KR20090072756A - Material for organic photoelectric device and organic photoelectric device using same - Google Patents

Abstract

A material for an organic photoelectric device is provided to ensure excellent phosphorescence, high thermal stability, amorphousness, and high solubility to organic solvent, and to prepare an organic photoelectric device with high efficiency and long lifetime. A material for an organic photoelectric device comprises a symmetrical or asymmetrical cycloalkylsilicone derivative compound represented by chemical formula 1. In chemical formula 1, the substituent represented by Ra - Rf is selected from the group consisting of hydrogen, substituted or unsubstituted C6-30 aryl group, substituted or unsubstituted C6-30 arylene group, substituted or unsubstituted C2-30 heteroaryl group, substituted or unsubstituted C2-30 heteroarylene group, substituted or unsubstituted C1-30 aryl group or substituted or unsubstituted alkylene group; and m and n are an integer of 0-6 and m+n >= 2.

Description

Material for organic photoelectric device and organic photoelectric device using same {MATERIAL FOR ORGANIC PHOTOELECTRIC DEVICE AND ORGANIC PHOTOELECTRIC DEVICE USING SAME}

The present invention relates to a material for an organic photoelectric device and an organic photoelectric device using the same, and more particularly, phosphorescent light emission, high thermal stability, high amorphousness, high solubility in organic solvents, and film characteristics during wet deposition. An organic photoelectric device material exhibiting this improved characteristic and an organic photoelectric device using the same.

An electro-optical device is a device that converts light energy into electrical energy or vice versa in a broad sense. Examples of such an optoelectronic device include an organic light emitting device, a solar cell, Transistors and the like.

Among such optoelectronic devices, organic light emitting diodes (OLEDs), in particular, have attracted attention as the demand for flat panel displays increases.

The organic light emitting device converts electrical energy into light by applying current to the organic light emitting material, and has a structure in which a functional organic material layer is inserted between an anode and a cathode.

The electrical characteristics of the device are similar to that of LEDs. After holes are injected from the anode and electrons are injected from the cathode, the holes and electrons move toward each other and then energy is generated by recombination. It forms high excitons. In this case, light having a specific wavelength is generated as the excitons move to the ground state.

In 1987, Eastman Kodak Co., Ltd. developed for the first time an organic light emitting device using a low molecular weight aromatic diamine and an aluminum complex as a material for forming a light emitting layer [Appl. Phys. Lett. 51, 913, 1987]. In 1987, C. W. Tang et al. Reported a device having practical performance for the first time in organic light emitting devices [Applied Physics Letters, Vol. 51, No. 12, 913-915 (1987)].

The document describes a structure in which a thin film (hole transport layer) of a diamine derivative and a thin film (electron transport light emitting layer) of Alq3 (tris (8-hydroxy-quinolate) aluminum) are laminated as an organic layer.

In general, the organic light emitting device has a structure formed on the glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region and a metal electrode (cathode). In this case, the organic thin film may include a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer or an electron injection layer, and may further include an electron blocking layer or a hole blocking layer due to the light emission characteristics of the light emitting layer.

When an electric field is applied to the organic light emitting device having such a structure, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the light emitting layer through the respective hole transporting layer and the electron transporting layer, and the excitons are excited. To form.

The light-excited excitons thus formed emit light while transitioning to ground states.

Light emission is divided into fluorescence using singlet excitons and phosphorescence using triplet states according to its mechanism.

Recently, it has been known that not only fluorescent light emitting materials but also phosphorescent light emitting materials can be used as light emitting materials for organic light emitting devices [D. F.O'Brien et al., Applied Physics Letters, 74 (3), 442-444, 1999; MA Baldo et al., Applied Physics letters, 75 (1), 4-6, 1999]. These phosphorescent luminescences triplet singlet excitons through intersystem crossing after electrons transfer from the ground state to the excited state. After the non-luminescent transition to the excitons, the triplet excitons are made to emit light while transitioning to the ground state.

At this time, the transition to the triplet excitons does not directly transition to the ground state (spin forbidden), since the process of transition to the ground state after the flipping of the electron spin proceeds (lifetime) than fluorescence (lifetime) It has a longer characteristic.

That is, the emission duration of fluorescence emission is only several nanoseconds, but the phosphorescence emission corresponds to several micro seconds, which is a relatively long time.

In addition, quantum mechanically, when the holes injected from the anode and the electrons injected from the cathode are recombined to form a light-emitting excitons, the ratio of the singlet and triplet is 1: 3, which is triple in the organic photoelectric device. Anti-light emitters are generated three times more than single-emitting light emitters.

Therefore, in the case of fluorescence, the probability of singlet excited state is 25% (triple state 75%) and there is a limit of luminous efficiency, while phosphorescence can be used to triplet 75% and singlet excited state 25%. Can be up to 100% internal quantum efficiency. Therefore, in the case of using the phosphorescent material, there is an advantage that can achieve a light emission efficiency about three times higher than the fluorescent light emitting material.

In the organic light emitting device having the structure as described above, in order to increase the efficiency and stability of the light emitting state, a light emitting dye (dopant) may be added to the light emitting layer (host).

In such a structure, the efficiency and performance of the light emitting device varies depending on which host material is used for the light emitting layer, and naphthalene, anthracene, phenanthrene, tetracene, pyrene, benzopyrene, chrysene, pisene, Carbazole, fluorene, biphenyl, terphenyl, triphenylene oxide, dihalobiphenyl, trans-stilbene and 1,4-diphenylbutadiene are shown as examples of organic host materials. Has been.

Carbazole derivatives, such as 4,4-N, N-dicarbazolebiphenyl (CBP), are commonly used as host materials. These compounds have low thermal stability with a glass transition temperature of 120 ° C or lower and excessive symmetry. Because of this, it is easy to crystallize and its solubility in organic solvents is very low. Therefore, when the film is manufactured by the wet process using the compound, it is impossible to manufacture the organic light emitting device due to poor film formation characteristics or has a disadvantage of showing very low device performance when manufacturing the device.

Recently, many technical advances have been made on organic light emitting diodes, but the luminous efficiency, color purity, electrical and thermal stability, etc., have not been reached to a satisfactory level. There is a need for the development of wet manufacturing techniques such as ink jetting and screen printing techniques. Therefore, there is an urgent need to develop a phosphorescent light emitting material that has high efficiency, high color purity, excellent electrical and thermal stability, and is capable of wet film formation.

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic photoelectric device having high thermal stability, improved amorphousness, to provide a high efficiency and long-life organic photoelectric device, and to increase solubility in organic solvents, thereby exhibiting improved film characteristics during wet deposition. To provide the material.

Another object of the present invention is to provide an organic photoelectric device using the organic photoelectric device material.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first embodiment of the present invention for achieving the above object is to provide a material for an organic photoelectric device comprising a cyclic or asymmetric cycloalkylsilicon derivative compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

Substituents represented by Ra to Rf are each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms,

Ra to Rf may be the same as or different from each other, may form a ring,

Substituents represented by Ar ₁ and Ar ₂ are each independently substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 60 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

M and n are integers between 0 and 6, and m + n ≧ 2.)

The organic photoelectric device material may be used alone of the cycloalkylsilicone derivative compound of Formula 1, the derivative compound may be used as a host material, and may further include a dopant.

A second embodiment of the present invention provides an organic photoelectric device comprising at least one organic thin film layer disposed between an anode and a cathode, wherein at least one of the organic thin film layers includes the material. It is.

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

The organic photoelectric device material of the present invention uses phosphorescent light emission, has a three-dimensional structure, and has a bulky substituent, thereby suppressing intermolecular interactions, thereby improving luminous efficiency and solubility.

In addition, when the organic photoelectric device is manufactured using the compound, due to its excellent solubility, the organic photoelectric device may be easily manufactured by a wet process such as spin coating, inkjet printing, and casting, thereby reducing the manufacturing cost of the organic photoelectric device. Applicable to large area displays.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic photoelectric device material, and more particularly to an organic photoelectric device material using phosphorescent light emission.

According to the first embodiment of the present invention, the material for an organic photoelectric device includes a symmetrical or asymmetric cycloalkylsilicon derivative compound represented by the following general formula (1).

[Formula 1]

In Chemical Formula 1,

Substituents represented by Ra to Rf are each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms,

Ra to Rf may be the same or different from each other and may form a ring.

Substituents represented by Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted arylene groups having 6 to 60 carbon atoms; Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 60 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

At this time, substituted aryl group, arylene group, heteroaryl group, heteroarylene group, alkyl group, alkylene group is one or more hydrogen atoms of the functional group substituents containing amine, substituents including carbazole, substituents containing pyridine, pyri Substituents including midines, substituents containing pyrazine, substituents containing quinoline, substituents containing isoquinoline, substituents containing triazine, substituents containing phenanthrine or one or more substituents containing fluorene It means. However, the present invention is not limited thereto.

M and n are integers between 0 and 6, and m + n ≧ 2.

The organic photoelectric device material represented by Chemical Formula 1 specifically includes a compound represented by Chemical Formula 2 to Chemical Formula 5, but the present invention is not limited thereto.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, the substituents represented by R ₁ to R ₁₀ are each hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an arylene group, a substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms, respectively. A group or a heteroarylene group, and a substituent selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or an alkylene group,

R ₁ to R ₁₀ may be the same as or different from each other, may be integrated with each other or form a ring.

Ar ₁ and Ar ₂ each represent a substituted or unsubstituted aryl group or arylene group having 6 to 60 carbon atoms, a substituted or unsubstituted alkyl group or alkylene group having 1 to 60 carbon atoms, and a substituted or unsubstituted carbon number. It is a functional group selected from the group which consists of a heteroaryl group or a heteroarylene group of 2-60.

More specific examples of the material for an organic photoelectric device of the present invention may include a compound represented by the following Chemical Formulas 6 to 25 or a combination thereof, but the present invention is not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

The cycloalkylsilicon derivative compound represented by Formula 1 has a high thermal stability with a glass transition temperature (Tg) of 120 ° C. or higher and a pyrolysis temperature of 450 ° C. or higher. In addition, the compound may not easily form crystals, and may improve amorphousness, thereby enabling high efficiency and long life organic photoelectric devices. In addition, the derivative compound may exhibit high solubility in an organic solvent, and thus, when the film is formed by a wet process using the compound, the film properties may be improved.

The cycloalkylsilicone derivative compound represented by Formula 1 of the present invention may be used alone or as a host material used in combination with a dopant. Since the cycloalkylsilicon derivative compound represented by the formula (1) is more preferably used as a host material, the material for an organic photoelectric device of the present invention includes a host containing the cycloalkylsilicone derivative compound represented by the formula (1), and the dopant It may further include.

The dopant itself is a compound having a high luminescence ability and is called a guest or dopant because a small amount of the dopant is mixed and used in the host.

That is, the 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 excitaion that excites above a triplet state is used. .

As dopants that can be used together, a red (R) fluorescent dopant, a green (G) fluorescent dopant, a blue (B) fluorescent dopant, a white (W) fluorescent dopant, or a phosphorescent dopant material can be used. It should be a material that satisfies the property of being unaggregated, not well aggregated, and uniformly distributed in the host material.

The phosphorescent dopant is an organometallic compound including an element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, and combinations thereof.

Specific examples of red phosphorescent dopants include PtOEP (2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine platinum (2)), Ir (Piq) ₂ (acac) (Piq = 1-phenylisoquinoline, acac = pentane-2,4-dione), Ir (Piq) ₃ , UD's RD 61 and the like can be used, and green phosphorescent dopants include Ir (PPy) ₂ (acac) and Ir (PPy) _3. (PPy = 2-phenylpyridine), Ir (mPPy) ₃ , GD48 from UDC, etc. may be used, and the blue phosphorescent dopant may be (4,6-F2PPy) ₂ Irpic [Ref . Appl. Phys. Lett., 79, 2082-2084, 2001].

1 to 5 are cross-sectional views illustrating various embodiments of the organic photoelectric device according to the second embodiment, which may be manufactured using the material for the organic photoelectric device according to the first embodiment of the present invention.

1 to 5, the organic photoelectric device 100, 200, 300, 400, and 500 according to the second embodiment of the present invention is further disposed with the anode 120 and the cathode 110 interposed therebetween. The organic thin film layer 105 may have a structure including an indium tin oxide (ITO) transparent electrode for the anode 120 and a metal electrode such as aluminum for the cathode 110.

First, referring to FIG. 1, FIG. 1 illustrates an organic photoelectric device in which only the emission layer 130 exists as the organic thin film layer 105.

Referring to FIG. 2, FIG. 2 illustrates a two-layered organic photoelectric device 200 in which an emission layer 230 including an electron transport layer (not shown) and a hole transport layer 140 exist as the organic thin film layer 105. The hole transport layer 140 is a separate layer made of a film having excellent bonding property or hole transport property with a transparent electrode such as ITO. In the structure shown in FIG. 2, the light emitting layer serves as an electron transport layer.

Referring to FIG. 3, in FIG. 3, the three-layer organic photoelectric device 300 having the electron transport layer 150, the light emitting layer 130, and the hole transport layer 140 as the organic thin film layer 105 is an independent form of the light emitting layer 130. The film | membrane which is excellent in the electron transport property and the hole transport property is laminated | stacked in the other layer, and is shown.

4, in FIG. 4, 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 an organic thin film layer 105. As shown in FIG. 3, the hole injection layer 170 is added in consideration of the adhesiveness to ITO used as the anode layer in the characteristic of the three-layer organic photoelectric device 300 illustrated in FIG. 3.

Referring to FIG. 5, in FIG. 5, the organic thin film layer 105 has different functions such as an electron injection layer 160, an electron transport layer 150, an emission layer 130, a hole transport layer 140, and a hole injection layer 170. The five-layer organic photoelectric device 500 having five layers is present, and the organic photoelectric device 500 has an characteristic of effectively reducing the voltage by forming the electron injection layer 160 separately.

Although not shown in the drawings, an organic photoelectric device having a six-layer structure further including a hole blocking layer between the light emitting layer and the electron transport layer is, of course, included in the scope of the present invention.

In order to form the organic thin film layer 105 having one to six layers as described above, a dry film forming method such as evaporation, sputtering, plasma plating, and this temperature gold and spin coating Processes such as, for example, inkjet printing, casting, dipping, flow coating, and the like can be used. Among them, wet coating methods such as spin coating, inkjet printing, casting, dipping, and flow coating in forming an organic thin film layer using the compound of the present invention are performed. It is preferable to maximize the effect of using the compound of the present invention. In addition, the surface roughness (Rq) of the organic thin film layer manufactured by the wet film method using the compound of the present invention may be formed very uniformly 1.0 nm or less. In the present invention, since the smaller the surface roughness (Rq) of the organic thin film layer means that the surface is uniform, it is preferably 1.0 nm or less, and most preferably 1.0 nm to 0 nm.

In the organic photoelectric device according to the second embodiment of the present invention, at least one of the light emitting layer, the electron transport layer and / or the electron injection layer, the hole transport layer and / or the hole injection layer, and the hole blocking layer may be represented by the compound represented by Chemical Formula 1 It is preferable to include.

The organic thin film layer 105 preferably contains a phosphorescent compound. As the phosphorescent compound, a metal complex or the like that emits light by multiplet excitation to be excited in a triplet state or more is preferable.

Hereinafter, when the actual organic photoelectric device is manufactured using the specific method for manufacturing the organic photoelectric device material according to the first embodiment of the present invention and the organic photoelectric device material manufactured using the method, the luminous efficiency is high. It will be described with reference to specific examples and comparative examples that the driving voltage is lowered. However, the contents not described herein are omitted because they are sufficiently technically inferred by those skilled in the art.

Synthesis of Materials for Organic Optoelectronic Devices

Example 1 Synthesis of Compound of Formula 6

(a) Synthesis of Intermediate Compounds

 According to the method described in Organometallics, 2006, 25 (5), 1188-1198, the following Inter-1 compound was prepared as in Scheme 1 below.

Scheme 1

(b) Synthesis of Compound of Formula 6

Intermediate chain Using Inter-1 and Inter-2, a compound of Chemical Formula 6 was prepared by synthesizing according to Scheme 2 according to the Suzuki coupling method.

Scheme 2

Example 2 Synthesis of Compound of Formula 8

Using the intermediate Inter-1 and Inter-3 was reacted as in Scheme 3 to synthesize a compound of formula (8).

Scheme 3

Example 3 Synthesis of Compound of Formula 14

The intermediate of Inter-1 and Inter-5 were used to react as in Scheme 4 to synthesize a compound of Formula 14.

Scheme 14

Example 4 Synthesis of Compound of Formula 15

A compound of Chemical Formula 15 was synthesized by reacting Inter-1 as an intermediate with Ultolmann coupling method of the dotolylamine as in Scheme 5 below.

Scheme 5

Example 5 Synthesis of Compound of Formula 18

Using the intermediate Inter-1 and Inter-3 was reacted as in Scheme 6 to synthesize a compound of formula (18).

Scheme 6

Example 6 Synthesis of Compound of Formula 24

The compound of Chemical Formula 24 was synthesized by using Inter-6 as an intermediate to react as in Scheme 7 below.

Scheme 7

Example 7 Synthesis of Compound of Formula 25

The reaction was performed as in Scheme 8 to synthesize a compound of Chemical Formula 25.

Scheme 8

Physical and Electrochemical Properties of Compounds

1) spectral characteristics

To prepare a solution by dissolving the compound prepared according to Examples 1 to 7 in chloroform at a concentration of 1wt%, this solution was deposited on a quartz substrate by spin coating and dried at 80 ^o C for 30 minutes to measure spectroscopic characteristics. Samples were prepared. UV absorption and PL emission (photoluminescence emission) of the prepared films were measured. Among the measured results, UV / PL spectrum results of the compound of Formula 18 prepared according to Example 5 are shown in FIG. 6.

 The energy bandgap (ΔEs) of the compound was calculated from the measured UV absorption spectrum and the results are shown in Table 1 below.

2) thermal analysis

The glass transition temperature (Tg) and thermal decomposition temperature (Td) of the compounds prepared in Examples 1 to 7 were measured by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and the results were measured. It is shown in Table 1 below.

3) Roughness of film during wet film formation

In order to determine the flatness of the film, the surface roughness (Rq) of the film surface of the sample for spectroscopic characteristics was measured and the results are shown in Table 1 below.

4) Thin film characteristics

The thin film properties of the compounds prepared in Examples 1 to 7 were measured by atomic force microscopy (AFM), and the thin film properties of the compound prepared in Example 5 are shown in FIG. 7.

compound UV (nm) PL (nm) ΔEs (eV) Tg (℃) Td (℃) Rq (nm) Example 1 6 295, 325 390 3.53 128 479 0.45 Example 2 8 296, 327 377 3.50 165 512 0.43 Example 3 14 313, 345 417 3.23 Not observed 479 0.31 Example 4 15 300, 312 433 3.48 Not observed 400 0.32 Example 5 18 295, 327 389 3.50 190 524 0.35 Example 6 24 296, 330 422 3.32 154 516 0.36 Example 7 25 296, 342 417 3.28 143 495 0.36

 As shown in Table 1, DSC analysis of the compounds prepared according to Examples 1 to 7 has a very high glass transition temperature (Tg) of more than 120 ℃ and very low crystallinity shows the crystallization temperature (Tc) Amorphous properties do not exhibit improved properties.

In addition, as a result of the TGA analysis, all of the compounds prepared according to Examples 1 to 7 exhibited a high pyrolysis temperature (Td) of 450 ° C. or higher, thereby confirming that the material has excellent thermal stability.

It was also well soluble in common organic solvents such as chloroform, methylene chloride and chlorobenzene. The compounds of Examples 1 to 7 all exhibited solubility of 4% by weight or more in an organic solvent at room temperature, and showed good coating properties and thin film properties despite being low molecular weight due to excellent solubility.

The surface roughness (Rq) of the compounds prepared in Examples 1 to 7 was found to form a uniform film of about 0.4 nm. Among them, the AFM photograph of the compound prepared according to Example 5 is shown in FIG. 7, and as shown in FIG. 7, it can be seen that the formed film is a flat film with little surface curvature.

As shown in Table 1, it can be seen that it can be usefully applied as a host material of the blue, green and red phosphorescent dopants according to the UV / PL spectroscopic properties and high energy bandgap of the compounds prepared in Examples 1 to 7 have.

Fabrication of Organic Optoelectronic Devices

Example 8 Fabrication of phosphorescent green organic photoelectric device

An organic photoelectric device having the following structure was manufactured using the compound of Formulas 6, 8, and 18 prepared according to Examples 1, 2, and 5 as a host material, and Ir (mPPy) ₃ as a dopant.

ITO was used as the cathode at a thickness of 1000 kPa, and aluminum (Al) was used as the cathode at a thickness of 1000 kPa.

Specifically, the method for manufacturing the organic photoelectric device, the anode is cut into 50mm × 50mm × 0.7mm size ITO glass substrate having a sheet resistance value of 15Ψ / cm ² for each 15 minutes in acetone, isopropyl alcohol and pure water After ultrasonic cleaning, UV ozone cleaning was used for 30 minutes.

A PEDOT (poly (3,4-ethylene dioxythiophene)) aqueous solution was spin-coated at 30 rpm for 30 seconds on a cleaned ITO glass substrate and dried to form a buffer layer with a film thickness of 600 kPa. At this time, the drying was performed for 20 minutes at 120 ℃.

The luminescent material solution of the compound host material of Formulas 6, 8 and 18 and the Ir (mPPy) ₃ dopant prepared according to Examples 1, 2 and 5 was dissolved in chlorobenzene so that the total solid content concentration was 3% by weight. Was prepared. At this time, the host material and the dopant were mixed in a ratio of 93: 7 wt%.

The light emitting material solution was spin-coated on a PEDOT film at a speed of 200 rpm for 30 seconds and dried to form a light emitting layer having a film thickness of 400 Pa. Drying was carried out at 120 ° C. for 20 minutes.

BAlq (Bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum) was deposited on the substrate at a vacuum degree of 650 ㅧ 10 ^-7 Pa and a deposition rate of 0.1 to 0.3nm / s to obtain a film thickness of 50Å. A hole blocking layer was formed. Subsequently, Alq3 was deposited under the same vacuum deposition conditions to form an electron transport layer having a film thickness of 200 μs. LiF and Al were sequentially deposited on the electron transport layer to complete the organic photoelectric device.

The fabricated organic photoelectric device is made of ITO / PEDOT (600kW) / emission layer (EML) (host material + phosphorescent dopant; 7 wt%, 400kW) / BAlq (50kW) / Alq ₃ (200kW) / LiF (5kW). It was a six-layer structure.

Example 9) Fabrication of phosphorescent red organic photoelectric device

A phosphorescent red organic photoelectric device was manufactured in the same manner as in Example 8, except that the compound of Formulas 24 and 25 prepared according to Examples 3 and 4 were used as a host material, and Ir (PiQ) ₃ was used as the dopant. Prepared.

For the organic photoelectric device manufactured according to Examples 8 and 9, the current density change, luminance change, and luminous efficiency according to voltage were measured by the following method.

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

With respect to the manufactured organic photoelectric device, while increasing the voltage from 0V to 10V using a current-voltmeter (Keithley 2400) to measure the current value flowing through the unit device, and dividing the measured current value by the area to obtain a result.

2) Measurement of luminance change according to voltage change

The resulting organic photoelectric device was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0V to 10V to obtain a result.

3) Luminous efficiency measurement

Luminous efficiency was calculated using the luminance, current density, and voltage measured from 1) and 2).

The performance evaluation results of the organic photoelectric device manufactured by the above conditions are shown in Table 2 below.

Dopant Material of Light Emitting Layer Host material of light emitting layer Luminance (nit) Drive voltage (V) Luminous Efficiency (cd / A) Color coordinates (x, y) Ir (mPPy) ₃ Compound of Formula 6 (Example 1) 500 8.2 19.4 0.32, 0.60 Ir (mPPy) ₃ Compound of Formula 8 (Example 2) 500 9.2 19.9 0.31, 0.60 Ir (mPPy) ₃ Compound of Formula 18 (Example 5) 500 8.8 20.2 0.32, 0.60 Ir (PiQ) ₃ Compound of Formula 24 (Example 6) 1000 7.8 5.4 0.31, 0.60 Ir (PiQ) ₃ Compound of Formula 25 (Example 7) 1000 8.2 5.6 0.32, 0.61

As shown in Table 2, when the light emitting layer is formed using the compound prepared according to Examples 1 to 7 as a host material, the organic photoelectric device manufactured by the spin coating method of the wet process, not the conventional vacuum deposition process, In the green device, the light emission efficiency is about 19 cd / A at 500 nit, and the red device has a high luminous efficiency of 5 cd / A or more at 1000 nit.

In addition, the luminous efficiency of the organic photoelectric device manufactured by using the compounds prepared according to Examples 1, 2 and 5 was measured and the results are shown in FIG. 8. As shown in FIG. 8, it can be seen that light starts emitting at around 4 V, that is, at a low voltage. In addition, as shown in FIG. 8 and Table 2, the driving voltage was measured to 7 to 8V.

As a result of Table 1 and Table 2, it can be seen that the compounds of Examples 1 to 7 are compounds having improved amorphous and solubility characteristics, and thus, the device may be easily manufactured by using a wet process as a host material. In addition, it can be seen from the results of FIGS. 6 to 8 that the compounds of Examples 1 to 7 can be usefully used as host materials for blue, green, and red phosphorescent dopants. The introduction of a three-dimensional structure and bulky substituents increases the intermolecular distance, thereby reducing the crystallinity, increasing the amorphousness, and improving the solubility. Seems to be. Therefore, the compounds of Examples 1 to 7 are expected to be useful as light emitting materials of organic photoelectric devices.

 Although embodiments of the present invention have been described with reference to the accompanying drawings and tables, the present invention is not limited to the above embodiments, but can be manufactured in various forms, and the general knowledge in the art to which the present invention pertains. Those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

1 to 5 are cross-sectional views illustrating various embodiments of an organic photoelectric device that may be manufactured using a material for an organic photoelectric device according to an embodiment of the present invention.

6 is a graph showing the UV / PL spectrum of the compound prepared according to Example 5 of the present invention.

7 is an atomic force microscope (AFM) photograph of a compound prepared according to Example 5 of the present invention.

8 is a graph showing the luminous efficiency of an organic photoelectric device manufactured using the compound prepared according to Examples 1, 2 and 5 of the present invention.

<Description of the reference numerals for the main parts of the drawings>

100, 200, 300, 400, and 500: organic photoelectric devices

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

Claims (10)

An organic photoelectric device material comprising a symmetrical or asymmetric cycloalkylsilicone derivative compound represented by Formula 1 below. [Formula 1]

(In Formula 1, Substituents represented by Ra to Rf are each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, Ra to Rf may be the same or different from each other and may form a ring, Substituents represented by Ar ₁ and Ar ₂ are each independently substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkylene group having 1 to 60 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, M and n are integers between 0 and 6, and m + n ≧ 2.)  The method of claim 1, The cycloalkylsilicone derivative compound represented by Chemical Formula 1 is selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 5 and mixtures thereof. [Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

(In Chemical Formulas 2 to 5, Substituents represented by R ₁ to R ₁₀ are each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Substituted or unsubstituted arylene groups having 6 to 30 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, R ₁ to R ₆ may be integrated with each other or form a ring, Substituents represented by Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituent selected from the group consisting of a substituted or unsubstituted C1-C60 alkylene group, a substituted or unsubstituted C2-C60 heteroaryl group, or a substituted or unsubstituted C2-C60 heteroarylene group to be) The method of claim 2, The cycloalkylsilicon derivative is selected from the group consisting of a compound represented by the following formulas 6 to 25 and combinations thereof. [Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

The method of claim 1, The organic photoelectric device material is a material for an organic photoelectric device further comprises a dopant. The method of claim 4, wherein The dopant is selected from the group consisting of a red fluorescent dopant, a green fluorescent dopant, a blue fluorescent dopant, a white fluorescent dopant, and a phosphorescent dopant. In an organic photoelectric device comprising at least one organic thin film layer disposed between the anode and the cathode, At least one of the organic thin film layers is an organic photoelectric device comprising the material of any one of claims 1 to 5. The method of claim 6, The organic thin film layer Organic photoelectric device comprising a light emitting layer. The method of claim 6, The organic thin film layer Light emitting layer; And An organic photoelectric device comprising a layer selected from the group consisting of a hole transport layer, a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer and combinations thereof. The method of claim 6, At least one of the organic thin film layers is an organic photoelectric device manufactured by the wet deposition method using the material. The method of claim 9, An organic photoelectric device having a surface roughness (Rq) of the organic thin film layer manufactured by the wet film forming method is 1.0 nm or less.

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