TWI391365B - Asymmetric trivalent anthracene and organic electroluminescent devices containing asymmetric trivalent anthracene - Google Patents

Description

Asymmetric trisubstituted fluorene and organic electroluminescent device containing asymmetric trisubstituted fluorene

This invention relates to an asymmetric trisubstituted terpenoid. Due to the good stability of such terpenoids, one of the applications of such materials is as the main illuminant of organic electroluminescent diodes. The present invention also relates to an organic electroluminescent device and an organic electroluminescent device using such a terpene compound, wherein the organic electroluminescent device can be a display.

Since Dr. Deng Qingyun from Keda Company of the United States has published a low-voltage organic electroluminescent device (CWTang, Applied Physics Letters, Vol. 51, p. 913, 1987), it has caused the application of organic compounds in organic electroluminescent devices. In the research boom, an organic electroluminescent device is sandwiched between two electrodes (anode and cathode) via an organic medium to form a sandwich structure. Wherein, the anode is a metal or a conductive compound having a high work function, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like, transparent metal oxide Or a thin film transistor (TFT) substrate such as poly-Si or amorphous germanium (a-Si); and the cathode is a metal or conductive compound having a low work function, such as gold (Au), Aluminum (Al), indium (In), magnesium (Mg), calcium (Ca) or similar metals, alloys, etc.; and at least one of the two electrodes is transparent or translucent so that the emitted light can penetrate efficiently The organic medium may be composed of several layers depending on the case, wherein the thickness of each layer is not strictly limited, and is usually between 5 nm and 5 μm, and representatively, three layers of organic molecular layers are sandwiched between the two electrodes, and the three layers include An electron transport layer, a light emitting layer and a hole transport layer.

Usually, in order to reduce the driving voltage, a hole or an electron injecting layer is additionally added, or a light hole or an electron blocking layer is added to improve the luminous efficiency, and an organic electroluminescent device composed of four to six organic molecular layers is formed; wherein the electron injecting layer is formed. Usually, it may be an alkali metal halide or a nitrogen or oxygen base metal chelate such as lithium fluoride, 8-quinolinolato lithium (Liq), etc.; and the hole injection layer may be generally derived from metal phthalocyanine. , stellate polyamine derivatives, polyaniline derivatives (Y. Yang et al, Syn. Met., 1997, 87, 171), perfluorinated, cerium oxide (SiO ₂ ) (ZBDeng) Et al, Appl. Phys. Lett., 1997, 74, 2227) or hole transport material doped oxides, etc., for example: copper phthalocyanine (CuPc) (SA Van Slyke et al, Appl. Phys. Lett., 1996, 69) , 2160), MTDATA (Y. Shirota et al, Appl. Phys. Lett., 1994, 65, 807), TPD ⁺ SbCl ₆ ^- (A. Yamamori et al, Appl. Phys. Lett., 1998, 72, 2147), PEDOT-PSS (A. Elschner et al, Syn. Met., 2000, 111, 139), etc.; the electron transport layer may be a metal chelate containing nitrogen and oxygen (T. Sano et al, J. Mater. Chem., 2000, 10,157), evil An oxadiazole derivative, a perfluorinated polyaromatic ring derivative, an aromatic or heterocyclic substituted fluorene derivative, an oligothiophene derivative or benzimidazole ) derivatives, for instance: three 8-hydroxyquinoline aluminum (tris (8-quinolinolato) aluminum , Alq 3), polybutadiene (PBD) (N.Johansson et al, Adv.Mater, 1998,10. , 1136), PyPySiPyPy (M. Uchida et al, Chem. Mater., 2001, 13, 2680), BMB-3T (T. Noda et al, Adv. Mater., 1999, 11, 283), PF-6P (Y. Sakamoto et al, J. Amer. Chem. Soc., 2000, 122, 1832), TPBI (YTTao et al, Appl. Phys. Lett., 2000, 77, 933), etc.; hole transport layers are commonly used in organic photoconductive materials. The charge transport material consists of a triazole derivative, an oxadiazole derivative, an imidazole derivative, a phenylenediamine derivative, or the like. A star-shaped polyamine derivative, a spiro-linked molecular derivative or an arylamine derivative, for example, NPB or a derivative thereof (Y. Sato et al, Syn. Met., 2000) , 111, 25), PTDATA (Y.Shi Rota et al, Syn. Met., 2000, 111, 387), spiro-mTTB (U. Bach et al, Adv. Mater., 2000, 12, 1060) and the like. Since OLEDs have low driving voltage characteristics and have been verified to be applicable to full color flat panel displays, research on organic electroluminescent devices and materials has attracted worldwide attention and investment.

In order to improve the luminescent color, luminescence efficiency, luminescence stability, component lifetime and component fabrication method of the organic electroluminescent device, these improvements can be found in the approved U.S. Nos. 4,356,429, 4,539,507, 4,720,432, 4,885,211. , 5,151,629, 5,150,006, 5,141,671, 5,073,446, 5,061,569, 5,059,862, 5,059,861, 5,047,687, 4,950,950, 4,769,292, 5,104,740, 5,227,252, Patent Nos. 5,256,945, 5,069,975, 5,122,711, 5,366,811, 5,126,214, 5,142,343, 5,389,444, 5,458,977.

One of the ultimate goals of organic electroluminescent devices is on flat-panel displays. Therefore, a commercially viable component does not have good luminous efficiency, illuminating color, and commercial components and good components. life.

In the case of a blue light-emitting illuminant, the use of a phenyl hydrazine derivative is reported in Japanese Laid-Open Patent Publication No. Hei 8-012600. Although an anthracene derivative can be used as a blue light-emitting illuminant, the lifetime must be further improved. Another use of anthracene derivatives is the use of 9,10(2-naphthyl)anthracene (ADN) as an organic light-emitting device in a U.S. patent of U.S. Patent No. 5,935,721, issued toK. The blue light is the main illuminant, but ADN has a phenomenon of easy crystallization, and the life expectancy still needs further improvement. Kodak, WO 042668, discloses an asymmetric fluorene derivative of 9-nyl-10-diphenylphosphonium as a host material for the light-emitting layer. An axial disubstituted asymmetric compound having ruthenium as a skeleton is disclosed as a luminescent material in the 2007 Patent No. 20070152565. Japanese Laid-Open Patent Publication No. 2000-182776, U.S. Patent No. 2006154076, and U.S. Patent No. 2006043858 disclose various kinds of anthracene derivatives as a hole transporting material or a light emitting layer host material, but no actual synthesis has been made. The components are actually tested for their optoelectronic properties. A symmetric 2-methyl-9,10(2-naphthyl)anthracene (MADN) is disclosed in the National Publication No. 593630 as a blue light illuminator in an organic light-emitting device.

The present inventors synthesized an asymmetric trisubstituted anthracene derivative having a novel structure. In the derivative of position 2 of hydrazine, we found through experiments that the bromination of 2-methyl hydrazine is highly selective and high yield, and can further synthesize asymmetric trisubstituted fluorene compounds, and mass production of high purity. Organic electroluminescent materials. Therefore, the present invention is selected based on a 2-methylindole compound, and is described in detail in the synthesis examples.

The present invention provides a 2-methylindole compound having the novel formula (I):

Wherein X is a substituted or unsubstituted aryl group having an aromatic carbon number of 6 to 20 carbon atoms, and Y is a substituted or unsubstituted aryl group having an aromatic carbon number of 6 to 20 carbon atoms. Group, and X is not equivalent to Y.

The tri-substituted asymmetric specific structure of the fluorene structure compound represented by the compound of the formula (I) has been found to reduce the driving voltage, greatly improve the stability of the film, and improve the lifetime of the organic electroluminescent device. The asymmetric three-substitution of the novel structure An anthracene derivative can be used in a general organic electroluminescent device, and the anthraquinone compound of the present invention can be used as a luminescent material for an organic electroluminescent device.

The present invention provides an organic electroluminescent device comprising: a substrate; two electrodes, wherein one electrode is disposed on the substrate; and an organic layer disposed between the electrodes and including the formula (I) a 2-methylindole compound having a structure wherein X is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms of an aromatic group, and Y is an aromatic carbon number of 6 to 20 carbon atoms. A substituted or unsubstituted aryl group consisting of, and X is not equivalent to Y.

The following are some examples of preferred specific 2-methylindole compound materials in the present invention: B601, B602, B603, B604, B605, B606, B607, B608, B609, B610, B611, B612, and B613.

The organic layer sequentially includes a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, and an electron injection layer from the near substrate to the direction away from the substrate, and the organic layer has the formula (I) The 2-methyl fluorene compound of the structure is contained in the layered structure of the hole injection layer, the hole transport layer, the organic light-emitting layer, the electron transport layer or the electron injection layer.

Preferably, the 2-methyl fluorene compound having the structure of the formula (I) is contained in the organic light-emitting layer.

Preferably, the thickness of the organic layer is no more than 500 nm.

Wherein, the organic electroluminescent device can be a display.

Wherein, the organic electroluminescent device emits red, blue, green, yellow or white light.

The present invention can increase the efficiency of luminescence by mixing the organic layer in the organic electroluminescent device into the 2-methyl fluorene compound having the structure of the formula (I), and can be mixed with other compounds as red, blue, Green, yellow, white light luminescent materials, it can be applied to a variety of organic electroluminescent devices.

The invention can be applied to several different organic electroluminescent devices, and The necessary composition includes a cathode, an anode, and an organic layer disposed between the cathode and the anode, and the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

The most typical structure is shown in the first figure, wherein the organic electroluminescent device (10) comprises a substrate (11), an anode layer (12) disposed on the substrate (11), and a An organic layer (20) on the anode layer (12), a metal cathode layer (18) disposed on the organic layer (20), and a power source connected to the anode layer (12) and the cathode layer (18), respectively (19) The organic layer (20) includes a hole injection layer (13), a hole transport layer (14), and a light-emitting layer (15) stacked from the anode layer (12) to the cathode layer (18). , an electron transport layer (16) and an electron injection layer (17), when a voltage is applied to the anode layer (12) and the cathode layer (18), the holes generated by the anode layer (12) and the cathode layer (18) The generated electrons are injected into the organic layer (20) to be combined into excitons, and when the excitons are reduced to the ground state, light is scattered.

The materials used in these layers are described carefully below. First of all, it must be noted that in other aspects, the positions of the cathode layer and the anode layer may be interchanged such that the cathode layer is disposed on the substrate, or the substrate may be directly formed as an anode layer or a cathode layer, and further, stacked in layers. The total thickness of the organic layer is preferably equal to or less than 500 nm.

It is to be noted that those skilled in the art can make organic electroluminescent devices or devices using the compounds of the present invention in accordance with conventional techniques or prior art or prior art methods described in the present specification. Hereinafter, suitable materials for the structure of each element other than the hole injection layer in the organic electroluminescent device or device of the present invention will be described.

Substrate

The substrate may be translucent or opaque depending on the direction in which the light is radiated. If the emission of the emitted light (EL) is to be observed from the substrate, the substrate must have light penetration, in which case, generally Whether glass or organic materials are used; if the EL emission is to be observed through the upper electrode, the light passage of the lower support will become irrelevant, and thus it may be light penetration, light absorption or light reflection. The material of the substrate can be used without limitation to glass, plastic, semiconductor materials, ceramics, and circuit board materials. Of course, such an element structure must provide a light-permeable upper electrode.

anode

The conductive anode layer is typically fabricated on a substrate, and when EL radiation is observed through the anode, the anode must be transparent or substantially transparent to certain radiation; the materials used as the anode of the present invention can be generally common. Transparent anode - indium tin oxide (ITO), but other metal oxides can still be used, including but not limited to aluminum or indium doped zinc oxide (IZO), Magnesium-indium oxide and nickel-tungsten oxide, in addition to these oxides, such as metal nitrides of gallium nitride, such as zinc selenide Metal selenides and metal sulfides such as zinc sulfide can be used as the material of the anode. In applications where EL radiation is observed through the upper electrode and the cathode is the upper electrode, the light transmission of the anode is no longer important, and any electrically conductive material can be used. Transparent, opaque or reflective materials can be used. Materials that can be used in this application include, but are not limited to, gold, ruthenium, molybdenum, palladium, and platinum. General anode material, Whether transparent or not, its work function is usually greater than or equal to 4.1 eV, and the required anode material is usually deposited in an appropriate manner, such as evaporation, sputtering, chemical vapor deposition, or electrochemical methods, and the anode can be well known. Photolithography etching patterning.

Hole-transporting layer (HTL)

The hole transport layer of the organic electroluminescent device comprises at least one hole conducting compound, such as an aromatic tertiary amine, and it is inferred today that the compound contains at least one trivalent nitrogen atom bonded only to a carbon atom. At least one of the carbon atoms is one of the aromatic rings; one of these aromatic tertiary amines may be an arylamine such as a monoarylamine, a bisarylamine, a triarylamine or a high Aromatic amine groups of the molecule; a model of a monomolecular triarylamine is described by Klupfel et al. in U.S. Patent No. 3,180,730; and other suitable triarylamines are disclosed by Brantley et al. in U.S. Patent No. 3,567,450 and Patent No. 3,658,520 is directed to one or more vinyl radicals and/or a triarylalkylamine substituted with at least one group containing an active hydrogen.

One of the most commonly used aromatic tertiary amines is described in U.S. Patent Nos. 4,720,432 and 5,061,569, the disclosure of which is incorporated herein by reference. Examples of useful aromatic tertiary amines including, but not limited to, 1,1-bis(4-di-p-tolylamidophenyl)cyclohexane, 1,1-bis(4-di-pair) -tolylaminophenyl)-4-phenyl-cyclohexane, 4,4'-bis(diphenylamino)tetraphenyl, bis(4-dimethylamino-2-methylphenyl) )-phenylmethane, N,N,N-tris(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4(di-p-tolylamino)- Styryl] N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diamino Biphenyl, N,N,N',N'-tetra-1-naphthyl-4,4'-diaminobiphenyl, N,N,N',N'-tetra-2-naphthyl-4, 4'-Diaminobiphenyl, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, 4,4'-double [N -(1-naphthyl)-N-(2-naphthyl)amino]biphenyl, 4,4"-bis[N-(1-naphthyl)-N-phenylamino]p-terphenyl , 4,4'-bis[N-(2-naphthyl)-N-phenylamino]biphenyl, 1,5-bis[N-(1-naphthyl)-N-phenylamino]naphthalene , 4,4'-bis[N-(9-fluorenyl)-N-phenylamino]biphenyl, 4,4''-bis[N-(1-indenyl)-N-phenylamino ] p-bitriphenyl, 4,4''-bis[N-(2-phenanthryl)-N-phenylamino]biphenyl, 4,4''-bis[N-(8-fluorodecene) -N-phenylamino]biphenyl, 4,4''-bis[N-(2-indolyl)-N-phenylamino]biphenyl, 4,4''-double [N- (2-fused tetraphenyl)-N-phenylamino]biphenyl, 4,4''-bis[N-(2-indolyl)-N-phenylamino]biphenyl, 4,4' '-Bis[N-(2-Acidyl)-N-phenylamino]biphenyl, 2,6-bis(di-p-tolylamino)naphthalene, 2,6-bis(di-(1) -naphthyl)amino)naphthalene, 2,6-bis[N-(1-naphthyl)-N-(2-naphthalene Amino]naphthalene, N,N,N',N'-tetrakis(2-naphthyl)-4,4''-diamino-p-terphenyl, 4,4'-bis{N-benzene Benzyl-N-[4-(1-naphthyl)-phenyl]amino}biphenyl, 4,4'-bis[N-phenyl-N-(2-indolyl)amino]biphenyl, 2 , 6-bis[N,N-bis(2-naphthyl)amino]indole or 1,5-bis[N-(1-naphthyl)-N-phenylamino]naphthalene.

Another useful hole transport material is the polycyclic aromatic compound described in EP 1,009,041. In addition, polymer type hole transport materials can also be used, such as poly(N-vinylcarbazole) (PVK), poly Thiophene, polypyrrole, polyaniline and copolymeric polymers such as poly(3,4-extended ethylenedioxythiophene)/poly(4-styrene-sulfonate), also known as PEDOT/PSS.

Light-emitting layer (LEL)

As described in U.S. Patent Nos. 4,769,292 and 5,935,721, the luminescent layer of the organic electroluminescent device is composed of a luminescent or fluorescent material, and this region is also an electron-hole pair recombination to generate electrical excitation. Where the light is; the luminescent layer may be composed of a single material, but usually contains any primary luminescent material and a guest luminescent material or any photochromic dopant that can illuminate; the primary luminescent material in the luminescent layer may be an electron transporting material (described below), or a hole transport material (as described above), or other material or combination of materials that can be recombined with electron-holes; the dopant is typically a dye selected from high fluorescence efficiency, but a phosphorescent compound, Transition metal complexes as described in WO 98/55561, WO 00/18851, WO 00/57676 and WO 00/70655 are also usable; the weight percentage of dopant doped to the primary luminescent material is typically 0.01% to 10%.

There is an important key in selecting a dye as a dopant, that is, it is necessary to compare the bandgap potential, and the band gap potential is one molecule of the highest occupied molecular orbital and the lowest unfilled. The difference between the lowest unoccupied molecular orbital, if it is desired to achieve high efficiency energy transfer from the main luminescent material to the dopant, the energy gap of the dopant must be smaller than the energy gap of the main luminescent material.

The main illuminators and luminescent materials which are known and used are disclosed in U.S. Patent Nos. 4,768,292, 5,141,671, 5,150,006, 5,151,629, 5,405,709, 5,484,922, 5,593,788, 5,645,948, Patent Nos. 5,683,823, 5,755,999, 5,928,802, 5,935,720, 5,935,721, and 6,020,078, but are not limited to the above patents.

A metal complex composed of 8-hydroxyquinoline and a similar derivative (Formula A) is one of useful primary illuminant compounds, particularly suitable for electroluminescent light having an emission wavelength greater than 500 nm, such as green, yellow, orange And red light.

A derivative of 9,10-di-(2-naphthyl)anthracene (Formula B) is one of the useful primary illuminants, particularly for electroluminescent light having an emission wavelength greater than 400 nm, for example, blue, green, Yellow, orange, red light.

The illustration includes 9,10-di-(2-naphthyl)anthracene and 2-tris-butyl-9,10-di-(2-naphthyl)anthracene; other anthracene derivatives which can serve as the main emitter of the light-emitting layer Including 9,10-bis[4-(2,2-diphenylvinyl)phenyl]indole derivatives and phenylindole derivatives as described in EP 681,019.

The distyryl extended aryl derivative described in U.S. Patent No. 5,121,029 is also an effective primary illuminant for the luminescent layer.

Suitable fluorescent dopants include derivatives derived from fused rings, heterocycles and other compounds such as ruthenium, tetracene, dibenzopyran, perylene, rubrene, coumarin Coumarin, rodamine, quinacridone, thiopyran, polymethine, pyrilium, thiapyrilium, and carbostyryl compounds. The following examples include some of the available dopants, but are not limited to this: Wherein R can be hydrogen, tert-butyl, or Wherein n=1 or 2, R ₁ , R ₂ , R ₃ , R ₄ are selected from substituted or unsubstituted phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, or R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are selected from substituted or unsubstituted phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, or Wherein R ₁₃ , R ₁₄ , X is selected from substituted or unsubstituted phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, or Wherein R can be hydrogen or a third butyl group, or Wherein R can be hydrogen, tert-butyl, or Wherein R can be hydrogen, phenyl, methyl, or

Among them, the formula VIII is 5,6,11,12-tetraphenylnaphthacene (rubrene), which is a widely studied and used yellow light dopant, according to some studies. Literature report (Y.Sato at al, Syn. Met., 1997, 91, 103), the compound has the following advantages: near 100% quantum efficiency, anti-concentration quenching up to 7%, bipolar, etc., and can increase component stability and lifetime. And a general main illuminant or a hole transmission material can be used as its main illuminant, as disclosed in Japanese Patent Publication No. I242595.

Electron transport layer (ETL)

In this invention, the thin film material of the electron transport layer of a suitable organic electroluminescent device is a metal chelate 8-oxoquinoline compound comprising an 8-oxoquine chelating group. Compounds can aid in the injection and transport of electrons and produce high-efficiency and easy-to-manufacture film types; others can be used as electron-transport materials including various butadiene derivatives disclosed in U.S. Patent No. 4,356,429 and U.S. Patent No. 4,539,507. The various heterocyclic optical brighteners are described, and the benzazepines are also useful as electron transport materials.

In some instances, the luminescent layer and the electron transport layer can be selectively combined into a single layer, which can simultaneously accommodate both luminescence and electron transport.

Cathode

If the electroluminescent light is designed to be permeable from the anode, almost any electrically conductive material in the invention can form a cathode, wherein the more desirable material property is good film formation, which ensures that the cathode and the underlying organic layer are good. Contact, which in turn enhances electron injection at low voltages, and has good stability; useful cathode materials are typically low work function metals (<4.0 eV) or metal alloys; as described in U.S. Patent 4,885,221 Magnesium-silver alloy (Mg: Ag) One of the suitable cathode materials, wherein the ratio of silver is 1% to 20%; another suitable cathode material is a two-layer structure comprising a thick conductive metal layer covering a low work function metal thin layer or a metal salt, US The cathode described in U.S. Patent No. 5,677,572 is comprised of a thin layer of LiF and a thick layer of Al; other useful cathode materials include, but are not limited to, U.S. Patent Nos. 5,059,861, 5,059,862 and 6,140,763. The material being exposed.

When the component is designed to emit light through the cathode, the cathode must be transparent or nearly transparent. In this case, the metal must be thin or a transparent conductive oxide must be used, or a combination of these materials; A detailed description of an optically transparent cathode is provided in Patent No. 5,776,623; the method of depositing the cathode material may be evaporation, sputtering, or chemical vapor deposition, and if necessary, the cathode may be Patterning, in many well known ways, including, but not limited to, through-mask deposition, integral mask technology as described in U.S. Patent No. 5,276,380 and EP 0 732 868. (integral shadow masking), laser ablation and selective chemical vapor deposition.

In addition, in order to improve the illuminating color, luminous efficiency, illuminating stability, component life, and component manufacturing method of the organic electroluminescent device, reference is made to the US Patent Nos. 4,356,429, 4,539,507, 4,720,432, 4,885,211. , 5,151,629, 5,150,006, 5,141,671, 5,073,446, 5,061,569, 5,059,862, 5,059,861, 5,047,687, 4,950,950, 4,769,292, 5,104,740, 5,227,252, 5,256,945, 5,069,975, Patent Nos. 5,122,711, 5,366,811, 5,126,214, 5,142,343, 5,389,444, 5,458,977.

In another preferred embodiment of the invention, the organic electroluminescent device is a display. In general, the display can be used in televisions, mobile phones, computer monitors, monitors, devices and/or electrical appliances or other devices that can use displays and/or devices used in various individuals, homes, offices, and/or vehicles. Electrical appliances.

Example

In order to further illustrate the method and advantages of the present invention, the following is a summary of the various embodiments and examples, but the spirit and details of the present invention are not limited thereto.

The following provides an introduction to the instruments that will be used in the examples of this case:

1. Nuclear Magnetic Resonance Spectrometer: Measurements were taken for VARIAN Unity 300 MHz to obtain nuclear magnetic resonance (NMR) spectra, and CDCl ₃ was used as a standard compound.

2. Mass spectrometer: Measured using MICROMASS TRIO-2000 GC/MS using the Rapid Atomic Impact (FAB) Free method.

3. Vacuum film evaporator (coater): is a TRC 18-inch rotary evaporator, which can hold 6 substrates, 2 motorized baffles, 8 electric enthalpy, 5 oscillation sensors, IC-5 Film thickness controller and diffusion pump.

4. Spectrophotometer (colorimeter): Measurements were performed using a PhotoResearch PR-650 instrument.

5. Programmable power supply: The current is supplied using a KEITHLEY 2400 instrument.

I. Synthesis of compounds

Synthesis Comparative Example 1: The same procedure as in Synthesis Example 1, in which 2-methylanthracene was changed to 2-ethylanthracene, 9-bromo-2-ethylanthracene (yellow powder 4 g, yield 57.8%, HPLC > 96%) was obtained.

Synthesis Comparative Example 2: The same procedure as in Synthesis Example 1, in which 2-methylanthracene was changed to 2-t-butylanthracene, 9-bromo-2-t-butylanthracene (yellow powder 2.5 g, yield 37.5%, HPLC > 96%) was obtained.

We have found that the bromination of 2-methylindole is particularly high, and further high-purity and mass-produced OLED materials can be obtained.

Synthesis Example 1: A 500 ml three-necked flask was taken, dichloromethane (30 ml) was added, 2-methylanthrancene (5 g, 25 mmole) was added, and NBS (N-Bromosuccinimide, 4.8 g, 28 mmole) was added thereto, and the mixture was stirred at normal temperature. The reaction was completed by HPLC, and after completion of the reaction, it was poured into water to precipitate. After filtration, it was washed with a small amount of methanol to give 9-bromo-2-methylanthrancene (deep yellow powder 3 g, yield 70%, HPLC > 96%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.53 (d, 1H); 8.27 (s, 1H); 8.21 (s, 1H); 7.87 (d, 1H); 7.75 (d, 1H); 7.58 (t , 1H); 7.45 (t, 1H); 7.24 (d, 1H); 2.60 (s, 3H).

Synthetic Examples 2 to 4 can be combined with the following chemical reaction formula:

Synthesis Example 2:

A 500 ml three-necked flask was taken, dichloromethane (30 ml) was added, 2-methylanthracene (5 g, 25 mmole) was added, and NBS (N-Bromosuccinimide, 4.8 g, 28 mmole) was added thereto, and the mixture was stirred at normal temperature. The reaction was completed by TLC, and after the reaction was completed, it was poured into water to precipitate. After filtration, it was washed with a small amount of methanol to give Intermediate A1 (deep yellow powder 3 g, HPLC >96%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.53 (d, 1H); 8.27 (s, 1H); 8.21 (s, 1H); 7.87 (d, 1H); 7.75 (d, 1H); 7.58 (t , 1H); 7.45 (t, 1H); 7.24 (d, 1H); 2.60 (s, 3H).

Synthesis Example 3:

Take 500 ml three-necked flask, add Toluene (100ml) / Ethanol (20ml) / DIwater (35ml), add intermediate A1 (20g, 0.074 mol), add 1-Naphthaleneboronic acid (14g, 0.081 mol), then add K ₂ Immediately after CO ₃ (20.6 g, 0.143 mol), Pd(pph ₃ ) ₄ (0.3% × 0.074 mol) was added. Heat to 100~105 °C, and check whether the reaction is completed 2 hours after reflux. After completion of the reaction, the mixture was poured into water and extracted with toluene. After extraction, water was removed with sodium sulfate. Filtration and concentration under reduced pressure gave Intermediate A2 (yield: 20 g,yield: 84%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.52 (s, 1H); 8.02-7.96 (m, 4H); 7.85-7.81 (m, 1H); 7.69-7.63 (dd, 1H); 7.51-6.79 ( m, 8H); 2.27 (s, 3H).

Synthesis Example 4:

A 500 ml three-necked flask was taken, and dichloromethane (40 ml) / Acetic acid (150 ml) was added, followed by the intermediate A2 (20 g, 0.063 mol), and the ice bath. After dropping to 0 to 5 ° C, Br 2 (11.2 g, 0.07 mol) was slowly dropped into a three-necked flask in a 50 ml addition tube, and the ice bath was removed after the completion of the dropping. After completion of the reaction, it was poured into water and poured into a reaction solution of Na2SO3 (aq) at 20 wt% until the color of the aqueous solution was no longer changed, and after stirring for 30 minutes. filter. Intermediate A3 (yellow green powder 22 g, yield 88%, HPLC >95%) was obtained. _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.61 (d, 1H0; 8.53 (d, 1H); 8.06 (d, 1H); 8.01 (d, 1H), 7.71-7.30 (m, 7H); 7.22- 7.02 (m, 3H); 2.33 (s, 3H).

Synthesis Example 5:

The same procedure as in the third synthesis example was carried out by using the intermediate A1 (16 g, 0.06 mol) and 2-Naphthalene boronic acid (11.2 g, 0.066 mol) for the Suzuki coupling reaction to obtain the intermediate A4, which yielded 20 g (yellow-brown thick liquid, produced). The rate was 84%, HPLC > 95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.54 (s, 1H); 8.10-8.06 (m, 3H); 8.01 (d, 1H); 7.97 (s, 1H); 7.96-7.94 (m, 1H) ; 7.96-7.94 (m, 1H); 7.77 (d, 1H); 7.67-7.62 (m, 3H); 2.44 (s, 3H).

Synthesis Example 6:

The same procedure as in the synthesis example 4 using Intermediate A4 (20 g, 0.06 mol) afforded Intermediate A5, yielding 20 g (yellow green powder, yield 84%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.59 (d, 1H); 8.52 (d, 1H); 7.96 (d, 1H); 7.94 (d, 1H); 7.87 (d, 1H); 7.86 (s , 1H); 7.61-7.48 (m, 5H); 7.47 (d, 1H); 7.42 (s, 1H); 7.30 (dt, 1H); 2.36 (s, 3H).

Synthesis Example 7:

The same procedure as in the synthesis example 3 was carried out by using the intermediate A1 (10 g, 0.037 mol) and 4-(2-Naphthalene) bezene boronic acid (10 g, 0.041 mol) for the Suzuki coupling reaction to obtain the intermediate A6, which yielded 12 g (light yellow powder). , yield 84%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): δ: 8.49 (s, 1H); 8.26 (s, 1H); 8.06 (d, 1H); 8.01-7.93 (m, 7H); 7.77 (d, 1H) ; 7.59-7.53 (m, 5H); 7.47 (dt, 1H) 7.38 (dd, 1H); 7.37 (d, 1H); 2.57 (s, 3H).

Synthesis Example 8:

The same procedure as in Synthesis Example 4 using Intermediate A6 (9.2 g, 0.023 mol) afforded Intermediate A7, yielding 10 g (yellow green powder, yield 84%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.61 (d, 1H); 8.54 (d, 1H); 8.02-7.90 (m, 7H); 7.72 (d, 1H); 7.59-7.50 (m, 5H) ;7.44 (d, 1H); 7.38 (dt, 1H); 2.46 (s, 3H).

Synthesis Example 9: Preparation of B601

Take a 500 ml three-necked flask, toluene (100 ml) / ethanol (20 ml) / DI water (35 ml), add intermediate A3 (7 g, 17.6 mmol), and add 4-(2-Naphthyl)phenylboronic acid (5 g, 20.1 mmol). Following the addition of K ₂ CO ₃ (5 g, 35.7 mmol), Pd(pph ₃ ) ₄ (0.3% x 17.6 mmol) was added immediately. Heat to reflux (about 100~105 ° C), and check whether the reaction is completed 2 hours after reflux. After completion of the reaction, the mixture was poured into water and extracted with toluene. After extraction, water was removed with sodium sulfate. Filtration, chromatography column, and concentration under reduced pressure. Filtration gave 7.3 g of a pale yellow powder (yield 80%, HPLC >99%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.22 (s, 1H); 8.08-7.83 (m, 9H); 7.72 (dt, 1H), 7.58-7.51 (m, 3H); 7.30-7.19 (m, 6H); 7.08-7.04 (m, 2H); 6.79 (d, 1H); 6.65 (s, 1H); 2.08 (s, 3H). T _d (TGA): 421.83 ° C; Tm (DSC) 265.90 ° C; _Abs (nm): 358, 377, 397; λ _em (nm): 425; MF: C ₄₁ H ₂₈ ; m/e (Mass, M ⁺ ): 520.67.

Synthesis Example 10: Preparation of B602

The same procedure as in Synthesis Example 9 was carried out using Intermediate A3 (2 g, 5.03 mmol) using 4-(1-Naphthal)phenylboronic acid (1.4 g, 5.6 mmol) for Suzuki coupling reaction to obtain B602, yielding 1.1 g of pale yellow powder. The rate was 42%, HPLC > 95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.22- 8.20 (m, 1H); 8.07 (d, 1H); 8.00 (d, 1H); 7.98-7.87 (m, 2H); 7.85 (d, 1H) ;7.82(d,1H); 7.78-7.68(m,4H); 7.68-7.55(m,10H);7.52-7.51(dt,2H);7.38(d,1H);7.37-7.35(dt,1H) ; 2.30 (s, 3H). T _d (TGA): 407.18 ° C; Tm (DSC) 221.37 ° C; λ _abs (nm): 358, 377, 398; λ _em (nm): 423; MF: C ₄₁ H ₂₈ ; m / e (Mass, M ⁺ ): 520.67 .

Synthesis Example 11: Preparation of B603

The same procedure as in Synthesis Example 9 was carried out using Intermediate A3 (2 g, 5.03 mmol) using 4-Biphenylboronic acid (1.1 g, 5.5 mmol) for Suzuki coupling reaction to obtain B603, yielding 1.4 g of pale yellow powder (yield 58%, HPLC>95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.13 (d, 1H); 8.11 (d, 1H); 7.93 (t, 2H); 7.88-7.82 (m, 3H); 7.81-7.76 (m, 3H) ; 7.70 (m, 1H); 7.67-7.42 (m, 8H); 7.38 (dt, 1H); 7.28-7.23 (m, 3H); 2.35 (s, 3H). T _d (TGA): 391.70 ° C; Tm (DSC) 239.31 ° C; λ _abs (nm): 358, 377, 398; λ _em (nm): 424; MF: C ₃₇ H ₂₆ ; m / e (Mass, M ⁺ ): 470.61 .

Synthesis Example 12: Preparation of B604

The same procedure as in Synthesis Example 9 was carried out using Intermediate A3 (2 g, 5.03 mmol) using 2-Naphthaleneboronic acid (1.2 g, 7.0 mmol) for Suzuki coupling reaction to obtain B604, yielding 1.3 g of pale yellow powder (yield 58%, HPLC) >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.20-8.09 (m, 6H); 8.02 (t, 1H); 7.85-7.63 (m, 7H); 7.57 (t, 1H); 7.46 (d, 1H) ; 7.37-7.22 (m, 4H); 2.36 (s, 3H). T _d (TGA): 373.70 ° C; λ _abs (nm): 358, 377, 397; λ _em (nm): 423; MF: C ₃₅ H ₂₄ ; m/e (Mass, M ⁺ ): 444.58.

Synthesis Example 13: Preparation of B605

Take a 500 ml three-necked flask, add toluene (40 ml) / ethanol (8 ml) / DI water (15 ml), add intermediate A5 (4 g, 10 mmole), then add 4-(2-Naphthal)phenylboronic acid (2.8 g, 11 mmole) After the addition of K ₂ CO ₃ (2.8 g, 20 mmol), Pd(pph ₃ ) ₄ (0.3%×10 mmole) was added immediately. The mixture was heated to a reflux temperature of about 100 to 105 ° C, and the reaction was completed 2 hours after the reflux. After the reaction was completed, it was poured into water and extracted with Toluene 100-150 ml. After extraction, water was removed with Na ₂ SO ₄ . Filtration, chromatography column, concentration under reduced pressure, and precipitation. Filtration gave B605, yielding 3.9 g of pale yellow powder (yield: 74%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.25 (s, 1H); 8.10 (d, 1H); 8.06-7.92 (m, 9H); 7.83 (d, 1H); 7.76 (d, 1H); 7.70 (d, 1H); 7.63-7.58 (m, 5H); 7.56-7.52 (m, 2H); 7.48 (s, 1H); 7.36-7.29 (m, 2H); 7.24-7.22 (dd, 1H); (s, 3H). T _d (TGA): 460.14 ° C; Tm (DSC) 248.13 ° C; λ _abs (nm): 358, 378, 398; λ _em (nm): 431; MF: C ₄₁ H ₂₈ ; m / e (Mass, M ⁺ ): 520.67 .

Synthesis Example 14: Preparation of B606

The same procedure as in Synthesis Example 13 was carried out by using Suzuki coupling reaction with Intermediate A5 (4 g, 10 mmol) and 4-Biphenylboronic acid (2.2 g, 11 mmol) to obtain B606, yielding 3.6 g of pale yellow powder (yield 76%, HPLC>95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.10-7.89 (m, 4H); 7.86 (d, 2H); 7.76 (d, 2H); 7.71-7.59 (m, 10H); 7.53 (s, 1H) ; 7.50 (t, 1H); 7.41-7.30 (m, 2H); 7.24 (dd, 1H); 2.36 (s, 3H). T _d (TGA): 434.51 ° C; Tm (DSC) 248.13 ° C; λ _abs (nm): 359, 378, 398; λ _em (nm): 429; MF: C ₃₇ H ₂₆ ; m / e (Mass, M ⁺ ): 470.61 .

Synthesis Example 15: Preparation of B607

The same procedure as in Synthesis Example 13 was carried out by using Suzuki coupling reaction with Intermediate A5 (4 g, 10 mmol) and 4-(1-Naphthal)phenylboronic acid (2.8 g, 11 mmol) to obtain B607, which yielded 3.4 g of pale yellow powder. Yield 65%, HPLC > 90%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.19 (dd, 1H); 8.09 (d, 2H); 8.06-8.03 (m, 2H); 8.01 (s, 1H); 7.99-7.97 (dd, 2H) ;7.96-7.93(m,3H);7.88-7.86(m,2H);7.84(s,1H);7.83-7.79(m,2H);7.77-7.75(m,3H);7.40-7.37(dt, 3H); 7.34-7.31 (m, 2H); 7.28 (dd, 1H); 7.23-7.21 (m, 1H); 2.39 (s, 3H). T _d (TGA): 433.41 ° C; Tm (DSC) 385.87 ° C; λ _abs (nm): 360, 378, 398; λ _em (nm): 429; MF: C ₄₁ H ₂₈ ; m / e (Mass, M ⁺ ): 520.67 .

Synthesis Example 16: Preparation of B608

Take a 500 ml three-necked flask, add toluene (40 ml) / ethanol (8 ml) / Dlwater (15 ml), add intermediate A7 (4.7 g, 10 mmole), add 1-Nephthaleneboronic acid (2.1 g, 11 mmol), then add Immediately after K ₂ CO ₃ (2.8 g, 20 mmol), Pd(pph ₃ ) ₄ (0.3% × 10 mmole) was added. The mixture was heated to a reflux temperature of about 100 to 105 ° C, and the reaction was completed 2 hours after the reflux. After the reaction was completed, it was poured into water and extracted with Toluene 100-150 ml. After extraction, water was removed with Na ₂ SO ₄ . Filtration, chromatography column, concentration under reduced pressure, and precipitation. Filtration gave B608, yielding 5.02 g of pale yellow powder (yield 80%, HPLC >95%). _{^{1 H NMR (CDCl 3, 300MHz}} , δ): 8.29 (s, 1H); 8.04 (d, 1H); 8.01-7.97 (m, 6H); 7.93 (d, 1H); 7.83 (d, 1H); 7.72 - 7.69 (m, 2H); 7.64 (d, 1H); 7.61-7.47 (m, 5H); 7.45 (d, 1H); 7.39 (s, 1H); 7.33 (dt, 1H); 7.25-2.22 (m) , 3H); 7.09 (dd, 1H); 2.42 (s, 3H). T _d (TGA): 442.19 ° C; Tm (DSC) 203.83 ° C; λ _abs (nm): 359, 377, 397; λ _em (nm): 426; MF: C ₄₁ H ₂₈ ; m / e (Mass, M ⁺ ): 520.67 .

II. Determination of color and brightness of components constituting the compound of the present invention

A specific embodiment of the organic electroluminescent device (OLED, 10) of the present invention is illustrated by a simplified cross-sectional view of the first figure. The OLED (10) comprises a transparent glass or plastic substrate (11), a transparent conductive anode layer (12) is deposited on the plane of the substrate (11), and an organic hole injecting material is deposited on the anode layer (12). On the surface, a hole injection layer (13) is formed. An organic hole transport layer material is deposited on the surface of the hole injection layer (13) to form an organic hole transport layer (14). An organic light-emitting layer (15) is deposited on the surface of the organic hole transport layer (14) by a primary luminescent material containing a fluorescent dopant. One of the electron transport layers (16) caused by the electron transporting material is deposited on the surface of the organic light emitting layer (15). Then, one electron injection layer (17) caused by the electron injecting material is deposited on the surface of the electron transport layer (16) and a metal conductive layer (18) is deposited on the surface of the electron injection layer (17) to form a cathode layer ( 18).

In this embodiment, the conductive anode layer (12) is a p-type contact and the conductive cathode layer (18) is an n-type contact. The negative terminal of the power source (19) is connected to the conductive layer (18) and the positive terminal is connected to the conductive layer (12). When a potential is applied between the conductive anode layer (12) and the conductive cathode layer (18) by the power source (19), electrons injected from the n-type contact point [conductive cathode layer (18)] will pass through the electron injection layer. (17) entering the organic light-emitting layer (15) with the organic electron transport layer (16) and passing the hole injected from the p-type contact point [conductive anode layer (12)] through the organic hole injection layer (13) and The organic hole transport layer (14) enters the organic light emitting layer (15). In the organic light-emitting layer (15), when electrons are recombined with the holes, photons are emitted.

The production process is as follows:

1. Cleaning of the substrate: preparing the ITO substrate that has been etched (the ITO The substrate size is 40×40 mm, and the ITO substrate is washed with acetone, methanol and deionized water, placed in an oven, and baked at a temperature of 130 ° C for 1 hour;

Second, the substrate before processing: the ITO substrate is taken out of the oven and placed in the plasma processor, activated according to the existing activation step;

3. Evaporation: The pre-processed ITO substrate is placed on a rotating carrier in the TRC vapor deposition machine. When the vacuum of the vapor deposition chamber reaches 10 ^-6 Torr, the evaporation of the vapor deposition material begins. The evaporation rate is monitored by a quartz sensor. The inventor vapor-deposited the hole injection layer at a rate of 2 Å/s, vapor-deposited NPB at a rate of 2 Å/s, vapor-deposited Alq ₃ at a rate of ₂ Å/s, and then vapor-deposited LiF at a rate of 0.1 Å/s, and Al is evaporated at a rate of 10 Å/s.

Fourth, component packaging: the package cover is glass material. After the glass cover is coated with UV glue, the newly fabricated component is placed in a nitrogen glove box together with the package cover, and the ITO substrate and the package cover are closely adhered by a heavy object, and the polymerization of the glue is performed by UV light. .

5. Measurement of component color and brightness: The packaged component is supplied with current by the power supply under the control of LabVIEW program, and the spectrum, brightness and luminosity (CIE _{x, y} ) of the component are measured by spectrophotometry. nature.

According to the above methods for measuring color and brightness, the color and brightness of the constituent elements of the compound as the organic light-emitting layer were measured, and the results were as follows:

Example 1 (comparative example)

The ITO (Indium Tin Oxide) glass substrate was 40 mm long x 40 mm wide x 0.7 mm thick, ultrasonically cleaned in methanol for 12 minutes, and then irradiated with ultraviolet light (ozone generation) for 10 minutes. The cleaned glass substrate is moved into a vacuum vapor deposition apparatus. On the surface with the transparent electrode, a thin film S707 (see the following structural formula) is formed to have a thickness of 180 nm, so that the thin film is formed Membrane cover transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). A 7 nm NPB is then formed on S707 (see the structural formula below). The formed film is a second hole injection layer (hole transport layer). 2% of the compound of the seventeenth formula and the compound of ADN were mixed by vacuum vapor deposition to form a light-emitting layer having a thickness of 30 nm. Then, a film having a thickness of 10 nm was formed as an electron injecting layer by Alq (see the following structural formula). Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device. Next, the device is hermetically sealed in a dry glove box for protection.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.69 V, blue light, CIE (0.159, 0.251), luminance of 2237 cd/m ² , and luminous efficiency of 11.18 cd/A were emitted. The fabricated components were operated at 20 mA/cm ² at room temperature for operational stability testing. The brightness decreased by 25% during 300 hours of operation.

Example 2 (comparative example)

The organic electroluminescent diode is fabricated according to the procedure of the first embodiment. The compound MADN replaces the ADN compound.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.45 V, blue light, CIE (0.154, 0.228), luminance of 1937 cd/m ² , and luminous efficiency of 9.68 cd/A were emitted. After 300 hours of operation, the brightness dropped by 20%.

Example 3 (inventive example)

The organic electroluminescent diode was fabricated, and the compound B601 was substituted for the ADN compound according to the procedure of Example 1.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.46 V, blue light, CIE (0.157, 0.242), luminance of 2146 cd/m ² , and luminous efficiency of 10.73 cd/A were emitted. After 300 hours of operation, the brightness dropped by 18%.

Example 4 (inventive example)

The organic electroluminescent diode was fabricated by substituting the compound of formula B603 for the ADN compound according to the procedure of Example 1.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.78 V, blue light, CIE (0.163, 0.234), luminance of 1890 cd/m ² , and luminous efficiency of 9.45 cd/A were emitted. After 300 hours of operation, the brightness dropped by 16%.

Example 5 (inventive example)

The organic electroluminescent diode was fabricated by substituting the compound of formula B605 for the ADN compound according to the procedure of Example 1.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.60 V, blue light, CIE (0.155, 0.238), brightness of 2043 cd/m ² , and luminous efficiency of 10.22 cd/A. After 300 hours of operation, the brightness dropped by 16%.

Example 6 (inventive example)

The organic electroluminescent diode was fabricated and the AND compound was replaced with a compound of formula B606 in accordance with the procedure of Example 1.

When the organic electroluminescent diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.44 V, blue light, CIE (0.158, 0.234), luminance of 2028 cd/m ² , and luminous efficiency of 10.14 cd/A. When it was operated for 300 hours, the brightness dropped by 14%.

Example 7 (inventive example)

Before the treatment in the same manner as in the first embodiment, a film S707 was formed to have a thickness of 90 nm, and the formed film was covered with a transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). A 7 nm NPB was then formed on S707. The formed film is a second hole injection layer (hole transport layer). A compound of 0.5% RD5, 60% of rubrene and 40% of B601 compound were vacuum-deposited to form a light-emitting layer having a thickness of 50 nm. A film having a thickness of 45 nm was formed as an electron injecting layer by Alq. Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device; then, the device was hermetically sealed in a dry glove box for protection.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 7.56 V, red light, CIE (0.642, 0.349), luminance of 1257 cd/m ² , and luminous efficiency of 6.28 cd/A. When it was operated for 300 hours, the brightness dropped by 6%.

Example 8 (inventive example)

Prior to the same manner as in Example 1, a film S707 was formed having a thickness of 75 nm to form a film cover transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). A 7 nm NPB was then formed on S707. The formed film is a second hole injection layer (hole transport layer). A compound of 5% GD54 and a compound of the formula B601 were mixed by vacuum vapor deposition to form a light-emitting layer having a thickness of 30 nm. A film having a thickness of 25 nm was formed as an electron injecting layer by Alq. Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device. Next, the device is hermetically sealed in a dry glove box for protection.

When the organic electroluminescent diode was driven at a current density of 20 mA/cm ² , the driving voltage was 5.78 V, and green light, CIE (0.329, 0.627), brightness of 4445 cd/m ² , and luminous efficiency of 22.23 cd/A were emitted. When it was operated for 300 hours, the brightness dropped by 8%.

Example 9 (inventive example)

Prior to the same manner as in Example 1, a film S707 was formed having a thickness of 180 nm to form a film cover transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). Then on S707 A 7 nm NPB was formed. The formed film is a second hole injection layer (hole transport layer). A compound of 3% BD5 was mixed with a compound of the formula B601 by vacuum vapor deposition to form a light-emitting layer having a thickness of 30 nm. A film having a thickness of 10 nm was formed as an electron injecting layer by Alq. Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device. Next, the device is hermetically sealed in a dry glove box for protection.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.34 V, and deep blue light, CIE (0.142, 0.141), luminance of 1131 cd/m ² , and luminous efficiency of 5.65 cd/A were emitted. When it was operated for 300 hours, the brightness dropped by 15%.

Example 10 (inventive example)

Prior to the same manner as in Example 1, a film S707 was formed having a thickness of 75 nm to form a film cover transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). A 7 nm NPB was then formed on S707. The formed film is a second hole injection layer (hole transport layer). A compound of 3% TBRb was mixed with a compound of the formula B601 by vacuum vapor deposition to form a light-emitting layer having a thickness of 30 nm. A film having a thickness of 25 nm was formed as an electron injecting layer by Alq. Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device. Next, the device is hermetically sealed in a dry glove box for protection.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 6.56 V, yellow light, CIE (0.477, 0.496), luminance of 2480 cd/m ² , and luminous efficiency of 12.40 cd/A. When it was operated for 300 hours, the brightness dropped by 11%.

Example 11 (inventive example)

Prior to the same manner as in Example 1, a film S707 was formed having a thickness of 75 nm to form a film cover transparent electrode. The film formed by S707 serves as a first hole injection layer (hole transport layer). Then, a film of 2% TBRb and NPB was formed into a second hole injection layer (hole transport layer) on S707. 2% of the compound of the seventeenth formula was mixed with a compound of the formula B601 by vacuum vapor deposition to form a light-emitting layer having a thickness of 40 nm. A film having a thickness of 10 nm was formed as an electron injecting layer by Alq. Thereafter, lithium fluoride (LiF) 0.1 nm was deposited on Alq as an electron injection layer (cathode). Finally, aluminum was vapor deposited at 150 nm to form a cathode, and the above sequence completed deposition of the device. Next, the device is hermetically sealed in a dry glove box for protection.

When the organic electroluminescence diode was driven at a current density of 20 mA/cm ² , the driving voltage was 7.35 V, white light, CIE (0.318, 0.317), luminance of 2710 cd/m ² , and luminous efficiency of 13.55 cd/A were emitted. When it was operated for 300 hours, the brightness dropped by 14%.

For the organic electroluminescent diode formed by the above embodiments and the comparative examples, a comparison table of driving voltage, brightness, current efficiency, and chromaticity value (CIE) is shown in Table 1 below.

It is confirmed from the above-mentioned Table 1 that when the main body of the light-emitting layer is selected to include the asymmetric trisubstituted europium 2-methylindole compound as the light-emitting layer main body, great improvement in voltage, efficiency and stability can be achieved. In addition, as is apparent from the CIE coordinates, the color purity of the element can be maintained when the body of the luminescent layer comprises an asymmetric trisubstituted fluorene 2-methyl fluorene compound. The second A picture, the second B picture, the second C picture and the second D picture, after the series of compounds are fabricated into components, the first embodiment can reduce the driving voltage by 0.23 V compared with the first embodiment. Example 1 can increase the luminous efficiency by about 10% compared with Comparative Example 2. The organic electroluminescent diode utilizes the compound of the present invention, the formula B601 to B607, which has high efficiency of luminescence and emits blue light (as shown in the second C diagram). It can be used as the main body of red, blue, green and yellow light (such as the second D picture).

An organic electroluminescent diode made of small organic molecules, the material itself (in the form of a uniform film) should be able to avoid crystallization during component operation (current flow). Crystallization causes molecular stacking, whether fluorescent or phosphorescent The quality of the electroluminescence will quenching, causing the brightness of the component to drop drastically and eventually become completely unlit. Therefore, the organic electroluminescent diode is fabricated, and its constituent materials are designed in molecular design to achieve an amorphous glass state. The third A, B, and C diagrams are respectively ADN unannealed. The surface morphology of the film was measured by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times. The fourth A, four B, and four C graphs are respectively ADN, and the surface morphology of the film is 5,000 times, 50,000 times, and 100,000 times measured by a scanning microscope after being held at 90 ° C for 1 hour in the atmosphere. The fifth, fifth, and fifth C diagrams are MADN, respectively, and the surface morphology of the film was measured by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times without annealing. The sixth A, six B, and six C diagrams are respectively MADN, and the surface morphology of the film is 5,000 times, 50,000 times, and 100,000 times measured by scanning microscopy after being held at 90 ° C for 1 hour in the atmosphere. The seventh, seventh, seventh, and seventh C diagrams are respectively the compound of the formula B601, which was obtained by scanning microscopy, and the surface morphology of the film was 5,000 times, 50,000 times, and 100,000 times as measured by scanning microscopy. The eighth, eighth, and eighth C graphs are respectively the compound of the formula B601, which is 5,000 times, 50,000 times, and 100,000 times the film surface measured by scanning microscopy after being held at 90 ° C for 1 hour in the atmosphere. form. The ninth, ninth, and ninth C diagrams are respectively shown in the form of the compound of the formula B603, which were obtained by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times of the surface morphology of the film of the formula B603. And the tenth A, XB, and C C diagrams are respectively the compound of the formula B603, and the film surface is 5,000 times, 50,000 times, 100,000 times as measured by a scanning microscope after being held at 90 ° C for 1 hour in the atmosphere. form. The eleventh A, eleventh, and eleventh C diagrams are respectively shown as compounds of formula B605, which are not annealed. The surface morphology of the film was measured by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times. The Twelfth A, Twelfth, and Twelve C diagrams are respectively the compound of formula B605, which is 5,000 times, 50,000 times, and 100,000 times as measured by scanning microscopy after being held at 90 ° C for 1 hour in the atmosphere. The surface morphology of the film. The thirteenth, thirteenth, and thirteenth C diagrams show the surface morphology of the film of the formula B606, which was obtained by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times, respectively, without annealing. And the fourteenth A, fourteenth B, and fourteenth C diagrams are respectively the compound of the formula B606, which is 5,000 times, 50,000 times, 100,000 times as measured by a scanning microscope after being held at 90 ° C for 1 hour in the atmosphere. The surface morphology of the film.

Wherein, as shown in the third A, B, and C diagrams, the film has a substantially crystalline form when not annealed; the fourth, fourth, fourth, and fourth C, after annealing, The crystal morphology of the film is more serious; the fifth, fifth, fifth, and fifth C diagrams are compared with the sixth, sixth, and sixth C diagrams, and the surface of the film is smooth after annealing, but the film is annealed. There is a slight crystalline form and MADN still has minor defects. But in the seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, and fourteenth drawings, A, B, and C are shown, with or without annealing. The film is smooth and has an amorphous form. A series of compounds having the structure of the formula (I) is shown to effectively improve the crystallinity of AND and MADN, and is a good amorphous compound.

(10)‧‧‧Organic electroluminescent device

(11) ‧‧‧Substrate

(12) ‧ ‧ anode layer

(13)‧‧‧ hole injection layer

(14) ‧‧‧ hole transport layer

(15) ‧‧‧Lighting layer

(16) ‧‧‧Electronic transport layer

(17)‧‧‧Electron injection layer

(18) ‧‧‧ cathode layer

(19) ‧‧‧Power supply

(20) ‧‧‧Organic layer

The first figure is a schematic structural view of a general organic electroluminescent device.

The second A and B diagrams are respectively a BIV diagram of the light emitted by the blue light element of individual materials and the current density is plotted against the luminous efficiency. The second C picture shows the luminescence spectrum of the blue light element after the individual materials are made. The second D picture is a luminescence spectrum diagram of the B601 material made of red, green, dark blue, light blue, and yellow light elements.

The third A, three B, and three C patterns are ADN, respectively, and the surface morphology of the film was measured by scanning microscopy at 5,000 times, 50,000 times, and 100,000 times without annealing.

The fourth A, four B, and four C maps were respectively 5,000 times and 50,000 measured by scanning microscopy after ADN was held at 90 ° C for 1 hour in the atmosphere. Double, 100,000 times the film surface morphology.

The fifth, fifth, and fifth C-patterns are 5,000-fold, 50,000-fold, and 100-000-fold film surface morphology measured by scanning microscopy of MAND without annealing.

The sixth A, six B, and six C graphs are 5,000-fold, 50,000-fold, and 100-000-fold film surface morphology measured by scanning microscopy after MADN was held at 90 ° C for 1 hour in the atmosphere.

The seventh A, seventh B, and seven C graphs are the surface morphology of the film of the formula (II), which was not annealed, and was 5,000 times, 50,000 times, and 100,000 times as measured by a scanning microscope.

The eighth, eighth, and eighth C graphs are the surface morphology of the film of 5,000 times, 50,000 times, and 100,000 times as measured by a scanning microscope after the compound of the formula (II) was heated at 90 ° C for 1 hour in the atmosphere.

The ninth, ninth, and ninth C-patterns are the surface morphology of the film of 5,000 times, 50,000 times, and 100,000 times as measured by scanning microscopy, respectively, of the compound of the formula (IV).

The tenth A, XB, and X C drawings are the surface morphology of the film of 5,000 times, 50,000 times, and 100,000 times as measured by a scanning microscope after the compound of the formula (IV) was kept at a temperature of 90 ° C for 1 hour.

The eleventh A, eleventh, and eleventh C-patterns are film surface morphology of 5,000 times, 50,000 times, and 100,000 times as measured by a scanning microscope, without annealing the compound of the formula (VI).

The 12th, 12th, and 12th C pictures are films of 5,000 times, 50,000 times, and 100,000 times as measured by scanning microscopy after the compound of formula (VI) is held at 90 ° C for 1 hour in the atmosphere. Surface morphology.

The thirteenth, thirteenth, and thirteenth Cth views are the surface morphology of the film of the formula (VII), which is 5,000 times, 50,000 times, and 100,000 times as measured by scanning microscopy, without annealing.

The fourteenth A, fourteenth, and fourteenth C-thraw films are 5,000-fold, 50,000-fold, and 100,000-fold films measured by scanning microscopy after the compound of the formula (VII) is held at 90 ° C for 1 hour in the atmosphere. Surface morphology.

(10)‧‧‧Organic electroluminescent device

(11) ‧‧‧Substrate

(12) ‧ ‧ anode layer

(13)‧‧‧ hole injection layer

(14) ‧‧‧ hole transport layer

(15) ‧‧‧Lighting layer

(16) ‧‧‧Electronic transport layer

(17)‧‧‧Electron injection layer

(18) ‧‧‧ cathode layer

(19) ‧‧‧Power supply

(20) ‧‧‧Organic layer

Claims (21)

A 2-methylindole compound having the novel asymmetric trisubstituted indole of formula (I): Wherein X is a substituted or unsubstituted aryl group having an aromatic carbon number of 6 to 20 carbon atoms, and Y is a substituted or unsubstituted aryl group having an aromatic carbon number of 6 to 20 carbon atoms. Group, and X is not equivalent to Y. An organic electroluminescent device comprising: a substrate; two electrodes, wherein one electrode is disposed on the substrate; and an organic layer disposed between the electrodes and including a 2-methylindole compound of the formula (I) wherein X is a substituted or unsubstituted aryl group having an aromatic carbon number of 6 to 20 carbon atoms, and Y is an aromatic carbon number of 6 to 20 A substituted or unsubstituted aryl group consisting of one carbon atom, and X is not equivalent to Y. The organic electroluminescent device of claim 2, wherein the 2-methylindole compound is selected from the group consisting of: B601, B602, B603, B604, B605, B606, B607, B608, B609, B610, B611, B612, and B613. The organic electroluminescent device of claim 2, wherein the organic layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer, and the like, from the near substrate to the substrate. An electron transport layer and an electron injection layer, wherein the 2-methyl fluorene compound having the structure of the formula (I) is included in the hole injection layer, the hole transport layer, the organic light-emitting layer, and the electron transport layer Or in a layered structure of the electron injecting layer. The organic electroluminescent device according to claim 4, wherein the 2-methylindole compound having the structure of the formula (I) is contained in the organic light-emitting layer. The organic electroluminescent device of claim 2, wherein the organic layer has a thickness of not more than 500 nm. The organic electroluminescent device of claim 4, wherein the organic layer has a thickness of not more than 500 nm. The organic electroluminescent device of claim 5, wherein the organic layer has a thickness of not more than 500 nm. The organic electroluminescent device of claim 6, wherein the organic electroluminescent device is a display device. The organic electroluminescent device of claim 6, wherein the organic electroluminescent device is a white light illumination device. The organic electroluminescent device of claim 7, wherein the organic electroluminescent device is a display device. The organic electroluminescent device of claim 7, wherein the organic electroluminescent device is a white light illumination device. The organic electroluminescent device of claim 8, wherein the organic electroluminescent device is a display device. The organic electroluminescent device of claim 8, wherein the organic electroluminescent device is a white light illumination device. The organic electroluminescent device of claim 2, wherein the organic electroluminescent device emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 9, wherein the display emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 10, wherein the display emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 11, wherein the display emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 12, wherein the display emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 13, wherein the display emits red, blue, green, yellow or white light. The organic electroluminescent device of claim 14, wherein the display emits red, blue, green, yellow or white light.