine was obtained.

2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-5-methylpyrimidine: mass spectrometry (FD+) m/z 328

(2) Synthesis of 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-(dibenzo[b,d]thiophen-1-yl)-5-methylpyrimidine

8 g (24.30 mmol) of 2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-5-methylpyrimidine and dibenzo[ b,d ]thiophen-1-yl boronic 6.1 g (26.73 mmol) of the acid and 0.28 g (0.24 mmol) of tetrakis (triphenylphosphine) palladium (0) are dissolved using 120 ml of tetrahydrofuran. After that, 40 ml of a 2 M potassium carbonate solution was added, and the mixture was stirred under reflux for 24 hours. After the reaction, the mixture was extracted with methylene chloride and purified by column chromatography with a mixed solvent of methylene chloride/hexane. As a result, 9.2 g (79% yield) of 2-chloro-4-(dibenzo[b,d]furan-4-yl) -6-(dibenzo[b,d]thiophen-1-yl)-5-methylpyrimidine was obtained.

2-Chloro-4-(dibenzo[b,d]furan-4-yl)-6-(dibenzo[b,d]thiophen-1-yl)-5-methylpyrimidine: mass spectrometry (FD+) m/z 476

(3) Synthesis of <P-96>

2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-(dibenzo[b,d]thiophen-1-yl)-5-methylpyrimidine 5 g (10.50 mmol) Dissolve 1.41 g (11.55 mmol) of phenylboronic acid and 0.32 g (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0) using 150 ml of tetrahydrofuran. After that, 50 ml of a 2 M potassium carbonate solution was added, and the mixture was stirred under reflux for 24 hours. After the reaction, extraction was performed with methylene chloride, followed by purification by column chromatography with a mixed solvent of methylene chloride/hexane, and finally, 4.8 g of a pure white solid was obtained through sublimation purification.

<P-96>: Yield 88%, mass spectrometry (FD+) m/z 518, elemental analysis theoretical value C ₃₅ H ₂₂ N ₂ OS: C,81.06%, H,4.28%, N,5.40%, O,3.08% , S, 6.18%. Measured value: C,81.03%, H,4.31%, N,5.36%, O,3.10%, S, 6.20%

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.45 (d, 1H), 8.28 (d, 2H), 7.98 (d, 1H), 7.94 (d, 1H), 7.89 (d, 1H), 7.85 (d , 1H), 7.82 (d, 1H), 7.66 (d, 1H), 7.56 (t, 1H), 7.52 (m, 4H), 7.41 (t, 1H), 7.38 (m, 2H), 7.32 (t, 1H), 2.34 (s, 3H)

Synthesis example of <P-120>

(1) Synthesis of 9-(6-chlorodibenzo[ b,d ]furan-1-yl)-9H-carbazole

6-chloro-1-fluorodibenzo[ b,d ]furan 10 g (45.32 mmol), 9H-carbazole 11.37 g ( 67.99 mmol), potassium carbonate 25 g (181.30 mmol) using 300 ml of dimethylformamide After dissolution, the mixture was stirred under reflux for 24 hours. After the reaction, the mixture was extracted with methylene chloride and purified by column chromatography with a mixed solvent of methylene chloride/hexane. As a result, 14.7 g (88% yield) of 9-(6-chlorodibenzo[ b,d ]furan-1-yl)- 9H-carbazole was obtained.

9-(6-chlorodibenzo[ b,d ]furan-1-yl)-9H-carbazole: mass spectrometry (FD+) m/z 367

(2) 9-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-1-yl)- Synthesis of 9 H -carbazole

9-(6-chlorodibenzo[ b,d ]furan-1-yl)-9H-carbazole 14 g (38.06 mmol) and bis(pinacolato)diboron 14.50 g (57.09 mmol), [1,1 '-bis(diphenylphosphino)ferrocene]palladium(2)dichloride 0.84 g (1.14 mmol) and potassium acetate 11.21 g (114.18 mmol) were dissolved using 350 ml of 1,4-dioxane, and then for 24 hours It was stirred at reflux. After the reaction, extraction was performed with methylene chloride, and as a result of purification by column chromatography with an ethyl acetate/hexane mixed solvent, 16.1 g (92% yield) of 9-(6-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-1-yl) -9H -carbazole was obtained.

9-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-1-yl) -9H- Carbazole: Mass Spectrometry (FD+) m/z 459

(3) 9,9'-(6,6'-(2-chloro-5-methylpyrimidine-4,6-diyl)bis(dibenzo[ b,d ]furan-6,1-diyl))bis Synthesis of (9 H -carbazole)

2,4,6-trichloro-5-methylpyrimidine 2 g (10.13 mmol) and 9-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-) 2-yl) dibenzo [b, d] furan-1-yl) -9H -carbazole 11.63 g (25.32 mmol), tetrakis (triphenylphosphine) palladium (0) 0.35 g (0.30 mmol) tetra Dissolve using 120 ml of hydrofuran. After that, 40 ml of a 2 M potassium carbonate solution was added, and the mixture was stirred under reflux for 24 hours. After the reaction, the mixture was extracted with methylene chloride and purified by column chromatography with a mixed solvent of methylene chloride/hexane. As a result, 5.6 g (69% yield) of 9,9'-(6,6'-(2-chloro-5-methylpyri) Midin -4,6-diyl)bis(dibenzo[ b,d ]furan-6,1-diyl))bis(9H-carbazole) was obtained.

9,9'-(6,6'-(2-chloro-5-methylpyrimidine-4,6-diyl)bis(dibenzo[ b,d ]furan-6,1-diyl))bis( 9H -carbazole): mass spectrometry (FD+) m/z 790

(4) Synthesis of <P-120>

9,9'-(6,6'-(2-chloro-5-methylpyrimidine-4,6-diyl)bis(dibenzo[ b,d ]furan-6,1-diyl))bis( 9H -carbazole) 5 g (6.32 mmol), phenylboronic acid 0.85 g (6.95 mmol), tetrakis (triphenylphosphine) palladium (0) 0.22 g (0.19 mmol) using 90 ml of tetrahydrofuran melt it Then, 30 ml of a 2 M potassium carbonate solution was added, and the mixture was stirred under reflux for 24 hours. After the reaction, the mixture was extracted with methylene chloride, purified by column chromatography with a methylene chloride/hexane mixed solvent, and finally purified by sublimation to obtain 4.1 g of a pure white solid.

<P-120>: Yield 77%, mass spectrometry (FD+) m/z 832, elemental analysis theoretical value C ₅₉ H ₃₆ N ₄ O ₂ : C,85.08%, H,4.36%, N,6.73%, O,3.84 %. Measured value: C,85.03%, H,4.33%, N,6.76%, O,3.89%

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.55 (d, 2H), 8.28 (d, 2H), 8.12 (d, 2H), 7.94 (d, 2H), 7.85 (d, 2H), 7.66 (m) , 6H), 7.51 (t, 4H), 7.44 (d, 2H), 7.41 (t, 1H), 7.38 (t, 4H), 7.33 (t, 2H), 7.29 (t, 4H), 2.34 (s, 3H)

of organic light emitting diodes Manufacturing evaluation

( Example One) delayed fluorescence organic light emitting diode Produce

(ITO/ PEDOT:PSS / TAPC / mCP /compound P- 1:DMAC - DPS / TSPO1 / TPBi / LiF /Al)

The glass substrate on which the anode, ITO was deposited, was washed in ultrasonic waves for 30 minutes using tertiary distilled water and isopropyl alcohol. After surface treatment of the washed ITO substrate using short-wavelength ultraviolet light, poly(3,4-edylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS) was spun to a thickness of 60 nm. A hole injection layer was formed by coating.

Then, (1,1-bis[4-[ N , N' -di( p -tolyl)amino]phenyl]cyclohexane) (TAPC) at a pressure of 1x10 ^{- 6} torr at a rate of 0.1 nm/s By deposition, a hole transport layer of 20 nm was formed.

Thereafter, N , N -dicarbazolyl-3,5-benzene (mCP) was deposited at a rate of 0.1 nm/s at a pressure of 1x10 ^-6 torr to form an exciton blocking layer of 10 nm.

Then, the compound P-1 synthesized in Synthesis Example 1 as a host material at a pressure of 1x10 ^-6 torr at a rate of 0.1 nm/s, and TmCz-Trz as a delayed fluorescence dopant material at a rate of 0.005 nm/s. Deposited to form a light emitting layer doped with a dopant 20% on the host.

Diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1) and 1,3,5-tris( N -phenylbenzimidazol-2-yl)benzene (TPBi) were mixed with 0.1 at a pressure of 1x10 ^-6 torr They were sequentially deposited at a rate of nm/s to form an exciton blocking layer and an electron transport layer of 5 nm and 30 nm, respectively.

Then, as an electron injection material, LiF was deposited at a pressure of 1x10 ^-6 torr at a rate of 0.01 nm/s to form an electron injection layer of 1 nm. Thereafter, Al was deposited at a rate of 0.5 nm/sec under a pressure of 1x10 ^-6 torr to form a 100 nm cathode, thereby forming an organic light emitting diode. After device formation, the device was sealed using a CaO desiccant and a glass cover glass.

( Example 2) to ( Example 4)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 1 was used instead of the compound P-1 of the present invention in Example 1.

( comparative example One)

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Comparative Compound 1 below was used instead of Compound P-1 of the present invention in Example 1.

<Comparative compound 1>

The electroluminescence characteristics were measured by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 4 and Comparative Example 1, and the evaluation results of the manufactured devices are shown in Table 1 below.

light emitting layer
(host) drive voltage
(V)

(%)

(%) luminance
(

) current density
(

) color coordinates
(x:y) Comparative Example 1 DPEPO 3.2 13.5 7025 18.5 0.20:0.49 Example 1 P-1 3.4 14.5 7156 4.6 0.20:0.48 Example 2 P-4 3.3 14.2 7089 16.7 0.21:0.49 Example 3 P-96 3.1 15.8 8152 58.2 0.20:0.48 Example 4 P-120 3.5 16.2 9251 83.5 0.20:0.49

As can be seen from the results of Table 1, when the organic light emitting diode was manufactured using the compound of the present invention, the luminous efficiency of the organic light emitting diode was significantly improved compared to the case of using Comparative Compound 1.

In addition, in the evaluation result of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied only to the light emitting layer has been described, but the compound of the present invention may be applied to one or more of the light emitting layer and the electron transport layer.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains include other compounds in the light emitting layer within a range that does not depart from the essential characteristics of the present invention. Various modifications are possible.

Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the scope of the spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

10: anode 20: hole conductive layer
23: hole injection layer 25: hole transport layer
40: light emitting layer 50: electron conductive layer
53: electron injection layer 55: electron transport layer
70: cathode

Claims (7)

A compound represented by the following formula (1):
<Formula 1>

In Formula 1,
A ¹ and A ² are each independently O or S,
R ₁ is a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, R ₂ is a substituted or unsubstituted C ₆ to C ₃₀ aryl group or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group,
R ₂ is a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, R ₁ is a substituted or unsubstituted C ₆ to C ₃₀ aryl group or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group,
R ₃ to R ₁₀ are each independently hydrogen or deuterium; One of R ₃ to R ₁₀ is a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, the rest are independently hydrogen or deuterium;
R ₁₁ to R ₁₈ are each independently hydrogen or deuterium; One of R ₁₁ to R ₁₈ is a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, and the rest are independently hydrogen or deuterium. The compound according to claim 1, wherein the compound of Formula 1 is one of the following compounds P-1 to P-128:

anode; cathode; and an organic layer formed between the anode and the cathode,
The organic layer is an organic light emitting diode, characterized in that it comprises the compound represented by Formula 1 of claim 1 alone or in combination. 4. The method of claim 3,
The organic layer comprises at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, and an electron injection layer. 5. The method of claim 4,
The organic layer is an organic light emitting diode, characterized in that it comprises the light emitting layer. 4. The method of claim 3,
The organic layer comprises at least two stacks including a hole transport layer, a light emitting layer and an electron transport layer sequentially formed on the anode. A display device comprising the organic light emitting diode of claim 3; and a controller for driving the display device.

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