KR20120130074A - Composition for organic photoelectric device and organic photoelectric device using the same - Google Patents

Abstract

PURPOSE: A composition for organic photoelectric device is provided to be used for applying to a wet process and to have high luminous efficiency even under low driving voltage and to improve life time I n case used in an organic thin film layer of an organic photoelectric device. CONSTITUTION: A composition for organic photoelectric device comprises a first host compound combined with substituents indicated in chemical formula 1, chemical formula 2a-2c, and chemical formula 3, and a second host compound indicated in chemical formula 4 or 5. The weight ratio of the first host compound and the second host compound is 50:1-2,500. An organic photoelectric device comprises a positive electrode, a negative electrode, an organic thin film layer inserted between the positive electrode and negative electrode. The organic thin film layer is formed by using the composition for organic photoelectric device.

Description

Composition for organic photoelectric device and organic photoelectric device using same {COMPOSITION {FOR ORGANIC PHOTOELECTRIC DEVICE AND ORGANIC PHOTOELECTRIC DEVICE USING THE SAME}

The present disclosure relates to a composition for an organic photoelectric device and an organic photoelectric device using the same.

A photoelectric device is a device that converts light energy into electrical energy or converts electrical energy into light energy in a broad sense. Examples of the optoelectronic device may include organic light emitting diodes (OLEDs), solar cells, and transistors. In particular, the organic light emitting device is attracting attention as the demand for flat panel displays increases.

When current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the emission layer through the respective hole transport layer and the electron transport layer to form a light emission exciter. The light-excited excitons thus formed emit light while transitioning to ground states. The light may be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons, and the fluorescence and phosphorescence may be used as light emitting sources of organic light emitting devices (DFO'Brien et al., Appl. Phys). Lett., 74 (3), 442, 1999; MA Baldo et al., Appl. Phys. Lett., 75 (1), 4, 1999).

When the electrons transition from the ground state to the excited state, the singlet excitons are non-luminescent transition to triplet excitons through intersystem crossing, and the triplet excitons are transferred to the ground state to emit light. At this time, the generated light is called phosphorescence. The triplet excitons cannot spin directly to the ground state (spin forbidden) and must undergo a flipping step of electron spin. Therefore, phosphorescence has a characteristic that the half life (luminescence time, lifetime) is longer than that of fluorescence.

In addition, when holes and electrons recombine to form luminescent excitons, triplet excitons are generated about three times more than singlet excitons. Therefore, the fluorescence using only singlet excitons has a 25% probability of generating singlet excitons and thus has a limit in luminous efficiency. However, phosphorescence can be used not only with a 75% probability of generating triplet excitons but also up to 25%, which is a probability of generating singlet excitons, so that the luminous efficiency can be theoretically 100%. That is, phosphorescence has an advantage of achieving about 4 times higher luminous efficiency than fluorescence.

Meanwhile, in order to increase efficiency and stability of the organic light emitting diode, a host material and a dopant may be added together to the light emitting layer. As a host material, 4,4-N, N-dicarbazole biphenyl (CBP) is used in the green phosphorescent dopant and 1,3-bis (carbazole-9-yl) benzene (1,3- is used in the blue phosphorescent dopant. Organic compounds containing carbazoles such as bis (carbazol-9-yl) benzene, MCP), and organic metal compounds such as aluminum (Al) complexes and beryllium (Be) complexes are mainly used for red phosphorescent pants. However, most of these low molecular weight host materials have low solubility in organic solvents and are difficult to apply to wet processes due to problems such as easy crystallization after film formation.

Therefore, in order to implement an organic photoelectric device having excellent efficiency and lifespan, it is necessary to develop a host material having bipolar characteristics which are excellent in electrical and stability and can transfer both holes and electrons well.

One embodiment of the present invention is to provide a composition for organic photoelectric devices that can transfer both holes and electrons well.

Another embodiment of the present invention is formed using the composition for an organic photoelectric device is to provide an organic photoelectric device excellent in efficiency, driving voltage and lifespan characteristics.

Another embodiment of the present invention is to provide a display device including the organic photoelectric device.

In one embodiment of the present invention, Formula 1; Any one of the following Formulas 2a to 2c; And a first host compound in which a substituent represented by Formula 3 is sequentially bonded; And it provides a composition for an organic photoelectric device comprising a second host compound represented by the following formula (4) or (5).

[Formula 1] [Formula 3]

In Formulas 1 and 3, R ¹ and R ² are the same as or different from each other, and each independently an amine group, carbazolyl group, C1 to C30 alkyl group, C6 to C30 aryl group or a combination thereof, R ³ and R ⁴ is the same as or different from each other, and each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,

[Formula 4] [Formula 5]

In Formulas 4 and 5, Q ¹ to Q ¹⁰ are the same as or different from each other, and each independently N or CR ⁵ , provided that at least one selected from Q ¹ to Q ⁶ in Formula 4 is N, and at least one being in the general formula 5 selected from Q ¹ to Q ⁵ is N, Q ⁶ to at least any one selected from Q ¹⁰ is N, wherein R ⁵ is an amine group, a carbazolyl group, a fluorenyl group, C1 to An alkyl group of C 60, an aryl group of C 6 to C 60, or a combination thereof, R ⁵ ′ is a fluorenylene group, an alkylene group of C 1 to C 60, an arylene group of C 6 to C 60, or a combination thereof,

[Formula 2a] [Formula 2b] [Formula 2c]

In Formulas 2a to 2c, R ⁶ and R ⁷ are the same as or different from each other, and each independently an amine group, carbazolyl group, C1 to C30 alkyl group, C6 to C30 aryl group, or a combination thereof.

The first host compound may be represented by the following Chemical Formulas 6 to 12.

[Formula 6] [Formula 7]

8 [Formula 9]

[Formula 11]

[Chemical Formula 12]

In Formulas 6 to 12, R ¹ and R ² are the same as or different from each other, and each independently an amine group, carbazolyl group, C1 to C30 alkyl group, C6 to C30 aryl group, or a combination thereof, R ³ and R ⁴ is the same as or different from each other, and each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof, and R ⁶ and R ⁷ are the same or different. Each independently represents an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof.

The first host compound may be represented by the following Formula 22, 30, 33 or 42.

At least any one selected from Q ¹ to Q ⁶ of the second host compound represented by Formula 4 may be N.

The second host compound represented by Chemical Formula 4 may be represented by the following Chemical Formula 4a.

[Chemical Formula 4a]

In Formula 4a, R ^{5a To} R ^5c Is  The same or different from each other, each independently is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 aryl group or a combination thereof.

At least any set selected from Q ¹ to Q ⁵ of the second host compound represented by Formula 5 may be N, and at least any set selected from Q ⁶ to Q ¹⁰ may be N.

The second host compound represented by Chemical Formula 5 may be represented by Chemical Formula 5a.

[Formula 5a]

In Formula 5a, R ^5d to R ^5g are  Equal to or different from each other, each independently is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 aryl group or a combination thereof, R ⁵ "is a fluorenylene group, C1 to C60 Alkylene group, C6 to C60 arylene group or a combination thereof.

The second host compound may be represented by the following Chemical Formulas 43 to 56.

The composition for an organic photoelectric device may include a first host compound: second host compound in a weight ratio of 50: 1 to 2,500.

In another embodiment of the present invention, a positive electrode; cathode; And an organic thin film layer interposed between the anode and the cathode, wherein the organic thin film layer is formed using the composition for an organic photoelectric device described above.

The composition for an organic photoelectric device may be used as a host material for phosphorescence.

The organic thin film layer may be a light emitting layer.

The organic thin film layer may further include a dopant.

The dopant may be a phosphorescent dopant of red, green, or blue.

In another embodiment of the present invention, a display device including the organic photoelectric device described above is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

The composition for an organic photoelectric device according to the embodiment of the present invention is suitable for application to a wet process, and particularly, is used in an organic thin film layer of an organic photoelectric device, and has a high luminous efficiency even at a low driving voltage, and has an improved lifetime. And a display device.

1 to 5 are cross-sectional views showing various embodiments of the organic photoelectric device that can be manufactured using the composition for an organic photoelectric device according to an embodiment of the present invention.
Figure 6 shows the results of nuclear magnetic resonance spectroscopy analysis of the compound synthesized in Preparation Example 3.
7 is a graph illustrating current efficiency according to luminance change of organic light emitting diodes manufactured in Examples 1 to 4 and Comparative Example 5. FIG.
8 shows power efficiency graphs according to luminance changes of the organic light emitting diodes manufactured in Examples 1 to 4 and Comparative Example 5. FIG.
* Figure 9 shows a life graph of the organic light emitting device manufactured in Examples 1 to 4.
10 is a graph showing the life of organic light emitting devices manufactured in Comparative Examples 1 to 5. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Although the composition for an organic photoelectric device according to the exemplary embodiment of the present invention is a low molecular weight compound, it has high solubility in organic solvents and includes host compounds that may have excellent film quality when forming a thin film by a wet process.

More specifically, one embodiment of the present invention is a first host compound in which the substituents represented by the following formula 1 to 3 are sequentially bonded; And it provides a composition for an organic photoelectric device comprising a second host compound represented by the formula (4) or (5).

[Formula 1] [Formula 2] [Formula 3]

In Chemical Formulas 1 to 3

L is C2 or C3 alkenylene or C6 to C12 arylene. At this time, when L is C2 or C3 alkenylene, each ring containing N in the general formulas (1) and (3) forms a pentagonal ring or a hexagonal ring.

R ¹ and R ² are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof. In particular, the R ¹ and R ² is a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C20, an arylcarbazolyl group of C12 to C30, an alkylcarbazolyl group of C13 to C30, an arylamine of C6 to C30 Groups, C1 to C30 alkylamine groups, and the like. In this case, the substituents of R ¹ and R ² of the first host compound are bonded at an angle of 30 ° or more with respect to the plane of each ring including N in Formulas 1 and 3 to form a three-dimensional structure. This three-dimensional structure can prevent the first host compound from being easily crystallized. In addition, the solubility in organic solvents can be improved. However, the above R ¹ to R ⁴ are not limited thereto.

R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,

[Formula 4] [Formula 5]

In Chemical Formulas 4 and 5

Q ¹ to Q ¹⁰ are the same as or different from each other, and each independently N or CR ⁵ , provided that at least one selected from Q ¹ to Q ⁶ in Formula 4 is N, and Q ¹ to Q in Formula 5 At least one selected from ⁵ is N, at least one selected from Q ⁶ to Q ¹⁰ is N, wherein R ⁵ is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 Aryl group or a combination thereof,

R ⁵ ′ is a fluorenylene group, a C1 to C60 alkylene group, a C6 to C60 arylene group or a combination thereof.

The first host compound is a hole transport compound, and the second host compound is an electron transport compound. The hole transport compound refers to a compound having a function of having a conduction characteristic along the HOMO level and having a cationic characteristic by hole formation. In addition, the electron transport compound refers to a compound having a function capable of having an anion characteristic by electron formation having conduction properties along the LUMO level.

Therefore, the composition for an organic photoelectric device according to the embodiment of the present invention may have a bipolar characteristic. That is, the composition for an organic photoelectric device may exhibit excellent interfacial properties and charge charge transport capability in the light emitting layer of the organic photoelectric device that holes and electrons are bonded.

In addition, the substituent represented by Formula 2 may be represented by the following formula (2a) to 2c.

[Formula 2a] [Formula 2b] [Formula 2c]

In Chemical Formulas 2a to 2c

R ₆ and R ₇ are the same as or different from each other, and are each independently hydrogen, an amine group, a carbazole group, an alkyl group of C ₁ to C ₃₀ , an aryl group of C ₆ to C ₃₀ , or a combination thereof.

In particular, the substituent represented by Chemical Formula 2 may be represented by the following Chemical Formulas 2a to 2c.

[Formula 2a] [Formula 2b] [Formula 2c]

In Chemical Formulas 2a to 2c

R ⁶ and R ⁷ are the same as or different from each other, and are each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof.

In addition, the first host compound may be represented by the following Chemical Formulas 6 to 12.

[Formula 6] [Formula 7]

8 [Formula 9]

[Formula 11]

[Chemical Formula 12]

In Chemical Formulas 6 to 12

R ¹ and R ² are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,

R ³ , R ⁴ ,  R ⁶ and R ⁷ are the same as or different from each other, and are each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,

More specifically, the first host compound may be represented by Formulas 13 to 42. However, the first host compound is not limited thereto.

In addition, at least any one selected from Q ¹ to Q ⁶ of the second host compound represented by Formula 4 may be N. In particular, the second host compound represented by Formula 4 may be represented by the following Formula 4a.

[Chemical Formula 4a]

In Chemical Formula 4a

R ^5a to R ^5c are  The same or different from each other, each independently is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 aryl group or a combination thereof.

In addition, at least any set selected from Q ¹ to Q ⁵ of the second host compound represented by Formula 5 may be N, and at least any set selected from Q ⁶ to Q ¹⁰ may be N. In particular, the second host compound represented by Chemical Formula 5 may be represented by Chemical Formula 5a.

[Formula 5a]

In Chemical Formula 5a

R ^5d to R ^5g are  The same as or different from each other, each independently an amine group, a carbazolyl group, a fluorenyl group, an alkyl group of C1 to C60, an aryl group of C6 to C60, or a combination thereof,

R ⁵ ″ is a fluorenylene group, a C1 to C60 alkylene group, a C6 to C60 arylene group or a combination thereof.

In addition, the second host compound may be represented by Formulas 43 to 56. However, the second host compound is not limited thereto.

In addition, the composition for an organic photoelectric device includes a first host compound: second host compound in a weight ratio of 50: 1 2 to 2,500.

In addition, the composition for an organic photoelectric device may further be usefully applied to forming a thin film using a wet process further including a solvent. 　 Such solvents are generally used in the art and are not particularly limited in kind, but include, for example, aromatic organic solvents such as toluene, xylene, and xylene; Aromatic organic solvents substituted with halogen elements such as chlorobenzene and dichlorobenzene; Polar organic solvents such as pyridine, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone; Or these mixed solvent can be used. However, the solvent is not limited thereto.

The solvent may be included in an amount of 100 to 20,000 parts by weight based on 100 parts by weight of the total content of the first host compound and the second host compound. In particular, the solvent may be included in 100 to 7,000 parts by weight based on 100 parts by weight of the total content of the first host compound and the second host compound.

When the total content of the first host compound and the second host compound in the solvent is 0.5% by weight or more, it is applicable to the organic photoelectric device, and particularly preferably 1.5% by weight or more.

According to another embodiment of the present invention, a positive electrode; cathode; And an organic thin film layer interposed between the anode and the cathode, wherein the organic thin film layer is formed using the composition for an organic photoelectric device. In this case, the organic photoelectric device means an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, or an organic memory device. In the case of an organic solar cell, the quantum efficiency is increased by forming an electrode or an electrode buffer layer using the composition for an organic photoelectric device according to an embodiment of the present invention, and in the case of an organic transistor, a gate, a source-drain electrode, and the like are electrode materials. Can be used.

The organic thin film layer may include a light emitting layer, a hole transport layer, a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron blocking layer, or a combination thereof, wherein the light emitting layer is one of the present invention. It may be formed using a composition for an organic photoelectric device according to the embodiment.

The composition for an organic photoelectric device may be used as a host material for phosphorescence.

The organic thin film layer may further include a dopant, and the dopant may be a phosphorescent dopant of red, green, or blue.

The dopant is a compound having high luminous ability per se, and is also referred to as a guest because a small amount of the dopant is mixed with the host. That is, a dopant is a material that emits light by doping the host material, and generally, a material such as a metal complex that emits light by multiplet excitation that excites above a triplet state is used. . As such dopants, any fluorescent or phosphorescent dopants of red (R), green (G), and blue (B), which are generally used in the art, may be used, but in particular, red, green, or blue phosphorescent dopants may be used. It is good. In addition, it is possible to use those having high luminous efficiency, poor aggregation, and uniform distribution in the host material.

Examples of the phosphorescent dopant include an organometallic compound including an element which is Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. Can be. More specifically, what is represented by following formula 57-59 can be used. However, the phosphorescent dopant is not limited thereto.

[Formula 57] [Formula 58] [Formula 59]

Hereinafter, an organic photoelectric device will be described in detail.

1 to 5 are cross-sectional views of an organic photoelectric device according to an embodiment of the present invention.

1 to 5, the organic photoelectric device 100, 200, 300, 400, and 500 includes an anode 120, a cathode 110, and at least one organic thin film layer interposed between the anode and the cathode. It has a structure that includes (105).

The substrate used in the organic photoelectric device is generally used in the art, and is not particularly limited. More specifically, substrates such as glass substrates and transparent plastic substrates having excellent transparency, surface smoothness, ease of handling, and waterproofing properties can be used. have.

The anode 120 may include a material having a large work function to smoothly inject holes into the organic thin film layer. Specific examples of the positive electrode include metals such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or alloys of these metals; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like; Combinations of metal oxides and metals such as ZnO / Al, SnO ₂ / Sb, and the like; Poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (poly [3,4- (ehtylene-1,2-dioxy) thiophene]: PEDOT or PEDT ), Conductive polymers such as PEDOT / polystyrenesulfonate (PSS), polypyrrole, polyaniline, and the like. However, the anode is not limited to the above materials. More specifically, the anode may use a transparent electrode including ITO.

The cathode 110 may include a material having a small work function to smoothly inject electrons into the organic thin film layer. Specific examples of the negative electrode include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof; Multilayer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al, BaF ₂ / Ca and the like. However, the negative electrode is not limited to the above materials. More specifically, the cathode may use a metal electrode such as aluminum.

First, FIG. 1 illustrates an organic photoelectric device 100 in which only the light emitting layer 130 exists as the organic thin film layer 105, and the organic thin film layer 105 may exist only as the light emitting layer 130.

2 illustrates a two-layered organic photoelectric device 200 in which an emission layer 230 including an electron transport layer and a hole transport layer 140 exist as an organic thin film layer 105, and the organic thin film layer 105 includes an emission layer 230 and The hole transport layer 140 may include a two-layer type. In this case, the light emitting layer 130 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve the bonding property with a transparent electrode such as ITO and the hole transporting property.

The hole transport layer 140 is generally used in the art and is not particularly limited in kind. For example, a poly (3,4-ethylenedioxy- doped with a poly (styrenesulfonate) (PSS) layer. Thiophene) (PEDOT), PEDOT: PSS, N, N'-bis (3-methylphenyl) -N, N-diphenyl- [1,1'-biphenyl] -4,4'-diamine (TPD), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB) and the like can be used with the composition for an organic photoelectric device according to an embodiment of the present invention.

3 illustrates a three-layered organic photoelectric device 300 having an electron transport layer 150, a light emitting layer 130, and a hole transport layer 140 as an organic thin film layer 105. 130 is in an independent form, and has a form in which layers (electron transport layer 150 and hole transport layer 140) having excellent electron transport properties and hole transport properties are stacked in separate layers.

The electron transport layer 150 is generally used in the art, and is not particularly limited. For example, aluminum tris (8-hydroxyquinoline) (Alq ₃ ); 1,3,4-oxadiazole derivatives such as 2- (4-biphenyl-5-phenyl-1,3,4-oxadiazole (PBD); 1,3,4-tris [(3-phenyl- Quinoxarin derivatives such as 6-trifluoromethyl) quinoxalin-2-yl] benzene (TPQ), and triazole derivatives, and the like, can be used together with the composition for an organic photoelectric device according to an embodiment of the present invention. .

4 illustrates a four-layered organic photoelectric device 400 having an electron injection layer 160, an emission layer 130, a hole transport layer 140, and a hole injection layer 170 as the organic thin film layer 105. The hole injection layer 170 may improve adhesion to ITO used as an anode.

5 illustrates five layers having different functions as the organic thin film layer 105, such as the electron injection layer 160, the electron transport layer 150, the light emitting layer 130, the hole transport layer 140, and the hole injection layer 170. This 5-layered organic photoelectric device 500 is present, and the organic photoelectric device 500 is effective for lowering the voltage by forming the electron injection layer 160 separately.

The thicknesses of the hole transport layer 140,, and the electron transport layer 150 may be independently 10 to 10,000 독립적. However, the thickness range is not limited.

1 to 5, the light emitting layers 130 and 230 constituting the organic thin film layer 105 may be formed using the composition for an organic photoelectric device according to an embodiment of the present invention.

The above-described organic photoelectric device may include a dry film method such as an evaporation, sputtering, plasma plating, ion plating, etc. after forming an anode on a substrate; Manufactured by forming an organic thin film layer by a wet film method such as inkjet printing, screen printing, slit coating, spin coating, dipping, flow coating, etc., and then forming a cathode thereon. can do. In particular, the organic thin layer can be formed very easily by a wet film method.

According to another embodiment of the present invention, a display device including the organic photoelectric device is provided.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Manufacturing example  1: Synthesis of Compound of Formula 20

The compound of Formula 20 was synthesized by the same method as in Scheme 1 below.

[Reaction Scheme 1]

3.6 g of Compound p, 2.3 g of Compound q, 0.5 g of Pd (PPh ₃ ) ₄ , and 5 g of K ₂ CO ₃ were mixed with 50 mL of toluene, stirred at 100 ° C. for 24 hours, and then cooled to room temperature. . Then, 50 mL of distilled water was added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and 1.5 g of the product was separated by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 1 volume ratio) as a developing solution. 1.5 g of the separated product and 5 g of triphenylphosphine (PPh ₃ ) were mixed with 30 mL of dichlorobenzene, stirred at 160 ° C. for 12 hours, dichlorobenzene was distilled off, and then cooled to room temperature . The remaining solution was separated by 0.8 g of silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 3 volume ratio) as a developing solution.

0.8 g of the compound r, 1.5 g of 4-bromobenzene, 0.1 g of CuCl, and 2 g of K ₂ CO ₃ were mixed in 10 mL of dimethyl sulfoxide, stirred at 170 ° C. for 12 hours, and then cooled to room temperature. Then, 30 mL of dichloromethane and 30 mL of distilled water were added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and then 0.8 g of Compound 20 was obtained by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 4 vol. Ratio) as a developing solution.

The synthesized compound was analyzed by Mass Spectroscopy, and the results were as follows.

MS (ESI) m / z 409.15 (M + H) ⁺

Manufacturing example  2: synthesis of a compound of formula 38

The compound of Formula 38 was synthesized by the same method as in Scheme 2 below.

Scheme 2

45 g of the compound m of Scheme 2, 16 g of the compound n, and 1 g of sulfuric acid were mixed with 500 mL of ethanol, stirred at 65 ° C. for 12 hours, and then cooled to room temperature. Crystals formed in this process were filtered off and dried to obtain an intermediate product, which was mixed with 35 g of trifluoroacetic acid and 500 mL of acetic acid. The mixture was stirred at 100 ° C. for 24 hours and then cooled to room temperature to yield yellow crystals. The crystals were purified, washed three times with 200 mL of hexane and dried to afford 16 g of compound o.

2.5 g of the compound o, 4.0 g of 4-bromobenzene, 0.1 g of CuCl, and 10 g of K ₂ CO ₃ were mixed with 30 mL of dimethyl sulfoxide, stirred at 170 ° C. for 12 hours, and then cooled to room temperature. Then, 30 mL of dichloromethane and 30 mL of distilled water were added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and then 2.0 g of Compound 38 was obtained by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 4 vol. Ratio) as a developing solution.

The result of analyzing the synthesized compound by mass spectrometry was as follows.

MS (ESI) m / z 409.15 (M + H) ⁺

Manufacturing example  3: synthesis of a compound of formula 43

The compound of Formula 43 was synthesized by the same method as in Scheme 3 below.

Scheme 3

5.5 g of the compound bb of Scheme 3, 2.7 g of compound aa, 0.5 g of Pd (PPh ₃ ) ₄ , and 5 g of K ₂ CO ₃ were mixed with 50 mL of toluene, stirred at 100 ° C. for 24 hours, and then cooled to room temperature. It was. Then, 50 mL of distilled water was added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and then 4.8 g of the compound of Formula 43 was separated by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 3 volume ratio) as a developing solution.

For the synthesized compound, the results of analysis by nuclear magnetic resonance spectroscopy ( ¹ H NMR (nuclear magnetic resonance spectroscopy)) are shown in FIG. 6. In addition, the results of analyzing the synthesized compound by mass spectrometry were as follows.

MS (ESI) m / z 606.27 (M + H) ⁺

Manufacturing example  4: synthesis of a compound of formula 44

The compound of Formula 44 was synthesized by the same method as in Scheme 4 below.

Scheme 4

5.0 g of the compound z of the reaction scheme 4, 2.7 g of the compound aa, 0.5 g of Pd (PPh ₃ ) ₄ , and 5 g of K ₂ CO ₃ were mixed with 50 mL of toluene, stirred at 100 ° C. for 24 hours, and then cooled to room temperature. It was. Then, 50 mL of distilled water was added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and 4.0 g of Compound 44 was isolated by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 2 vol. Ratio) as a developing solution.

The result of analyzing the synthesized compound by mass spectrometry was as follows.

MS (ESI) m / z 550.27 (M + H) ⁺

Manufacturing example  5: synthesis of a compound of formula 50

The compound of Formula 50 was synthesized by the same method as in Scheme 5 below.

Scheme 5

8.0 g of the compound bb of Scheme 5, 1.8 g of the compound cc, 0.5 g of Pd (PPh ₃ ) ₄ , and 5 g of K ₂ CO ₃ were mixed with 50 mL of toluene, stirred at 100 ° C. for 24 hours, and then cooled to room temperature. It was. Then, 50 mL of distilled water was added and stirred for 10 minutes to separate the aqueous layer and the organic layer, and then the aqueous layer was removed. The organic layer was concentrated under reduced pressure, and 3.5 g of the compound of Chemical Formula 50 was separated by silica gel column chromatography using a mixed solvent of chloroform: hexane (1: 1 volume ratio) as a developing solution.

The result of analyzing the synthesized compound by mass spectrometry was as follows.

MS (ESI) m / z 460.17 (M + H) ⁺

Experimental Example  1: solubility and Tabernacle  Property evaluation

An organic solvent was added to 30 mg of each compound synthesized in Preparation Examples 1 to 5, and the total weight of the solution was mixed to 1.0 g. The mixture was rolled at room temperature for 1 hour, and then filtered through a syringe filter (Acrodisc) having an average porosity diameter of 0.2 μm. At this time, the solubility and film-forming properties of each compound synthesized in Preparation Examples 1 to 5 were compared using CBP, a host compound generally used in the art.

(1) Solubility Evaluation Method: 용해 The solubility was confirmed by removing the solvent of the filtered solution and measuring the mass of the remaining solid, and the results are shown in Table 1 below. At this time, toluene and chlorobenzene were selected and evaluated as the organic solvent.

(2) Film-forming property evaluation: The filtered solution was spin-coated on a glass substrate . The film-forming properties of the coated film were made by sensory evaluation. In this case, when the film is transparent and smooth, ○, transparent but not uniform or some fine crystals are visible △, and when the film is opaque, X is indicated and the results are shown in Table 1 below.

compound Solubility Film formation characteristics toluene Chlorobenzene Production Example 1 3 wt% or more 3 wt% or more ○ Production Example 2 3 wt% or more 3 wt% or more ○ Production Example 3 3 wt% or more 3 wt% or more ○ Production Example 4 3 wt% or more 3 wt% or more ○ Production Example 5 3 wt% or more 3 wt% or more △ CBP 0.5 wt% 1 wt% X

Referring to Table 1, it was confirmed that each of the compounds synthesized in Preparation Examples 1 to 5 are all dissolved at least 3% by weight in toluene and chlorobenzene.

On the other hand, in the case of CBP, it was almost insoluble in toluene and partially dissolved in chlorobenzene, but the coated membrane was opaque. This confirmed that CBP alone could not be used as a host for the organic light emitting device.

Example  1 to 4: fabrication of an organic light emitting device

First step: For organic photoelectric device  Preparation of the composition

The host compound synthesized in Preparation Examples 1 to 4 was used as a host by mixing in the combination and weight ratio shown in Table 2 below. In addition, the compound represented by Chemical Formula 59 was used as a dopant.

3 wt% of the host compound was dissolved in a toluene solvent, 0.5 wt% of the dopant was dissolved in a chlorobenzene solvent, and the two kinds of solutions were mixed to prepare a composition for an organic photoelectric device.

Second step: manufacturing an organic light emitting device

The organic light emitting device is ITO / PEDOT: PSS (40 nm) / EML (host compound (87 wt%) + dopant compound (13 wt%), 50 nm) / BAlq (5 nm) / Alq ₃ (20 nm) / LiF It was produced in the structure of (1 nm) / Al (100 nm).

An ITO substrate was used as the anode, and spin-coated PEDOT: PSS aqueous solution on the substrate and dried at 200 ° C. for 10 minutes to form a 40 nm thick PEDOT: PSS film.

After the spin coating of the composition for the organic photoelectric device prepared in the first step on the PEDOT: PSS film, and dried at 110 ℃ for 10 minutes to form a light emitting layer. At this time, the light emitting layer was formed to have a thickness of 50 nm.

BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer having a thickness of 50 mV. In addition, Alq ₃ was vacuum-deposited on the hole blocking layer to form an electron transport layer having a thickness of 200 kHz.

An organic light emitting diode was manufactured by sequentially depositing LiF 10 Li (1 nm) and Al 1000 Å on the electron transport layer to form a cathode.

Comparative example  One

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the host compound synthesized in Preparation Example 1, instead of using the host compounds synthesized in Preparation Examples 1 to 4 alone.

Comparative example  2

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the host compound synthesized in Preparation Example 2 alone instead of using the host compound synthesized in Preparation Examples 1 to 4.

Comparative example  3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the host compound synthesized in Preparation Example 3 alone, instead of using the host compound synthesized in Preparation Examples 1 to 4.

Comparative example  4

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the host compound synthesized in Preparation Example 4 alone instead of using the host compound synthesized in Preparation Examples 1 to 4.

Comparative example  5

Instead of using a mixture of the host compounds synthesized in Preparation Examples 1 to 4, polyvinylcarbazole (polyvinylcabazole, PVK) polymer containing a repeating unit represented by the following formula (60) with excellent hole transportability and excellent electron transportability The compound represented by Chemical Formula 61 (butyl-2- (4-biphenyD-S- (4-tert-butylphenyl-1,3,4-oxadiazole, PBD)) was used in a 1: 1 weight ratio, except that An organic light-emitting device was manufactured in the same manner as in Example 1.

[Formula 60] [Formula 61]

　　　　　　　　　

　　　　　　　　　

Experimental Example  2: Performance Evaluation of Organic Light Emitting Diode

For each organic light emitting device manufactured in Examples 1 to 4 and Comparative Examples 1 to 5, the current density change, luminance change, and luminous efficiency according to voltage were measured. Specific measurement methods are as follows, and the results are shown in Table 2 below .

(1) Measurement of change of current density according to voltage change

For the organic light emitting device manufactured, the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain a result.

(2) Measurement of luminance change according to voltage change

For the organic light emitting device manufactured, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained. The results are shown in Table 2 below.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) and power efficiency (lm / W) were calculated at the same luminance of 2000 cd / m ² using the luminance, current density, and voltage measured from (1) and (2). The results are shown in Table 2, FIG. 7 and FIG. 8.

(4) Color coordinates were measured using a luminance meter (Minolta Cs-100A), the results are shown in Table 2 below.

(5) The lifetime is shown in Table 2, FIG. 9 and FIG. 10 by measuring the time at 50% halving at the initial luminance of 2000 cd / m ² .

Host compound
(Weight ratio) Measurement results at 2000 cd / m ² Driving voltage
(V) Current efficiency
(cd / A) Power efficiency
(lm / W) Color coordinates
(x, y) 50% halving
Life (hr) Example 1 Preparation Example 1 Preparation Example 3 (1: 1) 6.4 26.9 13.3 0.317, 0.635 260 Example 2 Preparation Example 1 Preparation Example 4 (1: 1) 5.0 27.5 17.3 0.323 0.627 > 250 Example 3 Preparation Example 2 Preparation Example 3 (1: 1) 5.1 27.1 16.6 0.326 0.627 > 250 Example 4 Preparation Example 2 Preparation Example 4 (1: 1) 6.4 25.5 12.4 0.320, 0.630 250 Comparative Example 1 Preparation Example 1 12.2 4.4 1.1 0.318, 0.613 7 Comparative Example 2 Preparation Example 2 9.8 11.2 3.6 0.313, 0.616 17 Comparative Example 3 Production Example 3 8.5 12.5 4.6 0.326 0.625 13 Comparative Example 4 Production Example 4 5.6 3.6 2.0 0.314 0.636 9 Comparative Example 5 PVK: PBD (1: 1) 4.5 18.1 12.6 0.326 0.627 9

Referring to Table 2, in Comparative Examples 1 to 4 using the host compound alone, the luminous efficiency was low from 3.6 cd / A to 12.5 cd / A. In particular, the compound synthesized in Preparation Example 4 was not formed uniformly during the spin coating process, the device performance such as luminous efficiency and life was very low.

In the case of Comparative Example 5, PBD, which is an electron transporting low molecular weight alone, was difficult to form a film, and thus, a device was manufactured by mixing with PVK, a hole-aqueous polymer, and the device performance showed relatively excellent luminous efficiency. However, it showed very short device life within 20 hours.

In comparison, the results of Examples 1 to 4 using the host compounds synthesized in Preparation Examples 1 to 4 showed excellent device performances in which driving voltage reduction, luminous efficiency, power efficiency, and lifetime were all greatly improved.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: organic photoelectric device 110: cathode
120: anode 105: organic thin film layer
130: light emitting layer 140: hole transport layer
150: electron transport layer 160: electron injection layer
170: hole injection layer 230: light emitting layer + electron transport layer

Claims (15)

Formula 1; Any one of the following Formulas 2a to 2c; And a first host compound in which a substituent represented by Formula 3 is sequentially bonded; And
A composition for an organic photoelectric device comprising the second host compound represented by Formula 4 or Formula 5 below:
[Formula 1] [Formula 3]

In Chemical Formulas 1 and 3,
R ¹ and R ² are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,
R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,
[Formula 4] [Formula 5]

In Chemical Formulas 4 and 5
Q ¹ to Q ¹⁰ are the same as or different from each other, and each independently N or CR ⁵ , provided that at least one selected from Q ¹ to Q ⁶ in Formula 4 is N, and Q ¹ to Q in Formula 5 At least one selected from ⁵ is N, at least one selected from Q ⁶ to Q ¹⁰ is N, wherein R ⁵ is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 Aryl group or a combination thereof,
R ⁵ ′ is a fluorenylene group, a C1 to C60 alkylene group, a C6 to C60 arylene group or a combination thereof,
[Formula 2a] [Formula 2b] [Formula 2c]

In Chemical Formulas 2a to 2c,
R ⁶ and R ⁷ are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof.
The method of claim 1,
The first host compound is a composition for an organic photoelectric device represented by the formula 6 to 12:
[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Chemical Formula 12]

In Chemical Formulas 6 to 12
R ¹ and R ² are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,
R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof,
R ⁶ and R ⁷ are the same as or different from each other, and each independently an amine group, a carbazolyl group, an alkyl group of C1 to C30, an aryl group of C6 to C30, or a combination thereof.
The method of claim 1,
The first host compound is a composition for an organic photoelectric device represented by the following formula 22, 30, 33 or 42.

The method of claim 1,
At least any three selected from Q ¹ to Q ⁶ of the second host compound represented by Formula 4 is N composition for an organic photoelectric device.
The method of claim 1,
The second host compound represented by Formula 4 is a composition for an organic photoelectric device is represented by the formula (4a):
[Chemical Formula 4a]

In Chemical Formula 4a
R ^5a to R ^5c are  The same or different from each other, each independently is an amine group, carbazolyl group, fluorenyl group, C1 to C60 alkyl group, C6 to C60 aryl group or a combination thereof.
The method of claim 1,
At least any set selected from Q ¹ to Q ⁵ of the second host compound represented by Formula 5 is N, and at least any set selected from Q ⁶ to Q ¹⁰ is N.
The method of claim 1,
The second host compound represented by Formula 5 is a composition for an organic photoelectric device is represented by the formula (5a):
[Formula 5a]

In Chemical Formula 5a
R ^5d to R ^5g are  The same as or different from each other, each independently an amine group, a carbazolyl group, a fluorenyl group, an alkyl group of C1 to C60, an aryl group of C6 to C60, or a combination thereof,
R ⁵ ″ is a fluorenylene group, a C1 to C60 alkylene group, a C6 to C60 arylene group or a combination thereof.
The method of claim 1,
The second host compound is represented by the following formula 43 to 56 composition for an organic photoelectric device.

The method of claim 1,
The composition for an organic photoelectric device is a composition for an organic photoelectric device comprising a first host compound: the second host compound 50: 1 to 2,500 by weight.
anode; cathode; And an organic thin film layer interposed between the anode and the cathode,
The organic thin film layer is formed using the composition for an organic photoelectric device according to claim 1.
The method of claim 10,
The organic photoelectric device composition is used as a phosphorescent host material.
The method of claim 10,
The organic thin film layer is an organic photoelectric device that is a light emitting layer.
The method of claim 10,
The organic thin film layer is an organic photoelectric device further comprises a dopant.
The method of claim 13,
The dopant is an organic photoelectric device that is a phosphorescent dopant of red, green, or blue.
A display device comprising the organic photoelectric device according to claim 10.

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