KR101154185B1 - Organosilane Compounds, Materials Comprising Them, and Electroluminiscent Device Containing the Materials - Google Patents

Abstract

The organosilane-based compound according to the present invention has a structure of formula (I):

[Formula 1]

N is an integer from 1 to 4, m is an integer from 1 to 2, l is an integer from 0 to 1; Ar ₁ is selected from the group consisting of phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl and derivatives thereof, Ar ₂ is phenyl, naphthalene, anthracene, thiophene, Oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and derivatives thereof, and Ar ₃ and Ar ₄ are Phenyl, naphthalene and derivatives thereof, and R1, R2 are each selected from the group consisting of hydrogen, fluorine, trifluoro methyl, cyanide, methoxy, methyl and vinylphenyl.

Organic EL device, blue light emission, organosilane compound, phosphorescence

Description

Organic Compounds, Materials Comprising Them, and Electroluminiscent Device Containing the Materials}

1 is a graph showing UV and PL spectra of an organic EL device using an organosilane compound I according to Example 1 of the present invention.

2 is a graph showing CIE color coordinates of an organic EL device using the organosilane-based compound I according to Example 1 of the present invention.

3 is a graph showing UV and PL spectra of an organic EL device using the organosilane compound II according to Example 2 of the present invention.

4 is a graph showing CIE color coordinates of an organic EL device using the organosilane-based compound II according to Example 2 of the present invention.

5 is a graph showing UV and PL spectra of an organic EL device using the organosilane-based compound III according to Example 3 of the present invention.

6 is a graph showing UV and PL spectra of an organic EL device using the organosilane compound IV according to Example 4 of the present invention.

7 is a graph showing UV and PL spectra of an organic EL device using the organosilane compound V according to Example 5 of the present invention.

8 is a graph showing UV and PL spectra of an organic EL device using the organosilane compound VI according to Example 6 of the present invention.

9 is a graph showing UV and PL spectra of an organic EL device using the organosilane-based compound (VIII) according to Example 6 of the present invention.

10 is a schematic view showing an organic electroluminescent device according to the present invention.

Brief description of symbols in the drawings

1: Substrate 2: Anode

3: hole transport layer 4: light emitting layer

5: electron transport layer 6: cathode

Field of invention

The present invention relates to a silane phosphor and an organic electroluminescent device using the same. More specifically, the present invention relates to a silane-based phosphor having excellent blue light emission efficiency by introducing a silicon compound and an organic electroluminescent device using the same.

Background of the Invention

The most widely used liquid crystal display (LCD) is a non-light-emitting display device, which consumes little power and is light in weight, but the device driving system is complicated and the response time, contrast and other characteristics are not satisfactory. Therefore, research on organic electroluminescent devices (Organic Electroluminiscence Devices), which are recently attracting attention as a next-generation flat panel display, is being actively conducted. The organic electroluminescent device is a self-luminous device and has several advantages as compared to the liquid crystal display, having excellent characteristics such as brightness, driving voltage, and response speed, and having no dependency on viewing angle.

The light emitting mechanism of the organic EL device is as follows. Holes injected from the anode into the valence band or highest occupied molecular orbital (HOMO) of the hole injection layer (HIL) proceed to the emitting layer through the hole transporting layer (HTL). At the same time, electrons move from the cathode to the emission layer through the electron injection layer to combine with holes to form excitons. The exciton falls to the ground and emits light.

Using the principle of the organic EL device described above, Eastman Kodak Co., Ltd. in 1987 used TPD (N-N'-DiphenyI-N-N'-bis (methylphenyl-1,1'-biphenyl-) as a hole transport layer. An electroluminescent device was developed using Alq ₃ (tris (8-hydroxy- quinoline) aluminum complex) as a light emitting layer (4,4'-diamine) ( Appl. Phys. Lett. , 51, 913, 1987). The research on the electroluminescent device using the A has become active.

Up to now, Eastman Kodak's Alq3 is widely used as a green light emitting material, but blue light emitting material and red light emitting material have much improvement such as luminous efficiency and lifetime.

Eastman Kodak's Korean Patent Publication Nos. 2000-48008 and 2000-48009 disclose the use of anthracene derivatives for hole transport materials and blue light emitting materials. In addition, Korean Patent Publication No. 2002-26864 of Idemitsu Co., Ltd. discloses a material emitting blue light using an anthracene-based and a bianthracene-based. In addition, European Patent Publication No. 0388768 discloses a blue light emitting compound in which a phenyl group of a side branch interferes with crystallization using an aromatic dimethylidine compound.

On the other hand, the light emitting material which introduce | transduced silicon into the main chain is also developed. The introduction of silicon can have several excellent properties. First of all, introduction of silicon imparts steric hindrance between molecules, thereby preventing packing between molecules and suppressing concentration quenching, thereby increasing luminous efficiency. Poly (para-phenylenevinylene) derivatives synthesized by introducing such silicones have also been known ( Chem. Mater. , 6, 171, 1994, J. Electron. Mater. , 23, 453, 1994). The silicon here acts as an electron donor group or serves to increase the electron bandgap. Also disclosed is a technique in which an alkylsilyl group is introduced as a derivative of poly (para-phenylenevinylene) to increase solubility and bandgap ( J. Am. Chem. Soc. , 124, 22, 2002). Korean Patent Laid-Open Publication No. 2001-18900 discloses an electroluminescent polymer having excellent interfacial properties with an electrode and thin film formation ability by introducing phenyl silicon.

Silicon-based materials lower the lower unoccupied molecular orbital (LUMO) and have a relatively short π-conjugation length due to the d-orbital involvement of the elemental silicon, thus increasing the band gap to create blue light emitting materials ( Macromolecules Vol. 35 , No. 18, 2002). In addition, the organosilicon compound having an aromatic chromophore has excellent charge transporting ability, thereby making it possible to make a highly effective organic electroluminescent device ( Organometallics , 22, 321, 2003). It also acts as an electron transporting material in π-electronic systems containing silicon ( Appl. Phys. Lett. , 74, 865, 1999).

Fuji Photo Film, US Patent No. 6,307,083 discloses a blue light emitting monomolecular material having a silane and a vinyl group. Meanwhile, blue light emitting compounds have also been developed by introducing phenylsilicon and triphenylamine into oxadiazoles ( Ade. Mater. , 13, No. 21, 1636, 2001, J. Am. Chem. Soc. , 124, 6469). -6479, 2002).

The present inventors intend to disclose a material for an organic light emitting device in which a novel compound including silicon having strong electron affinity and an isol amine derivative having excellent hole transporting ability is introduced to increase luminous efficiency.

It is an object of the present invention to provide organosilane-based compounds suitable for use as blue light emitting materials.

Another object of the present invention is to provide a light emitting material including an organosilane compound having excellent blue light emission efficiency.

Yet another object of the present invention is to provide an electron transport material comprising an organosilane compound.

Another object of the present invention is to provide a hole transport material comprising an organosilane-based compound.

Another object of the present invention is to provide a hole blocking material or an electron transporting material in a phosphorescent device.

Still another object of the present invention is to provide an organic EL device made of a material containing an organosilane compound.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

The organosilane-based compound according to the present invention has a structure of formula (I):

[Formula 1]

N is an integer of 1 to 4, m is an integer of 1 to 2, and l is an integer of 0 to 1; Ar ₁ is selected from the group consisting of phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl and derivatives thereof, Ar ₂ is phenyl, naphthalene, anthracene, thiophene, Oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and derivatives thereof, and Ar ₃ and Ar ₄ are Phenyl, naphthalene and derivatives thereof, and R 1 and R 2 are each hydrogen, fluorine (F), trifluoro methyl (CF ₃ ), cyanide (CN), methoxy (OMe), methyl ( CH ₃ ) and vinylphenyl.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

The silane compound according to the present invention has a structure represented by the following Chemical Formula 1.

N is an integer of 1 to 4, m is an integer of 1 to 2, and l is an integer of 0 to 1; Ar ₁ is selected from the group consisting of phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl and derivatives thereof, Ar ₂ is phenyl, naphthalene, anthracene, thiophene, Oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and derivatives thereof, and Ar ₃ and Ar ₄ are Phenyl, naphthalene and derivatives thereof, and R 1 and R 2 are each hydrogen, fluorine (F), trifluoro methyl (CF ₃ ), cyanide (CN), methoxy (OMe), methyl ( CH ₃ ) and vinylphenyl.

Specific examples of Ar _{1 in} the present invention include compounds having the structure:

In the above, R is selected from the group consisting of an aryl group having 6 to 20 carbon atoms having an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms having an alkoxy group having 1 to 20 carbon atoms.

Specific examples of Ar ₂ include compounds having the following structure:

In the above, R is selected from the group consisting of an aryl group having 6 to 20 carbon atoms having an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms having an alkoxy group having 1 to 20 carbon atoms.

The silane-based compound according to the present invention can lower the lower unoccupied molecular orbital (LUMO) by introducing silicon, and has a relatively short π-conjugation length because the silicon element is involved in the d-orbital. In addition, the silyl derivative is suitable for use as a light emitting device that emits blue light by acting as an electron pulling body and increasing a band gap. Furthermore, by introducing silicon, it can act as an effective electron transport material in a π-electronic system containing silicon, and at the same time, the hole transport ability of arylamine, carbazole, fluorene, etc. By introducing a superior material it can act as a hole transport material.

In the silane compound according to the present invention, since Ar ₁ and Ar ₂ and the tetravalent silicon compound of Chemical Formula 1 are not all present on the same plane, the luminescence efficiency is increased by preventing concentration quenching by preventing packing between molecules. It plays a role. In addition, the phenyl silicon introduced in the present invention improves the interfacial properties with the electrode and the thin film forming ability. In addition, by increasing the planarity by introducing naphthalene and anthracene in the amine of Formula 1, it is possible to increase the conjugation length. In addition, by introducing fluorene or carbazole in addition to the amine at the terminal, the hole transporting ability can be improved to act as a hole transporting material, and there is a possibility of use as a host of a blue light emitting material. In order to improve the electron transport ability, by introducing a triazine, which is an electron deficient group, at the end, it may also act as an electron transport material or a hole blocking material. In addition, by introducing thiophene instead of phenyl in the silicon, the conjugation length can be increased by reducing the band gap, and the energy levels of HOMO and LUMO can be adjusted according to the reduction of the band gap.

Below is a look at a specific example of the silane compound according to the present invention.

In Formula 1, when L is 0, m is 1 and n is 1, and Ar ₁ is a phenyl group, it has the structure of Formula 1-1.

[Formula 1-1]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 2 and n is 1, and Ar ₁ is a phenyl group, it has the structure of Formula 1-2.

[Formula 1-2]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 1 and n is 2, and Ar ₁ is a phenyl group, it has the structure of Formula 1-3.

[Formula 1-3]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 2 and n is 2, and Ar ₁ is a phenyl group, it has the structure of Formula 1-4.

[Formula 1-4]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 1 and n is 3, and Ar ₁ is a phenyl group, it has the structure of Formula 1-5.

[Formula 1-5]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 2 and n is 3, and Ar ₁ is a phenyl group, it has the structure of Formula 1-6.

[Formula 1-6]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 1 and n is 4, and Ar ₁ is a phenyl group, it has the structure of Formula 1-7.

[Formula 1-7]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

In Formula 1, when L is 0, m is 2 and n is 4, and Ar ₁ is a phenyl group, it has the structure of Formula 1-8.

[Formula 1-8]

Ar ₂ in the above formula is phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and these It is selected from the group consisting of derivatives of.

On the other hand, when in the formula 1 l is 1, n is 1, it has the structure of formula 1-9.

[Formula 1-9]

In Formula 1, when 1 is 1 and n is 2, it has the structure of Formula 1-10.

[Formula 1-10]

In Formula 1, when 1 is 1 and n is 3, it has the structure of Formula 1-11.

[Formula 1-11]

In Formula 1, when 1 is 1 and n is 4, it has the structure of Formula 1-12.

[Formula 1-12]

Specific examples of the silane compound of the present invention include, but are not limited to, compounds having the following structure:

Meanwhile, the branched intermediate used in the silane compound according to the present invention may have the following structure.

The organosilane compound of the present invention may be used as a light emitting material, a charge transport material, or a hole transport material in an organic electroluminescent device. In particular, the organosilane compound of the present invention can be used not only as an electron transporting material in a fluorescent device, but also plays a role of hole blocking in a phosphorescent device, and can be used as an electron transporting material.

Specifically, in the organic electroluminescent device comprising an anode, a cathode and an organic film between the anode and the cathode, the organic film is a phosphorescent host material, hole blocking material, electron transport material, hole It can be used as a blocking material and an electron transporting material.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example

Example 1: Preparation of Organosilane Compound I

Preparation of Bis- (4-Bromophenyl) -Diphenyl Silane

As shown in Scheme 1, 5 g (21.2 mol) of dibromobenzene was dissolved in ether, the temperature was lowered, n-BuLi was added thereto, and dichlorodiphenylsilane was added thereto to react at room temperature. After the reaction was completed, the reaction was extracted with ether and then the solvent was removed under reduced pressure. The product was separated into a column and then dried by filtration under reduced pressure. 49% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.54-7.5 (m, 8H, Ar-H), 7.45 (2H, Ar-H), 7.40-7.35 (m, 8H, Ar-H). IR (KBr, cm ⁻¹ ): 1568, 1477-1376, 1110, 810, 727, 698. MS (EI) (calcd for C ₂₄ H ₁₈ Br ₂ Si, 494; Found: 494).

Preparation of (4-bromo-phenyl) -diphenyl-amine

As shown in Scheme 2 below, 20.3 g (0.12 mol) of diphenylamine, 13.8 g of Na-t-BuO, 0.67 g of palladium acetate, 28.3 g of dibromobenzene, and 1.83 g of triosotorylphosphine were refluxed in toluene for 24 hours. I was. 34% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.3-7.2 (m, 8H, Ar-H), 7.00-6.9 (m, 6H, Ar-H). IR (KBr, cm ⁻¹ ): 1578, 1485, 1283, 1267, 823, 757, 698. MS (EI) (calcd for C ₁₈ H ₁₄ BrN, 324; Found: 324).

Preparation of Diphenylamino-phenyl-4-boronic Acid

7 g (21.6 mmol) of (4-bromo-phenyl) -diphenyl-amine and tetrahydrofuran (THF) were added, the temperature was lowered to low temperature, n-BuLi was added, and trimethylborate was added thereto. . After cooling the reaction, it was poured into diluted hydrochloric acid solution and stirred for 30 minutes. After extraction with methyl chloride, the solvent was removed under reduced pressure, and ether was added to obtain diphenylamino-phenyl-4-boronic acid. 56% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.0 (d, 6H, Ar-H), 6.62-6.46 (d, 8H, Ar-H), 2.0 (s, 2H, B- (OH) ₂ ). IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695. MS (EI) (calcd for C ₁₈ H ₁₆ BNO ₂ , 289; Found: 289).

Preparation of Organosilane-Based Compound I

As shown in Scheme 4 below, in 1.5 g (3 mmol) of bis- (4-bromophenyl) -diphenyl silane prepared by the above method, diphenylamino-phenyl-4-boronic acid, 2M of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. It was extracted with methyl chloride to remove the solvent, and then columned with hexane. 66% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.68 (4H, Ar-H), 7.58 (4H, Ar-H), 7.36 (6H, Ar-H), 7.23 (4H, Ar-H), 7.01 (8H , Ar-H), 6.62 (4H, Ar-H), 6.52 (4H, Ar-H), 6.46 (8H, Ar-H). MS (EI) (calcd for C ₆₀ H ₄₆ N ₂ Si, 822.34; Found: 823).

UV and PL intensities of the organosilane compound I prepared as described above are shown in FIG. 1, and the CIE color coordinates are shown in FIG. 2.

Example 2: Preparation of Organosilane Compound II

Preparation of Tris (4-bromo-phenyl) -phenyl-silane

As shown in Scheme 5, 9.8 g (35.4 mmol) of dibromobenzene was dissolved in ether, the temperature was lowered, n-BuLi was added, and trichlorophenylsilane was added to react at room temperature. After the reaction, the reaction was extracted with ether and the solvent was removed under reduced pressure. The product was separated by column and then dried by filtration under reduced pressure. 54% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.31-6.95 (m, 17H, Ar-H). IR (KBr, cm ⁻¹ ): 3065, 1569, 1478, 1427, 1110, 1064, 1009, 809, 727, 698.

Preparation of Organosilane Compound II

Diphenylamino-phenyl-4-boronic acid prepared in Example 1 to 1.5 g (2.64 mmol) of tris (4-bromo-phenyl) -phenyl-silane prepared as above, as shown in Scheme 6 below. , 2 moles of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexanes. 50% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.68 (2H, Ar-H), 7.60 (4H, Ar-H), 7.58 (6H, Ar-H), 7.36 (3H, Ar-H), 7.23 (6H , Ar-H), 7.01 (12H, Ar-H), 6.62 (6H, Ar-H), 6.52 (6H, Ar-H), 6.46 (12H. Ar-H). MS (EI) (calcd for C ₇₈ H ₅₉ N ₃ Si, 1065.45; Found: 1066).

The UV and PL intensities of the organosilane compounds II prepared as described above are shown in FIG. 3, and the CIE color coordinates are shown in FIG. 4.

Example 3: Preparation of Organosilane Compound III

Preparation of 4-bromophenyl-triphenyl silane

As shown in Scheme 7 below, 4 g (17 mmol) of dibromobenzene was dissolved in ether, the temperature was lowered, n-BuLi was added thereto, and trichlorophenylsilane was added thereto, followed by reaction at room temperature. After the reaction was completed, the reaction was extracted with ether, and the solvent was removed under reduced pressure. The product was separated into a column and then dried by filtration under reduced pressure. 66% yield ¹ H-NMR (CDCl ₃ , ppm): 7.54-7.5 (m, Ar-H), 7.45 (Ar-H), 7.40-7.35 (m, Ar-H). IR (KBr, cm ⁻¹ ): 1568, 1477-1376, 1110, 810, 727, 698. MS (EI) (calcd for C ₂₄ H ₁₉ BrSi, 414; Found: 414).

Preparation of Organosilane Compound III

Diphenylamino-phenyl-4-boronic acid prepared in Example 1 in 5 g (12 mmol) of tris (4-bromo-phenyl) -phenyl-silane prepared as above, as shown in Scheme 8 below. , 2 moles of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexanes. 50% yield ¹ H-NMR (CDCl ₃ , ppm): 7.68 (Ar-H), 7.60 (Ar-H), 7.58 (Ar-H), 7.36 (Ar-H), 7.23 (Ar-H), 7.01 (Ar-H), 6.62 (Ar-H), 6.52 (Ar-H), 6.46 (Ar-H). MS (EI) (calcd for C ₄₂ H ₃₃ NSi, 579.24 Found: 579).

UV and PL intensities of the organosilane compound III prepared as described above are shown in FIG. 5.

Example 4: Preparation of Organosilane Compound IV

Preparation of (4-bromophenyl) -naphthalen-1-yl-phenyl amine

As shown in Scheme 9 below, 30 g (0.14 mol) of naphthyl-phenylamine, 15.8 g of Na-t-BuO, 0.77 g of palladium acetate, 32.3 g of dibromobenzene, and 2 g of triosotorylphosphine in toluene for 24 hours. At reflux. 32% yield ¹ H-NMR (CDCl ₃ , ppm): 7.3-7.2 (m, 8H, Ar—H), 7.00-6.9 (m, 6H, Ar—H). IR (KBr, cm-1): 1578, 1485, 1283, 1267, 823, 757, 698. MS (EI) (calcd for C ₂₂ H ₁₆ BrN, 373.05 Found: 373).

Preparation of Naphthyl-phenyl Amino-phenyl-4-boronic Acid

6 g (21.4 mmol) of (4-bromo-phenyl) -naphthalen-1-yl-phenyl-amine and tetrahydrofuran (THF) were added, the temperature was lowered to low temperature, and then n-BuLi was added. Trimethylborate was added. After cooling the reaction, it was poured into diluted hydrochloric acid solution and stirred for 30 minutes. After extraction with methyl chloride, the solvent was removed under reduced pressure, and ether was added to obtain diphenylamino-phenyl-4-boronic acid. 43% yield ¹ H-NMR (CDCl ₃ , ppm): 7.0 (d, 6H, Ar-H), 6.62-6.46 (d, 8H, Ar-H), 2.0 (s, 2H, B- (OH) 2 ). IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695. MS (EI) (calcd for C ₂₂ H ₁₈ BNO ₂ , 339.149; Found: 339).

Preparation of Organosilane Compound IV

Naphthyl-phenyl amino-phenyl-4-boronic acid prepared in Example 4 to 5 g (12 mmol) of tris (4-bromo-phenyl) -phenyl-silane prepared as above, as shown in Scheme 11 below. Acid, 2 moles of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexanes. 60% yield ¹ H-NMR (CDCl ₃ , ppm): 7.68 (Ar-H), 7.60 (Ar-H), 7.58 (Ar-H), 7.36 (Ar-H), 7.23 (Ar-H), 7.01 (Ar-H), 6.62 (Ar-H), 6.52 (Ar-H), 6.46 (Ar-H). MS (EI) (calcd for C ₄₆ H ₃₅ NSi, 629.25 Found: 629).

UV and PL intensities of the organosilane compound IV prepared as described above are shown in FIG. 6.

Example 5: Preparation of Organosilane Compound V

Preparation of (4'-bromobiphenyl-4-yl) -diphenyl amine

As shown in Scheme 12, 30.46 g (0.18 mol) of diphenylamine, 20.8 g of Na-t-BuO, 1 g of palladium acetate, 56.16 g of dibromobenzene, and 2.47 g of triosotorylphosphine were refluxed in toluene for 24 hours. I was. 33% yield ¹ H-NMR (CDCl ₃ , ppm): 7.3-7.2 (m, 8H, Ar—H), 7.00-6.9 (m, 6H, Ar—H). IR (KBr, cm ⁻¹ ): 1578, 1485, 1283, 1267, 823, 757, 698. MS (EI) (calcd for C ₂₄ H ₁₈ BrN, 399.06 Found: 399).

delete

Preparation of diphenyl-amino-biphenyl-4-boronic acid

17 g (42.6 mmol) of (4'-bromobiphenyl-4-yl) -diphenyl amine and tetrahydrofuran (THF) were added, the temperature was lowered to low temperature and then n-BuLi was added. Borate was added. After cooling the reaction, it was poured into diluted hydrochloric acid solution and stirred for 30 minutes. After extraction with methyl chloride, the solvent was removed under reduced pressure, and ether was added to obtain diphenylamino-biphenyl-4-boronic acid. 49% yield ¹ H-NMR (CDCl ₃ , ppm): 7.0 (d, 6H, Ar-H), 6.62-6.46 (d, 8H, Ar-H), 2.0 (s, 2H, B- (OH) 2 ). IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695. MS (EI) (calcd for C ₂₄ H ₂₀ BNO ₂ , 365.16 Found: 365).

Preparation of Organosilane Compound V

Naphthyl-phenyl amino-phenyl-4-boronic acid prepared in Example 4 to 5 g (12 mmol) of tris (4-bromo-phenyl) -phenyl-silane prepared as above, as shown in Scheme 14 below. Acid, 2 moles of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexane. 60% yield ¹ H-NMR (CDCl ₃ , ppm): 7.68 (Ar-H), 7.60 (Ar-H), 7.58 (Ar-H), 7.36 (Ar-H), 7.23 (Ar-H), 7.01 (Ar-H), 6.62 (Ar-H), 6.52 (Ar-H), 6.46 (Ar-H). MS (EI) (calcd for C ₄₈ H ₃₇ NSi, 655.27 Found: 655)

UV and PL intensities of the organosilane compound V prepared as described above are illustrated in FIG. 7.

Example 6: Preparation of Organosilane Compound VI

Preparation of Phenyl Boronic Acid Triphenyl Silane

After adding 8.3 g (0.02 mol) of bromophenyl-triphenyl silane synthesized in Example 3 and Tetrahydrofuran (THF), the temperature was lowered to low temperature, and then n-BuLi was added. Added. After cooling the reaction, it was poured into diluted hydrochloric acid solution and stirred for 30 minutes. After extraction with methyl chloride, the solvent was removed under reduced pressure, and ether was added to obtain phenyl boronic acid triphenyl silane. 50% yield ¹ H-NMR (CDCl ₃ , ppm): 7.0 (d, 6H, Ar-H), 6.62-6.46 (d, 8H, Ar-H), 2.0 (s, 2H, B- (OH) 2 ). IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695.MS (EI) (calcd for C ₂₄ H ₂₁ BO ₂ Si, 380.14 Found: 380)

Preparation of Bromonafnil-Diphenyl Amine

As shown in Scheme 16, 13.5 g (0.08 mol) of diphenylamine, 9.3 g of Na-t-BuO, 0.45 g of palladium acetate, 22.8 g of dibromobenzene, and 1.2 g of triosotorylphosphine were added to toluene for 24 hours. It was refluxed. 27% yield ¹ H-NMR (CDCl ₃ , ppm): 7.3-7.2 (m, 8H, Ar—H), 7.00-6.9 (m, 6H, Ar—H). IR (KBr, cm ^-1 ): 1578, 1485, 1283, 1267, 823, 757, 698.MS (EI) (calcd for C ₂₂ H ₁₆ BrN, 373 Found: 373)

Preparation of Organosilane Compound VI

5.5 g (12 mmol) of the pheniboronic acid triphenyl silane prepared as above was prepared as described in Scheme 17 below, 2 mol of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexanes. 93% yield ¹ H-NMR (CDCl ₃ , ppm): 7.68 (Ar-H), 7.60 (Ar-H), 7.58 (Ar-H), 7.36 (Ar-H), 7.23 (Ar-H), 7.01 (Ar-H), 6.62 (Ar-H), 6.52 (Ar-H), 6.46 (Ar-H). MS (EI) (calcd for C ₄₆ H ₃₅ NSi, 629.3 Found: 629).

UV and PL intensities of the organosilane compound VI prepared as described above are shown in FIG. 8.

Example 7: Preparation of Organosilane Compound (VIII)

Preparation of 4-bromo-N-benzylideneaniline

22.2 g (0.12 mol) of 4-bromobenzaldehyde and 13.4 g (0.12 mol) of aniline were dissolved in chloroform and subjected to azeotropic distillation for 7 hours. 99% yield IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695.MS (EI) (calcd for C ₁₃ H ₁₀ BrN, 259 Found: 259)

Preparation of 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine

25.9 g (0.1 mol) of 4-bromo-N-benzylideneaniline and 24 g (0.2 mol) of benzamidine prepared as described above were dissolved in anhydrous dimenylformamide and reacted at 80 ° C. for 24 hours. After cooling the reaction, the precipitate was filtered to give 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine. 5% yield IR (KBr, cm ⁻¹ ): 1589, 1491, 1374-1277, 829, 725, 695.MS (EI) (calcd for C ₂₁ H ₁₄ BrN ₃ , 387.04 Found: 387)

Preparation of organosilane compound VII

3.6 g (7.75 mmol) and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5 of pheniboronic acid triphenyl silane prepared in Example 6 as shown in Scheme 20 below. Triazine, 2 moles of K ₂ CO ₃ , Pd (PPh ₃ ) ₄ and toluene were added and refluxed for 10 hours. Extraction with methyl chloride and removal of solvent followed by column with hexanes. 63% yield ¹ H-NMR (CDCl ₃ , ppm): 7.68 (Ar-H), 7.60 (Ar-H), 7.58 (Ar-H), 7.36 (Ar-H), 7.23 (Ar-H), 7.01 (Ar-H), 6.62 (Ar-H), 6.52 (Ar-H), 6.46 (Ar-H). IR (KBr, cm-1): 1589, 1491, 1374-1277, 829, 725, 695. MS (EI) (calcd for C ₄₅ H ₃₃ N ₃ Si, 643.24 Found: 643).

The UV and PL intensities of the organosilane compound VII prepared as described above are shown in FIG. 9.

As can be seen from Figures 1 to 9, the silane compound according to the present invention is suitable for showing blue light emission.

Example 8 Preparation of Blue Organic Electroluminescent Device Using Silane Compound I as Emission Layer Material

As shown in FIG. 10, the ITO electrode 2 is formed on the glass substrate 1, and then subjected to UV-ozone cleaning or oxygen plasma cleaning. A phthalocyanine copper complex (CuPc) having a structure was deposited to a thickness of 100 kHz. In the hole transport layer (3), NPD (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine) having a structure represented by the following formula (2-2) was 400 mm thick. After the deposition, the silane compound I prepared in Example 1 was deposited to a thickness of 350 Å to form a light emitting layer (4).

Subsequently, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenathroline) having a structure represented by the following Chemical Formula 2-3 was deposited as 200 as the hole blocking layer, and then, as the electron transport layer 5, Alq3 (tris- (8-hydroxyquinoline) aluminum (III)) having a structure of Chemical Formula 2-4 was vacuum deposited to a thickness of 300 mm 3.

Thereafter, an Al: Li layer 6 was vacuum-deposited on the upper portion to form an aluminum lithium electrode having a thickness of 1000 kW, thereby manufacturing a blue organic electroluminescent device.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

Example 9 Fabrication of Blue Organic Electroluminescent Device Using Silane Compound II as Emission Layer Material

A blue organic electroluminescent device was manufactured in the same manner as in Example 8, except that the silane compound II obtained in Example 2 was used to form the emission layer 4.

Example 10 Fabrication of Green Organic Electroluminescent Device Using Silane-Based Compound I as Electron Transport Layer Material

After forming the ITO electrode (2) on the glass substrate (1), and then subjected to UV-ozone cleaning or oxygen plasma cleaning, the CuPc represented by the formula (2-1) to the hole injection layer on top of this to deposit a thickness of 100 Å I was. The NPD represented by Chemical Formula 2-2 was deposited to a thickness of 400 GPa as the hole transport layer 3, and then Alq 3 represented by Chemical Formula 2-4 was deposited to a thickness of 300 GPa to form the emission layer 4.

Subsequently, the silane-based compound I obtained in Example 1 was deposited to a thickness of 300 kHz to form an electron transport layer.

Thereafter, Al: Li was vacuum-deposited on the organic layer to form an aluminum lithium lithium electrode having a thickness of 1000 kHz, thereby manufacturing a green organic electroluminescent device using the silane compound I as the electron transport layer 5.

Example 11 Fabrication of Green Organic Electroluminescent Device Using Silane-Based Compound II as Electron Transport Layer Material

When forming the electron transport layer, green organic electrons using the silane compound II as the electron transport layer 5 were carried out in the same manner as in Example 10 except that the silane compound II was used instead of the silane compound I. A light emitting device was prepared.

Example 12 Fabrication of Green Organic Electroluminescent Device Using Silane-Based Compound I as a Hole Transport Layer Material

After forming the ITO electrode 2 on the glass substrate 1, and then subjected to UV-ozone cleaning or oxygen plasma cleaning, the CuPc represented by the formula (2-1) was deposited to a thickness of 100 Å as a hole injection layer thereon. . The silane-based compound I was deposited to have a thickness of 400 mW using the hole transport layer 3, and then Alq3 represented by Formula 4 was deposited at a thickness of 600 mW to form a light emitting layer.

Thereafter, Al: Li was vacuum-deposited on the organic layer to form an aluminum lithium lithium electrode 6 having a thickness of 1000 kW, thereby manufacturing a green organic electroluminescent device using the silane compound 1 as the hole transport layer 3.

Example 13: Fabrication of Green Organic Electroluminescent Device Using Silane-Based Compound II as Hole Transport Layer Material

In the case of forming the hole transport layer 3, the same procedure as in Example 12 was carried out except that the silane compound II was used instead of the silane compound I, and thus the silane compound II was used as the hole transport layer 3. A green organic electroluminescent device was manufactured.

Example 14 Preparation of Phosphorescent Green Organic Electroluminescent Device Using Silane-Based Compound I as a Host

After forming the ITO electrode (2) on the glass substrate (1), and then subjected to UV-ozone cleaning or oxygen plasma cleaning, the CuPc represented by the formula (2-1) as a hole injection layer on the top was deposited to a thickness of 100 Å . Here, the silane-based compound I was deposited to a thickness of 400 으로 with the hole transport layer 3, and the silane-based compound I was used as a dopant as a host. Ir (ppy) 3 (tris (2-phenylpyridine) iridium (III) ) Was co-deposited to form a light emitting layer 4 having a thickness of 300 kHz.

Subsequently, 200 Å of BCP represented by Chemical Formula 2-3 was deposited as the hole blocking layer, and Alq3 represented by the Chemical Formula 2-4 was vacuum deposited to 300 Å thickness using the electron transport layer 5.

Thereafter, Al: Li was vacuum-deposited on the organic layer to form an aluminum lithium electrode 6 having a thickness of 1000 kW, thereby preparing a phosphorescent green organic electroluminescent device using the silane compound I as a host.

Example 15 Fabrication of Phosphorescent Green Organic Electroluminescent Device Using Silane Compound II as a Host

Phosphorescent green organic electroluminescent device using silane-based compound II as a host in the same manner as in Example 14 except that silane-based compound II was used instead of silane-based compound I as the host. Was prepared.

Example 16: Preparation of Blue Organic Electroluminescent Device Using Silane Compound V as Emission Layer (Dopant) Material

After forming the ITO electrode (2) on the glass substrate (1), and then subjected to UV-ozone cleaning or oxygen plasma cleaning, the CuPc represented by the formula (2-1) to the hole injection layer on top of this to deposit a thickness of 100 Å I was. After depositing the NPD represented by the formula (2-2) to a thickness of 400 으로 with a hole transport layer (3), the silane-based compound V prepared in Example 5 to 4 wt% in DPVBi represented by the formula (2-5) The light emitting layer 4 was formed by evaporating to a thickness of 350 kHz.

Subsequently, Alq3 represented by Chemical Formula 2-4 was vacuum deposited to a thickness of 300 으로 with an electron transport layer 5 on the top.

Thereafter, Al: Li was vacuum-deposited on the organic layer to form a 1000 μm thick aluminum lithium electrode, thereby manufacturing a blue organic electroluminescent device.

Example 17 Preparation of Blue Organic Electroluminescent Device Using Silane Compound VI as Emission Layer (Dopant) Material

In the case of using the blue light emitting material dopant, blue light emitting organic electroluminescence using the silane-based compound VI as a dopant was carried out in the same manner as in Example 16 except that the silane-based compound VI was used instead of the silane-based compound V as the dopant. The device was manufactured.

The results carried out in Example 16 and Example 17 are shown in Table 1 below.

EL max Color coordinates Luminance efficiency Example 16 465 (0.15, 0.18) 3024 cd / m ² 3.39 cd / A Example 17 465 (0.15, 0.19) 3250 cd / m ² 3.25 cd / A

Example 18 Fabrication of Green Phosphorescent Electroluminescent Device Using Silane-Based Compound VII as Hole Blocking Material

After forming the ITO electrode (2) on the glass substrate (1), and then subjected to UV-ozone cleaning or oxygen plasma cleaning, a copper injecting layer on top of the CuPc (copper phthlocyanide) was deposited to a thickness of 100 Å. Here, the NPD represented by Chemical Formula 2-2 was deposited with a hole transport layer 3 to a thickness of 400 Å, and then CBP was used as a dopant as a host.Ir (ppy) 3 (tris (2-phenylpyridine) iridium ( III)) was simultaneously deposited to form a light emitting layer 4 having a thickness of 300 kHz.

Subsequently, 100 Å of the silane-based compound VII was deposited using the hole blocking layer, and Alq3 represented by Chemical Formula 2-4 was vacuum deposited to a thickness of 300 Å using the electron transport layer 5.

Thereafter, Al: Li was vacuum-deposited on the organic layer to form a 1000 Å thick aluminum-lithium electrode 6 to prepare a phosphorescent green organic electroluminescent device.

Example 19 Fabrication of Green Phosphorescent Electroluminescent Device Using Silane-Based Compound VII as Hole Blocking Material and Electron Transporting Material

When the silane compound VII is used as the hole blocking material and the electron transporting material, the silane compound VII is used as the hole blocking material and the electron transporting material instead of Alq3 represented by Formula 2-4 as the hole blocking material. A green phosphorescent organic electroluminescent device was manufactured according to the same method as Example 18 except for using the same as.

Comparative Example 1: Preparation of phosphorescent green organic electroluminescent device

A green phosphorescent organic electroluminescent device was manufactured in the same manner as in Example 18, except that the BAlq compound was used instead of the silane compound as the hole blocking material.

The results performed in Examples 18-19 and Comparative Example 1 are shown in Table 2 below.

EL max Color coordinates Luminance efficiency Example 18 515 (0.26, 0.64) 16280 cd / m ² 25.38 cd / A Example 19 515 (0.26, 0.63) 15680 cd / m ² 26.34 cd / A Comparative Example 515 (0.27, 0.64) 12160 cd / m ² 11.80 cd / A

As shown above, the silane compound VII can be used not only as an electron transporting material in the fluorescent device, but also serves as a hole blocking function in the phosphorescent device, and can be used as an electron transporting material.

The present invention provides an organic material comprising an organic silane compound suitable for use as a blue light emitting material and a light emitting material including an organic silane compound having excellent blue light emission efficiency, an electron transporting material and a hole transporting material, and a material containing an organosilane-based compound. It has the effect of providing the EL device.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (9)

An organosilane compound having a structure represented by Formula 1 below: [Formula 1]

N is an integer of 1 to 4, m is an integer of 1 to 2, l is a natural number 1; Ar ₁ is selected from the group consisting of phenyl, naphthalene, anthracene, thiophene, oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl and derivatives thereof, Ar ₂ is phenyl, naphthalene, anthracene, thiophene, Oxadiazole, carbazole, fluorene, diphenyl, vinylphenyl, 2,4,6-triphenyl-1,3,5-triazine and derivatives thereof, and Ar ₃ and Ar ₄ are Phenyl, naphthalene and derivatives thereof, and R 1 and R 2 are each hydrogen, fluorine (F), trifluoro methyl (CF ₃ ), cyanide (CN), methoxy (OMe), methyl ( CH ₃ ) and vinylphenyl. A light emitting material comprising the organosilane compound of claim 1. An organic electroluminescent device comprising an anode, a cathode and a light emitting layer, wherein the light emitting layer comprises the light emitting material of claim 2. An organic electroluminescent device comprising an anode, a cathode and a charge transport layer, wherein the charge transport layer comprises an electron transport material comprising the compound of claim 1. An organic electroluminescent device comprising an anode, a cathode and a hole transport layer, wherein the hole transport layer comprises a hole transport material comprising the compound of claim 1. An organic electroluminescent device comprising an anode, a cathode, and an organic film between the anode and the cathode, wherein the organic film contains the compound of claim 1 as a host material for phosphorescence. An organic electroluminescent device comprising an anode, a cathode and an organic film between the anode and the cathode, wherein the organic film comprises the compound of claim 1 as a hole blocking material for phosphorescence. An organic electroluminescent device comprising an anode, a cathode and an organic film between the anode and the cathode, wherein the organic film contains the compound of claim 1 as an electron transporting material of phosphorescence. An organic electroluminescent device comprising an anode, a cathode and an organic film between the anode and the cathode, wherein the organic film comprises the compound of claim 1 as a hole blocking material and an electron transporting material for phosphorescence device.

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