KR101352021B1 - Silicon type compound having bisphenylcarbazol in element and method for preparing of organic thin layer of organic light emitting devices using it - Google Patents

Abstract

The present invention relates to a silicon compound having a bis (phenylcarbazole) group in a molecule and a method for forming an organic thin film layer of an organic light emitting device using the same, in particular, the compound of the present invention is excellent in blue light emission characteristics and hole transport characteristics, and at the same time blue light emission. It can be used as a material or as a host for various phosphorescent or fluorescent dopants such as red, green, blue, white, etc., and can be applied to organic light emitting devices through the electrochemical deposition method. The present invention relates to a silicon compound having a bis (phenylcarbazole) group in a molecule capable of imparting high brightness, high brightness, and long life, and a method of forming an organic thin film layer of an organic light emitting device using the same.

Organic light emitting device, electrochemical vapor deposition, carbazole, silicon

Description

Silicon-based compound having a bis (phenylcarbazole) group in a molecule and a method of forming an organic thin film of an organic light emitting device using the same

1 is a cyclic voltamonogram showing electrochemical deposition with a silicon compound having a bis (phenylcarbazole) Bis (phenylcarbazol) group in a molecule represented by Chemical Formula 1 according to one embodiment of the present invention.

2 is a cyclic voltamonogram showing electrochemical deposition with a silicon compound having a bis (phenylcarbazole) Bis (phenylcarbazol) group in a molecule represented by Chemical Formula 1 according to another embodiment of the present invention.

3 is a cyclic voltamonogram showing electrochemical deposition with a silicon compound having a bis (phenylcarbazole) Bis (phenylcarbazol) group in a molecule represented by Chemical Formula 1 according to another embodiment of the present invention.

4 is a cyclic voltamonogram showing electrochemical deposition with a silicon compound having a bis (phenylcarbazole) Bis (phenylcarbazol) group in a molecule represented by Chemical Formula 2, which is another embodiment of the present invention.

5 is a UV spectrum taken when diluting a compound of Formula 2, which is another embodiment of the present invention, with chloroform,

6 is a PL spectrum taken by diluting a compound of Formula 2, which is another embodiment of the present invention, with chloroform.

The present invention relates to a silicon compound having a bis (phenylcarbazole) group in a molecule and a method for forming an organic thin film layer of an organic light emitting device using the same. It can be used as a host for various phosphorescent or fluorescent dopants such as red, green, blue, white, and the like, and can be applied to organic light emitting devices through electrochemical deposition method, high efficiency light emission, low voltage, high brightness In addition, the present invention relates to a compound having a bis (phenylcarbazole) group in a molecule capable of imparting long-life characteristics, and a method of forming an organic thin film layer of an organic light emitting device using the same.

In the display field, an organic light emitting diode (OLED) is a self-luminous display device, which has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed, and multicolor, in comparison with inorganic EL devices. It has a merit of being able to be made and it is attracting attention as a display element.

A general organic EL device has an anode in which an anode is formed on a substrate, an organic thin film emitting layer is formed on the anode, and cathodes are sequentially formed. In addition, a hole injection layer or a hole transport layer may be provided between the anode and the light emitting layer, and an electron transport layer or an electron injection layer may be provided between the light emitting layer and the cathode. Here, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer are organic thin film layers made of organic compounds.

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

First, 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 is emitted to the ground state through the singlet excited state is called fluorescence, and the emission is emitted 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 inno steel can be used to triplet 75% and singlet excited state 25%. Up to 100% internal quantum efficiency is possible.

On the other hand, it is effective to emit light in triplet state (phosphorescence) by using it (ppy) ₃ and PtOEP, which are phosphorescent pigments centered on heavy elements such as Ir and Pt with large spin-quado bonds, as dopants. Has developed a highly efficient organic electroluminescent device. At this time, CBP (4,4'-N, N'-dicarbazole-biphenyl) was used as a host.

However, since the glass transition temperature of CBP is lower than 100 ° C. and crystallization easily occurs, the organic EL device has a short life of less than 150 hours, which is insufficient from a commercial use point of view. There is a need for research on new compounds.

In order to solve the above problems of the prior art, the present invention is excellent in blue light emission characteristics and hole transfer characteristics, and at the same time used as a blue light emitting material or as a host for various phosphorescent or fluorescent dopants such as red, green, blue, white, etc. An object of the present invention is to provide a silicone-based compound having a bis (phenylcarbazole) group in the molecule and a method for producing the same.

Another object of the present invention is to apply a compound having a bis (phenylcarbazole) group in the molecule to the organic thin film layer of the organic light emitting device capable of high-efficiency light-emitting, it is possible to give a low voltage, high brightness, long life characteristics of the organic light emitting device An organic thin film layer, an organic light emitting device, and a display device including the same.

In order to achieve the above object, the present invention provides a silicone-based compound having a bis (phenyl carbazole) group in the molecule represented by the following formula (1) or (2).

[Formula 1]

(2)

In the formula of Formula 1 or 2,

Each R independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 50 carbon atoms, or a 6 to 50 carbon atoms A substituted or unsubstituted heterocyclic group,

Each R ₁ is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,

n is an integer of 1 to 3;

In the present invention, bromobenzene and carbazole are reacted to produce a (bromophenyl) carbazole compound, and n-butyllithium is added to the (bromophenyl) carbazole compound to prepare a (lithiumphenyl) carbazole compound. Thereafter, the method of preparing a silicone-based compound having a bis (phenylcarbazole) group in a molecule represented by Chemical Formula 1, wherein the (lithiumphenyl) carbazole compound is reacted with a silanecyclodichloride.

In another aspect, the present invention is to prepare a (bromophenyl) carbazole compound by reacting bromobenzene and carbazole, and to react the (bromophenyl) carbazole compound with dichlorotetraphenylsilane, the formula (2) It provides a method for producing a silicon compound having a bis (phenylcarbazole) group in the molecule represented by.

In another aspect, the present invention provides an organic thin film layer of an organic light emitting device formed of a silicon compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or (2).

The present invention also provides an organic light emitting device comprising at least one organic thin film layer in an organic light emitting device comprising at least one organic thin film layer between the anode and the cathode.

In another aspect, the present invention provides a display device comprising the organic light emitting device.

Hereinafter, the present invention will be described in detail.

The silicone-based compound having a bis (phenylcarbazole) group in a molecule represented by Chemical Formula 1 or 2 of the present invention has excellent blue light emission property, hole transport property or electron transport property, and is used as a blue light emitting material, phosphorescent or fluorescent host material. It is suitable to

In Formula 1, R is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 50 carbon atoms, or 6 to 50 carbon atoms. 50 substituted or unsubstituted heterocyclic group.

Specific examples of the alkyl group having 1 to 50 carbon atoms include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like. One or more hydrogen atoms of the alkyl group may be a halogen atom, a hydroxyl group, or a 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, indole, aziindole, alkyl group having 1 to 50 carbon atoms, alkenyl group having 1 to 50 carbon atoms, It may be substituted with an alkynyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group having 7 to 50 carbon atoms, a heteroaryl group having 2 to 50 carbon atoms, or a heteroarylalkyl group having 3 to 50 carbon atoms, among which Two or more may bond and fuse with each other to form a saturated or unsaturated ring.

In addition, the unsubstituted aryl group is used alone or in combination to mean a carbocyclic aromatic system having 6 to 50 carbon atoms containing at least one ring, the rings may be attached or fused together in a pendant method. The aryl includes an aromatic radical such as phenyl, naphthyl, tetrahydronaphthyl, and at least one hydrogen atom of the aryl group may be substituted with the same substituent as in the alkyl group described above.

In addition, the unsubstituted heterocyclic group includes 1, 2, or 3 heteroatoms selected from N, O, P, or S, and has 6 to 50 monovalent monocyclic or non-membered ring atoms having C ring atoms. It means a cyclic aromatic organic compound. At least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the alkyl group described above.

In addition, the unsubstituted heterocyclic group means a cyclic moiety in which two or more rings forming an aryl group or a heterocyclic group are fused with each other as defined above, and at least one hydrogen atom of the heterocyclic group is an alkyl group as described above. Substitutable with the same substituents as in the case of.

Preferred specific examples of the silicone-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) of the present invention include the compounds of the formulas (1-1) to (1-4), and are also preferred compounds of the compound represented by the formula (2) R or R ₁ is preferably hydrogen or methyl.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the formulas (1-1) to (1-4), R is as defined above, preferably R is hydrogen.

The silicone compound having a bis (phenylcarbazole) group in the molecule represented by Chemical Formula 1 of the present invention as described above reacts bromobenzene and carbazole to prepare a (bromophenyl) carbazole compound, and the (bromophenyl N-butyllithium is added to the carbazole compound to prepare a (lithiumphenyl) carbazole compound, and then reacted with the (lithylphenyl) carbazole compound and a silanecyclodichloride.

Specifically, the compound having a bis (phenylcarbazole) group in the molecule of the present invention can be prepared according to the following Scheme 1, which corresponds to an example for preparing a compound having a bis (phenylcarbazole) group in the molecule of the present invention However, the method for preparing the compound having a bis (phenylcarbazole) group in the molecule represented by Chemical Formula 1 of the present invention is not limited to the following Scheme 1.

[Reaction Scheme 1]

In Scheme 1, n is an integer of 1 to 3.

In addition, the silicone-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (2) of the present invention reacts bromobenzene and carbazole to produce a (bromophenyl) carbazole compound, and the (bromophenyl) carba The sol compound may be prepared by reacting dichlorotetraphenylsilane, and specifically, it may be prepared according to Scheme 2 below, which is an example for preparing a silicone-based compound having a bis (phenylcarbazole) group in a molecule of the present invention. Only corresponding to the above, the method for preparing a compound having a bis (phenylcarbazole) group in the molecule represented by the formula (2) is not limited to the following scheme 2.

[Reaction Scheme 2]

In addition, the present invention is an organic light-emitting device comprising an organic thin film layer and at least one organic thin film layer of an organic light emitting device formed of a silicon compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or (2) according to the present invention When provided, the method of manufacturing the organic light emitting device is as follows.

In general, an organic light emitting device includes a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), and an electron between an anode and a cathode It may include one or more organic thin film layers such as an injection layer (EIL), the organic thin film layer described in the present invention is one of the organic layer formed between the anode and the cathode of the organic light emitting device, a hole injection layer, a hole transport layer, a light emitting layer , A hole blocking layer, an electron transport layer, or an electron injection layer, preferably, a hole injection layer, a hole transport layer, or a light emitting layer.

First, an anode is formed by depositing a material for an anode electrode having a high work function on the substrate. In this case, the substrate may be a substrate used in a conventional organic light emitting device, in particular, it is preferable to use an organic substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity can be used. The anode electrode material can be deposited by a conventional anode formation method, and specifically, it can be deposited by a deposition method or a sputtering method.

Subsequently, a hole injection layer (HIL) material may be formed on the anode by vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), electrochemical deposition, and the like. It is preferable to form by a vapor deposition method.

When the hole injection layer is formed by the electrochemical deposition method, a silicon compound having an intramolecular bis (phenylcarbazole) group represented by Formula 1 or 2 and an electrolyte in which a hole injection layer is to be formed are avoided in a reaction tank in which a solvent is dissolved. It refers to a method of forming a hole injection layer by depositing a compound to be deposited by placing a deposition substrate and applying power.

The solvent that can be used in the reactor is not particularly limited as long as it is a solvent capable of dissolving the compound to be deposited and the electrolyte, and specific examples thereof include dichloromethane (CH ₂ Cl ₂ ), tetrahydrofuran (THF), and acetonitrile ( CH ₃ CN), benzonitrile (C ₆ H ₅ CN), propylene carbonate (1,2-propanediol cycliccarbonate), or toluene (C ₆ H ₅ CH ₃ ) . However, when it is desired to form two or more organic thin film layers, it is preferable not to use a solvent for dissolving the compound of the organic thin film layer formed first. In addition, the amount of the solvent is preferably 0.01 to 10 mM based on the concentration of the compound. If the concentration is too thin, the electrochemical deposition may not be performed. If the concentration is too high, problems such as thickness control and voltage drop of the electrochemical deposited film may occur.

In addition, the electrolyte that can be used in the reaction vessel is not particularly limited as long as it can dissolve in the solvent and ionize the compound to be deposited upon application of power applied in the reaction vessel, and specific examples are Me ₄ NBF ₄ , Et ₄ NBF ₄ , Pr ₄ NBF ₄ , Bu ₄ NBF ₄ , Me ₄ NClO ₄ , Et ₄ NClO ₄ , Pr ₄ NClO ₄ , Bu ₄ NClO ₄ , Me ₄ NPF ₆ , Et ₄ NPF ₆ , Pr ₄ NPF ₆ , Bu ₄ NPF ₆ , LiClO ₄ , LiBF ₄ , LiPF ₆ , or LiBOB and the like. The concentration of the supporting electrolyte in the reactor is preferably 50 to 500 mM. If the concentration of the electrolyte is too thin, problems such as voltage drop may occur.

The hole injection layer material which can be used in addition to the silicon compound of the present invention is not particularly limited, and TCTA, m-MTDATA, m-MTDAPB, which are phthalocyanine compounds or starburst amine derivatives such as copper phthalocyanine disclosed in US Pat. No. 4,356,429. It can be used as a hole injection layer material (Advanced Material, 6, p677 (1994)).

Next, a hole transport layer (HTL) material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, electrochemical deposition, and the like, in particular, by electrochemical deposition. desirable. In the case of forming the hole transport layer by the electrochemical vapor deposition method, the conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer.

In addition, the hole transport layer material is not particularly limited, but may be a silicon-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or (2) according to the present invention, or from among conventional known materials used in the hole transport layer It can be used arbitrarily selected. Specifically, the hole transport layer material is a carbazole derivative such as N-phenylcarbazole, polyvinylcarbazole, N, in addition to the silicone-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or (2) according to the present invention N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) Conventional amine derivatives having an aromatic condensed ring such as -N, N'-diphenyl benzidine (? -NPD) can be used.

Thereafter, the light emitting layer (EML) material may be formed on the hole transport layer by a vacuum deposition method, a spin coating method, a cast method, an LB method, an electrochemical deposition method, and the like, and in particular, an electrochemical deposition method. Do. In the case of forming the hole transport layer by the electrochemical vapor deposition method, the conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer.

In addition, the light emitting layer material is not particularly limited, and the silicon compound represented by Formula 1 or 2 of the present invention may be used alone or as a host.

When the silicon compound represented by Chemical Formula 1 or 2 is used as a light emitting host, a light emitting layer may be formed by using a phosphorescent or fluorescent dopant together. In this case, as the fluorescent dopant, IDE102 or IDE105 which can be purchased from Idemitsu Co., Ltd. may be used. As the phosphorescent dopant, green phosphorescent dopant Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium) and blue phosphorescent dopant may be used. Phosphorus F2Irpic (iridium (III) bis [4,6-di-fluorophenyl) -pyridinato-N, C2 '] picolinate), UDC's red phosphorescent dopant RD61, and the like can be commonly vacuum deposited (doped).

The doping concentration of the dopant is not particularly limited, but the concentration of the dopant to 100 parts by weight relative to the host is preferably 0.01 to 15 parts by weight. If the content of the dopant is less than 0.01 parts by weight, there is a problem in that the color development is not performed properly because the amount of the dopant is not sufficient, and if it exceeds 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon. In the case of using the phosphorescent dopant in the light emitting layer, it is preferable to further laminate the hole suppression material (HBL) by vacuum deposition or spin coating to prevent the triplet excitons or holes from diffusing into the electron transport layer (HTL). Do. At this time, the hole-inhibiting material that can be used is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1), and the like, and typical Balq and phenanthrolines ) -Based compound (e.g., BDC Co., Ltd.) may be used.

An electron transport layer (ETL) material is formed on the light emitting layer formed as described above, wherein the electron transport layer may be formed by a vacuum deposition method, a spin coating method, a cast method, an electrochemical deposition method, and the like. It is preferable to form by.

The electron transport layer material has a function of stably transporting electrons injected from an electron injection electrode (Cathode) is not particularly limited in kind, for example, quinoline derivatives, especially tris (8-quinolinorate) aluminum ( Alq3) can be used. In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li ₂ O, BaO, or the like. The substance of can be used.

Thereafter, an electron injection layer (EIL) material may be formed on the electron transport layer, wherein the electron transport layer may be formed on a method such as vacuum deposition, spin coating, casting, electrochemical deposition, or the like. It may be formed by, in particular, it is preferable to form by the electrochemical deposition method.

Finally, the cathode forming metal is formed on the electron injection layer by a vacuum deposition method or a sputtering method and used as a cathode. As the metal for cathode formation, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof can be used. Specific examples thereof include Li, Mg, Al, Al-Li, Ca, Mg-In, Mg-Ag, . In addition, a transmissive cathode using ITO and IZO may be used to obtain a top emitting device.

The organic light emitting device of the present invention has an organic structure of an anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), a cathode (cathode) structure Not only the light emitting device, but also the structure of the organic light emitting device of various structures is possible, it is also possible to further form one or two intermediate layers as needed. In addition, the hole injection layer (HIL), the electron injection layer (EIL), the hole blocking layer (HBL) and the like are not necessary, but by forming these layers, the luminous efficiency can be improved.

In the present invention, the anode, hole injection layer (HIT), hole transport layer (HTL), light emitting layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), between the selected film of the cathode If necessary, one or more intermediate layers may be further formed.

The thickness of the organic thin film layer formed according to the present invention as described above can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.

In addition, after the organic thin film layer is formed as described above, the washing step or the drying step may be further performed as necessary. Through the washing process, foreign matters that may be present in the organic thin film layer may be removed, and the drying process may be applied to conventional drying methods that may be performed after the formation of the organic thin film layer of a known organic light emitting device.

In addition, the present invention is an organic thin film layer formed by depositing a silicon-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or 2 has excellent adhesion to the substrate, the thickness of the organic thin film layer can be adjusted in molecular units Therefore, the surface is uniform, there is an advantage of excellent shape stability.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

In the examples of the present invention all work was done under nitrogen or argon atmosphere using standard Schlenk techniques. Tetrahydrofuran (THF) was distilled off immediately before use with potassium benzophenone. In addition, 1H and 13C NMR were measured using a Varian mercury 300 of 300.1 and 75.4 MHz. In addition, all hydrogen and carbon chemical shifts were measured using residual benzene in a locked solvent (99.5% CDCl 3) based on tetramethylsilane (Me 4 Si). Elemental analysis was performed using a CHNS-O EA 1108 analyzer from Carlo Erba. The fluorescence quantum yield was determined by the dilution method based on 9,10-diphenylanthracene. CV experiments were performed using a BAS 100 electrochemical analyzer. A three-electrode system was used for the glass carbon as the working electrode, the platinum wire as the counter electrode, and the silver wire as the reference electrode. In addition, clean distilled and degassed methylene chloride was used as a solvent, and 0.1 M tetra-normal-butylammonium hexafluorophosphate was used as an electrolyte. Normal-butyllithium diluted in 1,4-dibromobenzene 2.5 M hexane was purchased from Aldrich and used directly without purification.

Example 1 Synthesis of 9,9'-bis (phenylcarbazole) Derivatives Including Silicone Rings (Compounds of Formula A-D)

Synthesis of 9,9'-bis (phenylcarbazole) (compound of formula a-d) comprising a silicone ring was prepared according to Scheme 1 below. 1,4-dibromobenzene and carbazole were used to form a (bromophenyl) carbazole compound using a Ullman condensation reaction, followed by reaction of normal-butyllithium and silanecyclodichloride to 9,9'-bis ( Phenylcarbazole) derivative compound ad was synthesized. However, in the case of 4-CBP compound a, the ring bond angle was unstable and the rectangular ring was soon released. However, 9,9'-bis (phenylcarbazole) derivatives, including all silicone rings except squares, could be separated through a column with a yield of 40-50%.

(Synthesis of 9- (4-bromophenyl) carbazole (Compound a))

Teflon magnetic milk stick, 1,4-dibromobenzene (25.184 g, 200 mmol), carbazole (8.36 g, 50 mmol), K ₂ CO ₃ (13.82 g, 100 mmol), and CuSO in a 100 mL flask ₄ (7.98 g, 50 mmol) was added and stirred at 210 ° C. for 16 hours without solvent. After the reaction was completed, the mixture was diluted with methylene chloride and filtered, and then the filtered solution was washed with distilled water and brine. The organic layer thus obtained was dehydrated using MgSO ₄ .

¹ H NMR (CDCl ₃ ): δ 8.21 (d, 2H), 7.40 (d, 2H), 7.25 (t, 2H), 7.13 (t, 2H), 7.35 (d, 2H), 7.16 (d, 2H) 13 C NMR (CDCl ₃ ): δ 111.1, 122.5, 125.7, 128.1, 130.2, 133.3

(Synthesis of 9,9'-bis (phenylcarbazole) (Compound b) with a pentagonal silicone ring)

Dilute 9- (4-bromophenyl) carbazole (1) (2.25 g, 12.5 mmol) in distilled tetrahydrofuran (THF) (10 mL) and add dropwise 2.5 M normal-butyllithium dropwise at -78 ° C. It was. After stirring 30 minutes at this temperature, dichlorocyclopentylsilane (2 mmol) was slowly added dropwise. After the addition was completed, the mixture was heated to room temperature and stirred for another 3 hours. After the solvent was removed, the residue was separated with ethyl acetate / hexane (volume ratio 1:10) by a silica gel column using a developing agent, and then separated at a yield of 43%.

¹ H NMR (CDCl ₃ ): δ 8.055, 7.753, 7.320, 7.215 (m, 16H, Cz), 7.536, 7.408 (m, 8H, Ph), 1.839 (m, 4H, C H 2), 1.198 (t , 4H, C H 2). 13 C NMR (CDCl ₃ ): 12.741, 28.158 ( C H2), 110.098, 120.265, 120.538, 123.695, 126.145, 126.555, 135.963, 136.464, 139.05, 140.811 ( C H).

(Synthesis of 9,9'-bis (phenylcarbazole) (compound c) comprising a silicone ring with a pentagonal double bond)

This compound was synthesized in the same manner as Compound b using dichloropentenylsilane instead of dichlorocyclopentylsilane in the synthesis of Compound b, and isolated at a yield of 47%.

¹ H NMR (CDCl ₃ ): 8.152, 7.877, 7.414, 7.297 (m, 16H, Cz), 7.654, 7.501 (m, 8H, Ph), 6.145 (m, H, C H 2), 2.027 (d, 4H , C H ). 13 C NMR (CDCl ₃ ): 0.359, 17.361 ( C H2), 110.038, 120.265, 120.516, 123.672, 126.130, 126.600, 131.229, 134.787, 136.464, 140.743 ( C H).

(Synthesis of 9,9'-bis (phenylcarbazole) (compound d) comprising a silicon ring with a hexagon)

This compound was synthesized in the same manner as Compound b, using dichlorohexylsilane instead of dichlorocyclopentylsilane in the synthesis of Compound b, and isolated at a yield of 50%.

₁ H NMR (CDCl ₃ ): 8.125, 7.805, 7.380, 7.266 (m, 16H, Cz), 7.588, 7.474 (m, 8H, Ph), 1.890 (m, 4H, C H 2), 1.614 (m, 2H , C H 2), 1.334 (t, 4H, C H 2). 13 C NMR (CDCl ₃ ): 12.073, 24.789, 30.305 ( C H2), 110.159, 120.273, 120.561, 123.710, 126.168, 126.585, 135.902, 136.236, 138.930, 140.81 ( C H).

[Reaction Scheme 1]

Example 2. Synthesis of 1,1'-bis (9-phenylcarbozol) -2,3,4,5-tetraphenylcyrrole

(Bromophenyl) carbazole was dissolved in distilled THF (10 ml), followed by dropwise addition of normal-butyllithium diluted in 2.5 M hexane at -78 ° C. The mixture was stirred at the same temperature for 30 minutes and then added dropwise using a cannula to the dichlorotetraphenylsilane compound diluted in THF (20 ml). After dropping, the reaction temperature was raised to room temperature, followed by further stirring for 4 hours. Water was added to the mixture, which was then extracted using ethyl acetate, and washed with water and brine. Water was removed from the organic layer using MgSO 4. After the solvent was removed under reduced pressure, the residue was separated by silica gel column using ethyl acetate and a developer of hexane (volume ratio 1:10), and then 1,1-bis (9-phenylcarbazole) -2,3,4 , 5-tetraphenylcyrrole was obtained.

1 H NMR (CDCl 3): 8.15 (d, 4H), 7.97 (d, 4H), 7.66 (d, 4H), 7.53 (d, 4H), 7.43 (t, 8H), 7.30 (m, 8H), 7.28 ( m, 8H) 13 C NMR (CDCl 3): 111.1, 122.5, 125.7, 128.1, 130.2, 133.3

Example 3 Electrochemical Deposition

In order to see the electrochemical properties, HOMO and LUMO levels of the compounds synthesized in Examples 1 and 2, we conducted a CV experiment using a Pt working electrode, a Pt counter electrode, and an Ag / Ag + (0.1M) electrode as a reference electrode. Was done. CV was tested by varying the measurement rate by blowing nitrogen gas at room temperature by dissolving 0.1 M tetrabutylammonium tetrafluoroborate (Bu ₄ NBF ₄ ) as an electrolyte in a methylene chloride solvent. The measured values were assayed based on the lotion. Electrochemical deposition using CV was at a rate of 100 mV / s. First, the electrochemical properties of the 9,9-bis (phenylcarbazole) derivative including the silicone ring were investigated. While analyzing the electrochemical properties, it was confirmed that a certain amount of film was formed on the working electrode. CV picture of the compound synthesized in Example 1 is shown in Figures 1 to 3, CV picture of the compound synthesized in Example 2 is shown in FIG.

As shown in Figures 1 to 4 all confirmed that the electrochemical deposition.

In addition, the compound synthesized in Example 2 was diluted in chloroforum to measure the UV spectrum and the PL spectrum, the figure is shown in Figures 5 to 6.

The release of the cyclo compound increased significantly as the viscosity of the cyclo compound increased, and this result was caused by the aggregation-induced emission (AIE) effect by the rotation of an aromatic ring substituted at the end of a single bond centered on the cyclo compound. Shows that it brings That is, when the compound was dissolved in the acetone solution, the light did not emit light, but the strong PL spectrum was shown when water which did not dissolve the compound was added to the acetone solution to some extent. This confirmed that the compound of Example 2 has an AIE phenomenon.

Silicone-based compound having a bis (phenylcarbazole) group in the molecule represented by the formula (1) or (2) according to the present invention is excellent in blue light emission characteristics and hole transfer properties, at the same time used as a blue light emitting material or red, green, blue, white and the like Not only can be used as a host for a variety of phosphorescent or fluorescent dopants, but also can be applied to the organic light emitting device, high efficiency light emission, it has the effect of imparting low voltage, high brightness, long life characteristics.

Claims (10)

delete Compounds represented by any one of the following Chemical Formulas 1-1 to 1-4 as a light emitting compound of the organic light emitting device: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the formula of Formula 1-1 to 1-4, R is an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, a heterocyclic group having 6 to 50 carbon atoms, or a heterocyclic group having 6 to 50 carbon atoms. delete delete An organic thin film layer of an organic light emitting device formed of a compound represented by any one of Formulas 1-1 to 1-4 described in claim 2. The method of claim 5, The organic thin film layer is an organic light emitting device, characterized in that the hole injection layer (HIT), hole transport layer (HTL), light emitting layer (EML), hole blocking layer (HBL), electron transport layer (ETL), or electron injection layer (EIL) Organic thin film layer. The method of claim 5, The organic thin film layer of the organic light emitting device, characterized in that the organic thin film layer is a compound represented by any one of formulas 1-1 to 1-4 by electrochemical deposition. An organic light emitting device comprising at least one organic thin film layer between an anode and a cathode, the organic light emitting device comprising at least one organic thin film layer according to claim 5. 9. The method of claim 8, The organic light emitting device is an organic light emitting device, characterized in that at least two consecutive layers of the organic thin film layer of claim 5. A display device comprising the organic light emitting device of claim 7.

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