KR20070059689A - A carbazole ring-containing silicon compound and an organic light emitting diode employing an organic layer comprising the same - Google Patents

Abstract

Provided is a carbazole ring-containing silicon compound, which has electrical stability, high charge transfer performance, and high glass transition temperature, prevents crystallization, and produces a host material suitable for fluorescent and phosphorescent dopants of all colors. The carbazole ring-containing silicon compound has a structure represented by a formula 1, wherein Z is a substituted or unsubstituted C6-30 aryl group or substituted or unsubstituted C5-30 heteroaryl group, R1, R2, R3, R4, R5, and R6 are independently hydrogen, a halogen atom, hydroxyl group, cyano group, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 alkoxy group, substituted or unsubstituted C1-30 acyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 alkynyl group, substituted or unsubstituted C6-30 aralkyl group, substituted or unsubstituted C6-30 aryl group, substituted or unsubstituted C5-30 heteroaryl group, or -Si(Ar1)3(wherein, the Ar1 is a substituted or unsubstituted C6-30 aryl group or substituted or unsubstituted C4-30 heteroaryl group), at least neighboring two of R1 to R6 are bonded to each other to form a ring, Q1, Q2, Q3, and Q4 are independently of one another C or N, a, b, and n are independently an integer of 1-4, a R5s are identical to or different from one another.

Description

Carbazole ring-containing silicon compound and an organic light emitting diode employing an organic layer comprising the same}

1 is a view schematically showing the structure of an embodiment of an organic light emitting device according to the present invention,

2 shows a photoluminescent (PL) spectrum of a solution containing a compound of Formula 1a,

3 shows a PL spectrum of a membrane containing a compound of Formula 1a,

4 shows a PL spectrum of a solution containing a compound of Formula 1b,

5 shows a PL spectrum of a membrane containing a compound of Formula 1b,

6 shows a PL spectrum of a solution containing a compound of Formula 1c,

7 shows the PL spectrum of a membrane containing a compound of Formula 1c,

8 shows a PL spectrum of a solution containing a compound of Formula 1d,

9 shows the PL spectrum of a membrane containing a compound of Formula 1d.

The present invention relates to an organic light emitting device having a carbazole ring-containing silicon compound and an organic film including the same, and more particularly, a carba that can be used as a host for various phosphorescent or fluorescent dopants such as red, green, blue, and white. By providing a sol ring-containing silicon compound and an organic film including the same, the present invention relates to an organic light emitting device having high efficiency, high brightness, long life, and low power consumption.

Light emitting diodes are self-luminous display elements that have a wide viewing angle, excellent contrast, and fast response time.

Light emitting devices are classified into inorganic light emitting diodes and organic light emitting diodes (OLEDs) according to materials for forming an emitting layer. Herein, the organic light emitting device has an advantage of excellent luminance, driving voltage, and response speed, and multicoloring, compared to the inorganic light emitting device.

A general organic light emitting device has an anode formed on the substrate, and a hole transport layer, a light emitting layer, an electron transport layer and a cathode are sequentially formed on the anode. Here, the hole transport layer, the light emitting layer and the electron transport layer are organic thin films made of an organic compound.

The driving principle of the organic light emitting device having the structure as described above is as follows.

When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron transport layer, and carriers are recombined in the light emitting layer to generate excitons. The exciton is changed from the excited state to the ground state, whereby the fluorescent molecules in the light emitting layer emit light to form an image. At this time, the excited state of the light emission while falling to the ground state through the singlet excited state is called "fluorescence", and the emission of light while falling to the ground state through the triplet excited state is called "phosphorescence". In the case of fluorescence, the probability of singlet excited state is 25% (triple state 75%) and there is a limit of luminous efficiency, whereas phosphorescence can be used to triplet 75% and singlet excited state 25%. Internal quantum efficiencies up to 100% are possible.

An organic light emitting device using phosphorescence, which is a green and red high efficiency organic light emitting diode using phosphorescent dopants Ir (ppy) ₃ and PtOEP, which are phosphorescent dyes having a heavy element such as Ir and Pt having a large spin-orbit coupling with a CBP host A light emitting device has been developed (Phys. Lett., 4 (1999 vol. 75) & Nature 750 (2000 vol. 75)) However, since the organic light emitting device has a short lifespan of less than 150 hours, in terms of commercial use This is insufficient because the glass transition temperature of CBP is lower than 110 degrees and crystallization easily occurs.

As another example of an organic light emitting device using phosphorescence, an organic light emitting device employing a blue phosphorescent dopant (4,6-F2ppy) ₂ Irpic and an Ir compound based on a fluorinated ppy ligand structure has been developed. (1999 vol. 79, 2082-2084) & Chem. Commun., (1494-1495, 2001). In such an organic light emitting device, the energy gap of the triplet state of the CBP allows sufficient energy transfer to the energy gap of the green and red phosphorescent dopant materials, but is smaller than the energy gap of the blue material so that the PL peaks are 475 nm and 495 nm. It is reported that even in materials such as skyblue (4,6-F ₂ ppy) ₂ Irpic, very inefficient endothermic transitions occur rather than exothermic energy transitions. As a result, the CBP host is pointed to cause the problems of low blue light emission efficiency and short lifespan due to insufficient energy transfer to the blue phosphorescent dopant.

Recently, mCP (1,3-Bis (carbazol-9-yl) -benzene) compound having a triplet energy gap larger than CBP has been used, but this molecule has problems such as low molecular weight and poor stability. Improvements are needed.

The technical problem to be solved by the present invention is to solve the above problems, have electrical stability and high charge transport ability, high glass transition temperature and prevent crystallization, and all colors such as red, green, blue, white, etc. To provide a host material suitable for the fluorescent and phosphorescent dopant of.

Another object of the present invention is to provide an organic light emitting device having high efficiency, low voltage, high brightness and long life using the material.

In order to achieve the above technical problem, a first aspect of the present invention provides a compound having Formula 1 below:

<Formula 1>

In Formula 1, Z is a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, a halogen atom, a hydroxy group, a cyano group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, substituted or unsubstituted C ₁ -C ₃₀ acyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₃₀ alkynyl group, substituted or unsubstituted A C ₆ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group or -Si (Ar ₁ ) ₃ , wherein Ar ₁ is substituted Or an unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₄ -C ₃₀ heteroaryl group, two or more adjacent to each other of R ₁ to R ₆ may be connected to each other to form a ring; Q ₁ , Q ₂ , Q ₃ and Q ₄ are independently of each other C or N; a, b and n are, independently from each other, an integer from 1 to 4; a R ₅ may be identical to or different from each other, and b R ₆ may be identical to or different from each other.

In order to achieve the other technical problem of this invention, the 2nd aspect of this invention provides the organic light emitting element in which the said organic film contains the compound mentioned above in the organic light emitting element containing an organic film between a pair of electrode.

The compound represented by Chemical Formula 1 according to the present invention is a blue light emitting material and has a dark blue light emitting property than conventionally proposed molecules, and thus can be used as a blue host for a full color organic light emitting device. It is particularly useful as a blue phosphorescent host with triplet energy gaps and thermal stability suitable for blue phosphorescent dopants including Ir, Pt, Os, and Re metals, as well as for various phosphorescent or fluorescent dopants such as red, green, blue, and white. It can be used as a host to obtain an organic light emitting device having characteristics such as high efficiency, high brightness, long life, low power consumption.

Hereinafter, the present invention will be described in more detail.

Carbazole ring-containing silicone-based compounds according to the present invention have the formula (1) as described above. According to Formula 1, 1 to 4 phenyl groups substituted with a carbazole group are linked to Si. At this time, the carbazole group is necessarily substituted at the meta position of the phenyl group, as can be seen from the formula (1). If a carbazole group is present at the meta position of the phenyl group, it may be more electrically stable. Therefore, the film containing the compound having Formula 1 may be usefully used as an organic film of the organic light emitting device, in particular, a host material, a hole injection layer or a hole transport layer of the light emitting layer.

In Formula 1, Z may be a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group.

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen, a halogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted Or an unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₁ -C ₃₀ acyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkynyl group , Substituted or unsubstituted C ₆ -C ₃₀ aralkyl group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, or -Si (Ar ₁ ) ₃ have. In this case, Ar ₁ may be a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₄ -C ₃₀ heteroaryl group. On the other hand, two or more adjacent to each other of the R ₁ to R ₆ may be connected to each other to form a ring, for example, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ Adjacent pairs of substituents, such as and the like, may each form a benzene ring, a cyclohexane ring, and the like.

Specific examples of the unsubstituted C ₁ -C ₃₀ alkyl group used in Chemical Formula 1 of the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like. At least one hydrogen atom is a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, or C ₁ -C ₃₀ alkyl group, C ₁ -C ₃₀ alkenyl group, C ₁ -C ₃₀ alkynyl group, C ₆ -C ₃₀ aryl group, C ₇ -C ₂₀ arylalkyl group, C ₂ -C ₂₀ heteroaryl group or C ₃ -C ₃₀ heteroarylalkyl group Can be substituted.

Specific examples of the unsubstituted C ₁ -C ₃₀ alkoxy group used in Chemical Formula 1 of the present invention include methoxy, ethoxy, phenyloxy, cyclohexyloxy, naphthyloxy, isopropyloxy, diphenyloxy and the like. At least one hydrogen atom of these alkoxy groups may be substituted with the same substituent as in the alkyl group described above.

Specific examples of the unsubstituted C ₁ -C ₃₀ acyl group used in the general formula (1) of the present invention, acetyl, ethylcarbonyl, isopropylcarbonyl, phenylcarbonyl, naphthylenecarbonyl, diphenylcarbonyl, cyclohexyl Carbonyl and the like, and at least one hydrogen atom of these acyl groups may be substituted with the same substituent as in the alkyl group described above.

The unsubstituted C ₂ -C ₃₀ alkenyl group used in the general formula (1) of the present invention means that it contains a carbon double bond in the middle or the end of the alkyl group as defined above. Examples are ethylene, propylene, butylene, hexylene and the like. At least one hydrogen atom of these alkenyl groups may be substituted with the same substituent as in the alkyl group described above.

The unsubstituted C ₂ -C ₃₀ alkynyl group used in Formula 1 of the present invention means that it contains a carbon triple bond in the middle or the end of the alkyl group as defined above. Examples include acetylene, propylene, phenylacetylene, naph Acetylacetylene, isopropylacetylene, t-butylacetylene, diphenylacetylene and the like. At least one hydrogen atom of these alkynyl groups may be substituted with the same substituent as in the alkyl group described above.

The unsubstituted C ₆ -C ₃₀ aralkyl group used in the general formula (1) of the present invention is a group in which some of the hydrogen atoms in the aryl group as defined above are lower alkyl, for example methyl, ethyl, propyl, etc. It means substituted. For example benzyl, phenylethyl and the like. At least one hydrogen atom of the aralkyl group may be substituted with the same substituent as in the alkyl group described above.

The unsubstituted aryl group used in Formula 1 of the present invention is used alone or in combination to mean a carbocyclic aromatic system having 6 to 30 carbon atoms containing one or more rings, wherein the rings are attached or fused together in a pendant manner. Can be. At least one hydrogen atom of the aryl group may be substituted with the same substituent as in the alkyl group described above.

Examples of the aryl group include phenyl group, ethylphenyl group, ethyl biphenyl group, o-, m- and p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluoromethoxyphenyl group, o-, m-, and p-tolyl group, o-, m- and p-cumenyl groups, mesityl groups, phenoxyphenyl groups, (α, α-dimethylbenzene) phenyl groups, (N, N'-dimethyl) aminophenyl groups, (N, N'-diphenyl) aminophenyl groups Pentarenyl group, indenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group, fluorenyl group, anthraquinolyl group, methyl anthryl group, Phenanthryl group, triphenylene group, pyrenyl group, chrysenyl group, ethyl-crisenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexa Senyl group, rubisenyl group, coroneyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, pyrantrenyl group, obarenyl group, carbazole And the like groups.

Unsubstituted C ₄ -C ₃₀ heteroaryl group for use in the present invention comprises one, two or three heteroatoms selected from N, O, P or S, the monovalent monocyclic or bicyclic having the remaining ring atoms of C By click aromatic divalent organic compound is meant. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group described above.

Examples of the heteroaryl group include pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, triazolyl group, tetrazolyl group, oxadizolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, Triazinyl group, carbazolyl group, indolyl group, etc. are mentioned.

Preferably, Z is a phenyl group, lower alkylphenyl group, lower alkoxyphenyl group, cyanophenyl group, phenoxyphenyl group, halophenyl group, naphthyl group, lower alkyl naphthyl group, lower alkoxy naphthyl group, cyanonaphthyl group, halo naphthyl group, flu Orenyl group, carbazolyl group, lower alkylcarbazolyl group, biphenyl group, lower alkylbiphenyl group, lower alkoxybiphenyl group, thiophenyl group, indolyl group or pyridinyl group, and may be R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, phenyl group, lower alkylphenyl group, lower alkoxyphenyl group, cyanophenyl group, phenoxyphenyl group, Halophenyl group, naphthyl group, lower alkyl naphthyl group, lower alkoxy naphthyl group, cyanonaphthyl group, halonaphthyl group, fluorenyl group, carbazolyl group, lower alkyl carbazolyl group, biphenyl group, lower alkyl biphenyl group, lower alkoxy Biphenyl group, thiophenyl group, indolyl group Pyridinyl may be a. Among these, the carbon number of lower alkyl and lower alkoxy is preferably in the range of 1 to 5.

More preferably, Z may be a phenyl group, fluorenyl group, carbazolyl group, naphthyl group, phenanthrenyl group and the like, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, , Halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, phenyl group, fluorenyl group, carbazolyl group, naphthyl group, phenanthrenyl group and the like. In addition, at least one aromatic ring of the phenyl group, fluorenyl group, carbazolyl group, naphthyl group, or phenanthrenyl group has 3 or lower carbon atoms, lower alkoxy carbon 3 or less, cyano, phenoxy, phenyl or halogen. To 3, preferably 1 may be substituted.

In Formula 1, Q ₁ , Q ₂ , Q ₃ and Q ₄ may be C or N independently of each other.

In Formula 1, a, b, and n are each independently an integer of 1 to 4. Among these, a and b may be determined according to the case where Q ₁ , Q ₂ , Q ₃ and Q ₄ are N and C, which can be easily recognized by those skilled in the art.

According to an embodiment of the present invention, in Formula 1, R ₁ and R ₄ are each independently a halogen atom, a hydroxy group, a cyano group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C _{It may be a 1} -C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ -C ₃₀ acyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group or a substituted or unsubstituted C ₂ -C ₃₀ alkynyl group. That is, in Formula 1, R ₁ and R _{4, which} are ortho positions of the phenyl group in which the carbazole group is substituted, may be independently substituted with substituents as described above except hydrogen. In Formula 1, when R ₁ and R _4, which are ortho positions of the phenyl group, are independently substituted with each other as described above, steric hindrance may occur in the compound having Formula 1, and thus, Compounds that have can be twisted. As a result, the energy band gap of the compound having Formula 1 may be increased, and thus the hole transporting ability and the light emitting ability may be improved.

Compound having Formula 1 may have the following Formula 1a, 1b or 1c, but is not limited thereto:

<Formula 1a> <Formula 1b>

<Formula 1c>

Meanwhile, the compound having Chemical Formula 1 may have the following Chemical Formula 1d, 1e, or 1f, but is not limited thereto.

<Formula 1d> <Formula 1e>

<화학식 1f>

<Formula 1f>

이다.Ph in Formulas 1a to 1f

to be.

The compound having Formula 1 may be prepared using various known methods, which can be easily recognized by those skilled in the art.

Hereinafter, an organic light emitting device using the compound according to Chemical Formula 1 as an organic film forming material and a method of manufacturing the same will be described.

1 is a cross-sectional view showing an embodiment of the structure of an organic light emitting device.

First, an anode is formed by coating an anode electrode material on the substrate. Herein, a substrate used in a conventional organic light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, as the anode forming material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

The hole injection layer material is vacuum-heat-deposited or spin coated on the anode to form a hole injection layer (HIL). The hole injection layer material is not particularly limited, but copper phthalocyanine (CuPc) or starburst type amines TCTA, m-MTDATA, m-MTDAPB (where TCTA, m-MTDATA, m-MTDAPB are referred to in the literature) J. Chem. Inf. Comput. Sci. 2003 vol. 43, pages 970 to 977, whose chemical structure is shown). Apart from this, it is also possible to use the compound having the formula (1) according to the present invention as the hole injection layer material.

Subsequently, the hole transport layer material is vacuum-heat-deposited or spin-coated on the hole injection layer to form a hole transport layer (HTL). The hole transport layer material is not particularly limited, and N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine, N, N'-di (naphthalene-1-yl) -N, N'-diphenyl-benxidine: α-NPD) Etc. are used. Apart from this, it is also possible to use a compound having the formula (1) according to the invention as the hole transport layer material.

The emission layer (EML) is formed on the hole transport layer formed by the above process. Herein, the light emitting layer material is not particularly limited, and it is also possible to use the compound having the above formula (1) alone or as a host, and to use phosphorescent or fluorescent dopants in the visible region together.

As the fluorescent dopant, IDE102 and IDE105, which are available from Idemitsu, are used. Ir (ppy) ₃ (ppy is an abbreviation of phenylpyridine) (green), (4,6-F2ppy) as the phosphorescent dopant. ) ₂ Irpic (reference: Chihaya Adachi etc. Appl. Phys. Lett ., 79, 2082-2084, 2001), TEB002 from Cobion, PtOEP (platinum (II) octaethylporphyrin), a compound having the formula (2) See Publication No. 2005-0078472), Firpric et al.

<Formula 2> Firpic

The light emitting layer forming method may vary depending on the light emitting layer material, for example, vacuum thermal co-deposition is used.

The content of the dopant is preferably 0.1 to 20 parts by weight, particularly 0.5 to 12 parts by weight, based on 100 parts by weight of the light emitting layer forming material (ie, the total weight of the compound of Formula 1 and the dopant is 100 parts by weight). If the content of the dopant is less than 0.1 parts by weight, the effect of the addition of the dopant is insignificant, and if it exceeds 20 parts by weight, concentration phosphorescence or fluorescence, such as concentration quenching (quenching) is not preferable because it occurs.

An electron transport material is vacuum deposited or spin coated on the light emitting layer to form an electron transport layer (ETL). Herein, the electron transporting material is not particularly limited, and Alq3 (tris (8-quinolinolato) -aluminium) and BCP (2,9-dimethyl- is represented by the following structural formula. 4,7-diphenylphenanthroline), TAZ (3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4-triazole), OXD7 (1,3-bis (N, Nt-butyl-phenyl ) -1,3,4-oxadiazole).

In addition, when the phosphorescent dopant is used to form the emission layer, in order to prevent the triplet exciton or the hole from being diffused into the electron transport layer, a hole blocking material is further vacuum-heat-deposited to form a hole blocking layer (HBL) as shown in FIG. 1. . In this case, the hole blocking material is not particularly limited, but should have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically a Balq, phenanthrolines-based compound represented by the following structural formula (eg, UDC Co., Ltd., BCP) and the like are used.

     Alq3 BAlq

In addition, as shown in FIG. 1, an electron injection layer (EIL) may be stacked on the electron transport layer. Examples of the electron injection layer forming material here include LiF, NaCl, CsF, Li ₂ O, BaO, and the like.

Then, the organic light emitting device can be completed by forming a cathode by vacuum-heat-depositing a metal for forming a cathode on the electron injection layer. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) and the like are used. In addition, a transmissive cathode using a transparent material such as ITO and IZO is used as a cathode to obtain a top emission organic light emitting device.

As described above, the compound having Formula 1 may be used as a light emitting layer forming material, but may be used as a hole transporting layer or a hole injection layer forming material due to its excellent hole transporting ability.

In the organic light emitting device of the present invention, one or more intermediate layers may be further formed between the above-described anode, hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, and cathode. Do.

The following Synthesis Examples and Examples are intended to specifically illustrate the present invention, and thus the present invention should not be limited.

EXAMPLE

Synthesis Example  1a: Synthesis of Compound having Chemical Formula 1a (hereinafter referred to as "Compound 1a")

Compound 1a was synthesized according to the reaction route of Scheme 1a:

Synthesis of Intermediate a

Carbazole (1.67 g, 10 mmol), 1,3-dibromobenzene (3.0 mL, 25 mmol), CuI (0.38 g, ₂ mmol), K ₂ CO ₃ (5.53 g, 40 mmol), 18-crown-6 (53 mg , 0.2 mmol) was dissolved in DMPU (50 mL) and stirred at 170 ° C. for 3 hours. After cooling to room temperature, 250 mL of diethyl ether was added and washed with ammonia water (20 mL). The organic layer thus obtained was dried over magnesium sulfate, and the solvent was evaporated to obtain a crude product, which was then purified by silica gel column chromatography to obtain 2.16 g of intermediate a (yield 67%).

Synthesis of Compound 1a

After dissolving intermediate (a) (130 mg, 0.4 mmol) in THF (5 mL), add dropwise drop of 2.5 mol tertiary butyllithium (0.16 mL, 0.40 mmol) dissolved in normal hexane at -78 ° C, and then stir for 40 minutes. It was. Triphenylchlorosilane (80 mg, 0.27 mmol) was added to the reaction solution, followed by stirring at the same temperature for 30 minutes and at room temperature for 18 hours. After cooling to 0 ° C., 6 normal hydrochloric acid was added thereto, followed by extraction with 10 mL of diethyl ether 3 times. The organic layer thus obtained was dried over magnesium sulfate, the solvent was evaporated to obtain a crude product, and then separated and purified through silica gel column chromatography to obtain 115 mg of a compound 1a (yield: 57%).

¹ H NMR (CDCl ₃ , 400 MHz) δ (ppm) 8.10 (d, 2H), 7.78 (s, 1H), 7.58 to 7.63 (m, 9H), 7.23 to 7.44 (m, 15H)

Compound 1a obtained from Synthesis Example 1a was diluted with CHCl ₃ at a concentration of 10 mM and PL (photoluminescence) was measured at 293 nm to observe maximum luminescence at 365 nm (FIG. 2).

Meanwhile, Compound 1a (15 mg) and a compound having Formula 2 (phosphorantant, 3 mg, hereinafter referred to as "Compound 2") are dissolved in 4 mL of dichloromethane, and then in chlorobenzene (4 mL) in which PMMA (60 mg) is dissolved. 1 mL was added. The solution obtained therefrom was spin-coated on a glass at 1000 rpm for 30 seconds to form a film doped with Compound 1a Compound 1a, and PL was measured at 293 nm to observe maximum luminescence at 438 and 465 nm (FIG. 3).

Synthesis Example  1b: Synthesis of Compound having Chemical Formula 1b (hereinafter referred to as "Compound 1b")

Compound 1b was synthesized according to the reaction route of Scheme 1b:

Synthesis of Compound # 1b

Intermediate (a) (230 mg, 0.7 mmol) was dissolved in THF (5 mL) and then added dropwise to 2.5 mol tertiary butyllithium (0.28 mL, 0.7 mmol) dissolved in normal hexane at -78 ° C, followed by stirring for 40 minutes. Diphenyldichlorosilane (0.05 mL, 0.24 mmol) was added to the reaction solution and stirred for 30 minutes at the same temperature and 18 hours at room temperature. After the reaction solution was cooled to 0 ° C., 6 normal hydrochloric acid was added thereto, and 10 mL of diethyl ether was extracted 3 times. The organic layer thus obtained was dried over magnesium sulfate, the solvent was evaporated to obtain a crude product, and then purified by silica gel column chromatography to obtain 139 mg (yield 88%) of Compound 1b.

¹ H NMR (CDCl3, 400 MHz) δ (ppm) 8.09 (d, 4H), 7.83 (s, 2H), 7.64 to 7.69 (m, 10H), 7.24 to 7.44 (m, 18H)

Compound 1b was diluted with CHCl ₃ at a concentration of 10 mM and PL was measured at 293 nm to observe maximum luminescence at 349 and 364 nm (FIG. 4).

Meanwhile, Compound 1a (15 mg) and Compound 2 (phosphorantant, 3 mg) were dissolved in 4 mL of dichloromethane, and 1 mL was added to chlorobenzene (4 mL) in which PMMA (60 mg) was dissolved. The solution was spin-coated at 1000 rpm for 30 seconds on glass to form a film doped with Compound 1b, and then PL was measured at 293 nm to observe maximum luminescence at 438 and 466 nm (FIG. 5).

Synthesis Example  1c: Synthesis of Compound having Chemical Formula 1c (hereinafter referred to as "Compound 1c")

Compound 1c was synthesized according to the reaction route of Scheme 1c:

성 Synthesis of Compound 1c

Intermediate VIIa (426 mg, 1.32 mmol) was dissolved in THF (5 mL), and 2.5 mol butyl lithium lithium (0.53 mL, 1.32 mmol) dissolved in normal hexane at -78 ° C was added dropwise, followed by stirring for 40 minutes. Phenyltrichlorosilane (0.035 mL, 0.22 mmol) was added to the reaction solution, followed by stirring for 30 minutes at the same temperature and 18 hours at room temperature. After cooling the reaction solution to 0 DEG C, 6 normal hydrochloric acid was added thereto, and 10 mL of diethyl ether was extracted 3 times. The organic layer thus obtained was dried over magnesium sulfate, the solvent was evaporated to obtain a crude product, and then purified by silica gel column chromatography to obtain 63 mg of Compound 1c (yield: 34%).

¹ H NMR (CDCl3, 400 MHz) δ (ppm) 8.11 (d, 6H), 7.77 (s, 3H), 7.60 to 7.64 (m, 10H), 7.22 to 7.41 (m, 22H)

Compound 1c was diluted with CHCl ₃ at a concentration of 10 mM and PL was measured at 291 nm to observe maximum luminescence at 350 and 365 nm (FIG. 6).

Meanwhile, Compound 1c (15 mg) and Compound 2 (phosphorantant, 3 mg) were dissolved in 4 mL of dichloromethane and 1 mL was added to chlorobenzene (4 mL) in which PMMA (60 mg) was dissolved. The solution was spin-coated at 1000 rpm for 30 seconds on a glass to form a film doped with Compound 1c in Compound 1c, and PL was measured at 291 nm to observe maximum luminescence at 438 and 466 nm (FIG. 7).

Synthesis Example  1d: Synthesis of Compound Having Chemical Formula 1d (hereinafter referred to as "Compound 1d")

Compound 1d was synthesized according to the reaction route of Scheme 1d:

Synthesis of Intermediate b

Carbazole (1.67 g, 10 mmol), 2-bromo-4-chloro-1-fluoro-benzene (1.46 mL, 12 mmol), CuI (0.38 g, ₂ mmol), K ₂ CO ₃ (5.53 g, 40 mmol), 18-crown-6 (53 mg, 0.2 mmol) was dissolved in DMPU (50 mL) and stirred at 170 ° C. for 3 hours. After cooling to room temperature, 250 mL of diethyl ether was added and washed with ammonia water (20 mL). The organic layer was dried over magnesium sulfate, the solvent was evaporated to obtain a crude product, and the residue was purified by silica gel column chromatography to obtain 0.87 g (yield 30%) of intermediate a.

성 Synthesis of Compound 1d

After dissolving intermediate (a) (147 mg, 0.5 mmol) in THF (5 mL) and then dropping a drop of 2.5 mol tertiary butyllithium (0.2 mL, 0.5 mmol) dissolved in normal hexane at -78 ° C, the mixture was stirred for 40 minutes. Triphenylchlorosilane (98 mg, 0.33 mmol) was added to the reaction solution above, followed by stirring for 30 minutes at the same temperature and 18 hours at room temperature. After the reaction solution was cooled to 0 ° C., 6 normal hydrochloric acid was added thereto, and extracted 3 times with 10 mL of diethyl ether. The resulting organic layer was dried over magnesium sulfate and evaporated to give a crude product, which was purified by silica gel column chromatography to give 153 mg of compound 3-1 (yield 59%).

¹ H NMR (CDCl ₃ , 400 MHz) δ (ppm) 8.09 (d, 2H), 7.68 (s, 1H), 7.55 to 7.63 (m, 6H), 7.19 to 7.49 (m, 17H)

Compound 1d was diluted with CHCl ₃ at a concentration of 10 mM and PL was measured at 291 nm, and maximum luminescence was observed at 341, 356, and 375 nm (FIG. 8).

Meanwhile, compound 1d (15 mg) and compound 2 (phosphorantant, 3 mg) were dissolved in 4 mL of dichloromethane, and 1 mL was added to chlorobenzene (4 mL) in which PMMA (60 mg) was dissolved. The solution was spin-coated on a glass at 1000 rpm for 30 seconds to form a film doped with Compound 1d Compound 1d, and PL was measured at 291 nm to observe maximum luminescence at 438 and 466 nm (FIG. 9).

Example  1a

Corning's 10 Ω / cm 2 ITO substrate was used as an anode, and an IDE406 (Idemitsu Corp.) was vacuum deposited on the substrate to form a hole injection layer having a thickness of 600 μs. Subsequently, the IDE320 (Idemitsu Co., Ltd.) was vacuum deposited to a thickness of 300 kPa on the hole injection layer to form a hole transport layer. In a 90:10 mixed weight ratio on the hole transport layer, a mixture of Compound 1a and Firpic obtained from Synthesis Example 1a was vacuum deposited to form a light emitting layer having a thickness of 300 Å.

Thereafter, BAlq was vacuum-deposited on the emission layer to form a hole suppression layer having a thickness of 50 kHz. Thereafter, Alq3 was vacuum deposited on the emission layer to form an electron transport layer having a thickness of 200 kHz. LiF 10kV and Al 3000kV were sequentially vacuum deposited on the electron transport layer to form a cathode, thereby completing the organic light emitting device.

Example  1b

An organic light-emitting device was completed in the same manner as in Example 1, except that Compound 1b, obtained from Synthesis Example 1b, was used instead of Compound 1a, when forming the emission layer.

Example  1c

An organic light-emitting device was completed in the same manner as in Example 1, except that Compound 1c, obtained from Synthesis Example 1c, was used instead of Compound 1a, when forming the emission layer.

Example  1d

An organic light-emitting device was completed in the same manner as in Example 1, except that Compound 1d, obtained from Synthesis Example 1d, was used instead of Compound 1a, when forming the emission layer.

In the organic light emitting device manufactured according to Examples 1a to 1d, the driving voltage, the current density, the brightness, the current efficiency, the power efficiency, and the color purity were evaluated using a PR650 (Spectroscan) Source Measurement Unit. Table 1 shows.

division Voltage (V) Current density (mA / ㎠) Brightness (cd / ㎡) Current efficiency (cd / A) Power Efficiency (Im / W) Color coordinates (x, y) Example 1b 7.1668 8.3816 600 7.2090 3.1657 (0.16, 0.32) Example 1c 7.4254 7.4909 600 8.0558 3.4130 (0.15, 0.30)

Similar results as in Table 1 were obtained for the organic light emitting diodes manufactured according to Examples 1a and 1d. From this, it was confirmed that the organic light emitting elements of Examples 1a to 1d were excellent in voltage, current density, brightness, and efficiency characteristics, and also excellent in color coordinate characteristics.

The carbazole ring-containing silicone compound according to the present invention is excellent in blue light emission characteristics and hole transport properties, which can be used as a blue light emitting material or as a host for various phosphorescent or fluorescent dopants such as red, green, blue, and white. Can be. The organic light emitting device employing such a carbazole ring-containing silicon compound has high efficiency, high brightness, long life and It has low power consumption.

 Although the present invention has been described with reference to the synthesis examples and examples, this is merely illustrative, and those skilled in the art to which the present invention pertains various modifications and equivalent other embodiments. Will understand. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (8)

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

In Formula 1, Z is a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, a halogen atom, a hydroxy group, a cyano group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, substituted or unsubstituted C ₁ -C ₃₀ acyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₃₀ alkynyl group, substituted or unsubstituted A C ₆ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group or -Si (Ar ₁ ) ₃ , wherein Ar ₁ is substituted or An unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₄ -C ₃₀ heteroaryl group, two or more adjacent to each other of R ₁ to R ₆ may be linked to each other to form a ring; Q ₁ , Q ₂ , Q ₃ and Q ₄ are independently of each other C or N; a, b and n are, independently from each other, an integer from 1 to 4; a R ₅ may be identical to or different from each other, and b R ₆ may be identical to or different from each other. The method of claim 1, wherein, R ₁ and R ₄ are independently, a halogen atom, a hydroxy group, a cyano group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted each other Or an unsubstituted C ₁ -C ₃₀ acyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, or a substituted or unsubstituted C ₂ -C ₃₀ alkynyl group. A compound according to claim 1 having the formula 1a, 1b or 1c; <Formula 1a> <Formula 1b>

<Formula 1c>

In Formulas 1a to 1c, Ph is

to be. A compound according to claim 1 or 2, having the formula 1d, 1e or 1f: <Formula 1d> <Formula 1e>

<Formula 1f>

In Formulas 1d to 1f, Ph is

to be. In an organic light emitting device comprising an organic film between a pair of electrodes, An organic light-emitting device, characterized in that the organic film comprises the compound of any one of claims 1 to 4. The organic light emitting device according to claim 5, wherein the organic film is a light emitting layer. The organic light emitting device of claim 6, wherein the light emitting layer further comprises phosphorescent or fluorescent dopants in a visible region. The organic light emitting device of claim 5, wherein the organic layer is a hole injection layer or a hole transport layer.

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