TW200911018A - Arylamine compound and organic light-emitting device using the same - Google Patents

Abstract

The present invention discloses an arylamine compound which can be used as the hole injection or/and hole transporting material, or/and emitting host/guest in organic electroluminescence devices. The arylamine compound is expressed as equation (I) or (II): 096130305P01.bmp 096130305P02.bmp, of which A is the same or different, being selected from a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group; Z is the same or different, being selected from a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group. R1 to R11 are individually selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted heterocyclic group. The organic light-emitting device of the present invention includes a pair of the electrode pairs containing a cathode and an anode. There exists at least a light-emitting layer formed by arylamine compound of the present invention between the electrode pairs. That layer is characterized with high efficiency, high brightness, durable long-term operation, and the emission spectra is between 500 nm - 650 nm.

Description

200911018 IX. Description of the Invention: [Technical Field 3 of the Invention] Field of the Invention The present invention relates to an arylamine compound, and a light-emitting element having the same using the compound. In particular, the present invention relates to an arylamine compound having the formula (I) or (11), and a hole injection layer or/and a hole using the arylamine compound as an organic light-emitting element (OLED). The organic light-emitting element of the transport layer, or/and the light-emitting layer. The organic light-emitting element of the present invention can reduce power consumption by extending half-lifetime and improving efficiency. The arylamine 10 compound can also emit a wide range of fluorescent wavelengths from green to red (550 nm to 650 nm). BACKGROUND OF THE INVENTION Organic light-emitting elements (OLEDs) have received a lot of attention due to their potential for use in flat panel displays. OLEDs are generally composed of functionally differentiated organic multilayers such as a 'hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EML), and an electron transport layer (ETL). The hole injection layer (hil) and the light-emitting layer (EML) have good charge carrier mobility and excellent operational durability, which can reduce the dynamic voltage and 20 power consumption of the LEDs and improve their efficiency. Half life. In particular, good fluorescence energy conversion from the object to the main body will increase the efficiency and half-life of OLEDs and reduce their power consumption. Some literatures have used related arylamine compounds as luminescent layers (guest or host)', for example, "Diaminoanthracene derivatives as High-performance Green Host Electro- 5 200911018 luminescent Materials", Chem. Mater·, 2002, 14, 3958~ 3960, Chien-Hong Cheng et al.; US Patent Application No. 2005/0064233 A1 to the company of the Japanese Patent Application No. 2005/0064 233 A1, the disclosure of which is incorporated herein by reference. A phenylene-diamine derivative as a light-emitting layer or a hole transport layer; US 2006/0113528 A1 to Canon Inc. discloses an anthracene-based amine as a light-emitting layer; Sumitomo JP 2117971 to Chem, Co. Ltd., discloses an arylamine derivative as a hole transporting material; Patent No. 2,873,548 to Band 0 Chem 10 Ind., Ltd. also discloses a use as a hole injecting material. Triphenylamine compound. The arylamine derivative, which has been taught by the prior art to emit blue light to the green region, has a range of luminescence that must be extended to the red region to provide a wider range of applications. However, aromatic compounds still need to improve thermal stability and practical operation. Especially in the purpose of industrial production, it is particularly necessary to improve the half-life and driving voltage. C is a solution of L-dissolved L 3 [Description of the Invention] The present invention provides the use of an arylamine compound and the like as an electric 20-hole injection layer or/and a hole transport layer or/and a light-emitting layer of OLEDs. These arylamine compounds can overcome the disadvantages of the prior art. One of the objects of the present invention is to improve the thermophysical properties (higher Td) of the arylamine compound. Another object of the present invention is to use the base amine compound as a hole injection layer or/and a hole transport layer or/and a light-emitting layer of the 6 200911018 OLEDs and improve the half life thereof, reduce the driving voltage, and reduce the power consumption and improve the efficiency. . Still another object of the present invention is to expand the working wavelength of the arylamine compound to the red range to provide a wider range of industrial manufacturing. 5 Shuming has an economic advantage in manufacturing #工. The present invention discloses an arylamine compound which can be used as a hole injection layer or/and a hole transport layer or/and a light-emitting layer of OLEDs. The arylamine compound is represented by the following formula: _/ and formula (II):

(I)

(11) wherein A is the same or different from each other's choice from the substituted or unsubstituted anthryl,-substituted or unsubstituted secret (Qingzhen, and - two or unsubstituted flower bases) (perylenyi); 2 each identical or different, substituted or unsubstituted phenyl, _ silk substituted for the singularity of the rape 7 10 200911018 substituted or unsubstituted ketone, and one by one substituted or unsubstituted芘基. Heart to

Substituted amino, substituted or unsubstituted alkyl, substituted aryl, substituted by aryl, substituted or unsubstituted, substituted or unsubstituted or unsubstituted heterocyclic. More specifically, the above naphthalene group is represented by the following formula:

Wherein Ru is selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group. a substituted or unsubstituted heterocyclic group. Further, the above fluorenyl group is represented by the following formula (IV):

Wherein Rh is selected from the group consisting of a hydrogen atom, an i atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group. a substituted or unsubstituted heterocyclic group. Furthermore, the fluorene group is represented by the following general formula (V): 8 200911018

Wherein Ru is selected from the group consisting of a hydrogen atom, a quiescent atom, a substituted or unsubstituted gas group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group. a substituted or unsubstituted heterogeneous group. However, the thiol group is represented by the following general formula (VI):

Wherein Rm is selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group. a heterocyclic group substituted or unsubstituted. I: Embodiment 3 Preferred Embodiments of the Invention FIG. 1 shows an embodiment of an organic light-emitting element of the present invention. 1 is a transparent electrode, 5 is a metal electrode, 2 is a hole transport layer deposited on 1, 3 is a light-emitting layer deposited on 2, and 4 is an electron transport layer deposited on 3. FIG. 2 is an organic Another implementation of the light-emitting element is a cancer sample. 1 9 200911018 is a transparent electrode, 5 is a metal electrode, 2 is a hole transport layer deposited on 1, 3 is a light-emitting layer deposited on 2, 4 is an electron transport layer deposited on 3, and 6 is inserted in a transparent The hole injection layer on the electrode 1 can improve the adhesion between the transparent electrode 1 and the hole transport layer 2, or contribute to the improvement of the hole injection capability. 5 Inventively explored herein are arylamine compounds and organic light-emitting elements using the compounds. The process, structure and components will be described in detail below. However, the invention is of course not limited to the details of those skilled in the art. On the other hand, well-known general components and programs will be omitted. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail. It is a matter of course that the invention is to be construed as broadly equivalent to the scope of the invention, and the scope of the invention is intended to cover the scope of the invention and the various possible equivalents. In the present invention, "thermal degradation temperature (Td)" means a temperature at which a weight loss of a heated sample reaches 0.5% by weight, and "Tm" means a melting point. In the first embodiment of the present invention, an arylamine compound which can be used as a hole injection layer or/and a hole transport layer or/and a light-emitting layer of OLEDs will be explained. The arylamine compound is represented by the following formula (1) or / and formula (II): 10 (I) 200911018

/, A, respectively, the same or different, selected from thiol substituted or unsubstituted thiol, unsubstituted by $, and - substituted or unsubstituted kenyl 'Z are identical or different' It is selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 1 group, and a disubstituted or unsubstituted group. Ri to R" are each independently selected from a nitrogen', a subhalogen atom, a substituted or unsubstituted amino group, a substituted oxime, no (4) '--unreduced green,-substituted or unsubstituted aromatic silk , -Alternative or unsubstituted heterocyclic groups. In the present embodiment, a part of the arylamine compound of the present invention will be shown, and the arylamine compound is not limited to the examples shown below. 11 200911018

12 200911018

13 200911018

14 200911018

15 17200911018

18

16 20 21 200911018

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17 200911018 The present invention will be described in more detail based on the following examples. Example 1 Synthesis of Example Compound No. 2

Synthesis of N,N-dimethylphenyl)anthracene-10-amine (N,N-di-(p-tolyl) anthracene-10-amine) 15 g (58.3 mmol) of 9- Desert, 13.8 g (70 mmol) p, 〆-xylyleneamine (/^/?, -ditoylamine), 0.15 g (0.58 mmol) of acetic acid! A mixture of Palladium (II) acetate, 8.4 g (87.5 mmol) of sodium t-butoxide and 225 ml of dry toluene was refluxed under nitrogen for 24 hours, then cooled to room temperature, and the reaction mixture was washed with water. And dried with MgS04. Most of the solvent was removed under reduced pressure to give a yellow precipitate which was dried to give 13 g of product. Yield = 60%.

Synthesis of 9-bromo-N,N-dimethylphenyl)indole-10-amine 13 g (34.8 mmol) of N,N-dimethylphenyl)indole-10-amine and 18 200911018 260 ml of DMF were stirred at room temperature. A mixed solution of 6 lg (34.8 mmol) of N-bromosuccinimide and 60 ml of DMF was added dropwise, and then stirred overnight at room temperature. The reaction mixture was poured into water, and the precipitate was filtered and washed with toluene to afford 116 g of an orange product. Yield 5 = 75%.

N10' Synthesis of N10-(9-(di-cadaverium-nonylphenylamino)indole_10-yl)-7, N9 (p-fluorenylphenyl)fluorene-9,10-diamine 10 gives 〇.5g ( 4.67 mmol) of toluidine, 4 4 g (9 8 mmol) of 9-bromo-indole, fluorene-di-(/>-tolyl) 蒽-l〇-amine, 〇〇 5 g (〇234 A mixture of (II), 1.34 g (14 mm )l) of sodium t-butoxide and 3 〇mi of toluene was refluxed under nitrogen for 24 hours and then cooled to room temperature. The precipitate was filtered and washed with methanol to give an orange product. Received ‧ team noon ~ ~ 5〇%. Further purification is carried out by sublimation. The product was confirmed via FAB-M_, m/s = 850. 19 15 200911018 Example 2 Synthesis of Example Compound No. 6

Synthesis of N,N-di-indolyl-indenyl pyren-1-amine 3 g (0-107 mol) of 1-bromo, 25.3 g ( a mixture of 0.128 mol) of xylylamine, 0.24 g (1.07 mmol) of palladium(II) acetate, 15.4 g of sodium iodide and 450 ml of toluene was refluxed under nitrogen for 24 hours and then 10 hours. Cool to room temperature and rinse the reaction mixture with water and dry with MgS04. Most of the solvent was removed under reduced pressure to give a yellow precipitate which was dried to give 31.5 g. Yield = 74%.

Synthesis of 6-actino-indole, fluorene-di-toluene-forming amines 15 g (37-7 mmol) of hydrazine, hydrazine-di-(p-methylphenyl)-l-amine and i5 〇ml & CH2Cl2 at room temperature After stirring, a mixed solution of 6 g (37.7 mmol) of N-bromosuccinimide and 60 ml of CH 2 C 12 was added dropwise, followed by stirring at room temperature for 20 200911018 overnight. The reaction mixture was washed twice with water and washed with saturated NaHC.sub.3 and then dried. The solvent was removed by subtraction, and the residue was subjected to a secondary recrystallization procedure from CH.sub.2 C.s. Yield = 14%.

Synthesis of 1^-(6-(xylylamino)indol-1-yl)-N1,N6, N6-tris(/?-indolephenyl-1,6-diamine to give 0.5 g (4.67 mmol) Toluidine, 4.6 g (9-8 mmol) of 6-indolizine, hydrazine-di-(/?-tolyl)-l-amine, 0.05 g (0.234 mmol) of acetic acid! Bar (II), 1.34 A mixture of g (14 mmol) of sodium tert-butoxide and 30 ml of toluene was refluxed under nitrogen for 24 hours, then cooled to room temperature. The precipitate was filtered and washed with methanol to give an orange product. Yield = 55%. The sublimation effect was purified. The read product was determined by FAB-MS, m/s = 898. 15 Example 3 Synthesis of Example Compound No. 11 21 200911018

Synthesis of N9,N10-xylyl)hydrazine-9,10-diamine (>19,;1010-out-〇-tolyl) anthracene-9,10-diamine ) 10 g (29.7 mmol) of 9,10 - dibromofluorene, I9g (i78.2 mmol); ?-5 toluidine, 0.4 g (1.782 mmol) of palladium (II) acetate, i7.ig (i78.2 mmol) of sodium t-butoxide and 100 ml of toluene The mixture was refluxed under nitrogen for 24 hours' then cooled to room temperature. The precipitate was filtered and washed with methanol, and purified to afford a 6 g of orange precipitate. Yield = 52%.

Synthesis of N10-(4-(9-(di-homo-tolyl)indole-10-yl)tolyl)amino) 蒽-10-yl)-N9,N9,N10-tris(p-fluorenylphenyl)蒽_9,1〇_Diamine will be 0.76g (1.95mmol) of N9,N10-di-(p-tolyl)蒽_9,1〇_二22 200911018

(X〇2g_98mmol) of acetic acid, (11), 〇56 with a mixture of 5 85 〇1) of tert-butanol and 20 ml of toluene

Example 4 Synthesis of Example Compound No. 16

Synthesis of NW-di-tolyl) stupid 1}4-diamine (Nl, N4_di order t〇lyl) benzene-1,4-diamine) 10 g (42.4 mmol) of 1,4-dibromobenzene, 22.7 g (〇.2i2mol) of a mixture of toluidine, O.lg (〇.424 mmol) palladium acetate (II), 24.4 g (0.254 mol) of 15 sodium butoxide and 225 ml of toluene were refluxed under nitrogen for 24 hours. 'The mixture was then cooled to room temperature, and the reaction mixture was washed with water and dried with MgSO 4 to remove solvent. Yield = 73%. 23 200911018

Synthesis of N1G-(4-(9-(di-p-indolyl)amino)indole-10-ylindole phenyl)amino)phenyl)-N9,N9,N1()-triphenylene) - 蒽-9,10-diamine 5 0.7 g (2.42 mmol) of β, Ν4-di-(p-tolyl)benzene-1,4-diamine, 2.3 g (5.1 mmol) of 9-bromo- Ν, Ν-bis-(ρ-fluorenylphenyl)fluorene-10-amine, 0.025 g (0.121 mmol) of acetic acid, a mixture of (II), 0.7 g (7.26 mmol) of sodium t-butoxide and 20 ml of toluene It was refluxed under nitrogen for 24 hours and then cooled to room temperature. The precipitate was filtered and washed with methanol to give &lt Yield = 56%. Further purification is carried out by sublimation. The product was confirmed by FAB-MS, m/s = 1031. Example 5 Synthesis of Example Compound No. 22 24 200911018

Synthesis of 1^-(4-((6-di-n-phenyl)amino)3⁄4]•yl)(p•methylphenyl)amino)phenyltris(p-methylphenyl)H,6_2 Amine (#(4-((6-5 (di-〇?-tolyl)amino)pyren-1 -yl)(/?-tolyl)amino)phenyl)-N1 ,Ν6, N6-tri-(/?- Tolyl)pyrene-1,6-diamine ) 0.7 g (2.42 mmol) of W4-di-(/?-tolyl)benzene-1,4-diamine, 1.15 g (5.1 mmol) of 6-bromo-indole a mixture of bismuth-bis(p-methylphenyl)fluoren-1-amine, 0.025 g (0-121 mmol) of palladium acetate (n), 〇.7 g (7.26 mmol) of tert-butanol 10 sodium and 20 ml of toluene under nitrogen It was refluxed for 24 hours and then cooled to room temperature. The precipitate was filtered and washed with methanol to give 1.7 g of an orange product. Yield = 65%. Further purification is carried out by sublimation. Confirmation of product by FAB_MS determination, m/s = 1073 General method for the preparation of OLEDS 15 ITO-coated glass with 15 Ω α-1 and thickness 1500 μηη

Sanyo Vacuum 'hereinafter referred to as "substrate") is washed several times in an ultrasonic bath (ultrasonic 25 200911018 bath, for example, with detergent, or deionized water). After the vapor deposition of the organic layer, the cleaned IT substrate was further treated with UV and ozone. The organic layers are sequentially deposited on the ITO substrate by vapor deposition in high vacuum units (10-6 Torr) in 5, such as resistively heated quartz boats. The thickness of each layer and the vapor deposition rate (0_1 to 0.3 nm/sec) are closely monitored or controlled by means of a quartz crystal monitor. As noted above, the layers may individually contain more than one compound, i.e., typically doped with a guest 10 material in a host material. This is done by co-evaporation (c〇_vap〇riza_ tion) from two or more sources. The arylamine compound of the present invention represented by the above formula (I) and formula (II) can be used as a hole injection layer or/and a hole transport layer or/and a light-emitting layer of OLEDs. Other general and well-known OLED materials can be used in conjunction with the present invention 15 but are not limited to the examples shown below. Common and well-known hole injection materials for OLEDs include: Phthalocyanine, copper complex (CuPC), 4', 4"-tris(N-(2-naphthyl)-N -phenyl-amino)triphenyl-amine (2-TNATA), 4,4,4 di-(N-3-methylphenyl-N-phenyl-amino)triphenylamine 20 (m -MTDATA) N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), etc. Ν,Ν'-bis(naphthalen-1-yl)-N,N' - Bis(phenyl)-benzidine (NPB) is the most widely used material for the hole transport layer, and other examples are N, N'-bis(3-methylphenyl)·Ν, Ν, - Bis(phenyl)-benzidine (TPD), 26 200911018 2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9,-spiral bismuth (Spiro-TAD ), 9.9-bis[4-(vanosei-diphenyl-4-yl-amino)phenyl]-911-苐(8?8??), 9.9-bis[4-(N,N- Bis-naphthyl-2-yl-amino)phenyl]-9H-indole (NPAPF), 2,2',7,7'-tetra[N-naphthyl(phenyl)amino]-9,9 -Spiro-NPB, 5 Ν, Ν'-bis(phenanthr-9-yl)-N,N,-bis(phenyl)-benzidine (PAPB), 2.7- [N,N- (9,9-spiro-dip-2-yl)-9,9-spiral-biquinone ( Spiro-5), etc. Tris-(8-hydroxyquinoline)aluminum (Alq3) is most widely used as a material for the electron transport/light-emitting layer in OLEDs due to its high thermal stability and good film formability. The thermal degradation temperature (Td) is about 303. (: Other electric 10 transport materials may, for example, be 2-(4-biphenyl)-5-(4-tertl-butylphenyl)-1, 3,4-oxadiazole (PBD), 2,2,2-(l,3,5-Benzinetriyl)-tris(l-phenyl-lH-benzimidazole) (TPBi), 4.7-diphenyl-1,10 -Bphenyphene (Bphen), 15 H4_biphenyl)·4_stupyl-5-tert-butylphenyl-1,2,4-tris(TAZ), I,3·double [2 -(4-tert-butylphenyl)_ι,3,4·oxadiazolyl]benzene (〇XD_7), 1,3-bis[2-(2,2'-biazetidine)_ι,3 , 4-oxadiazol-5-yl]benzene (Bpy-OXD), 1,3-bis[2-(2,2'-bipyridin-5,5'-diindenyl)_1,3, 4- oxadiazol-5-yl]benzene 20 (Bfpy-OXD), 2.7-bis[2-(2,2'-bipyridin-6-yl)-l,3,4-oxadiazole-5- Benzo-9,9-dimethylhydrazine (Bpy-FOXD), 2.9-bis(naphthalen-2-yl)-4,7-diphenyl-l,l-phenanthroline (NBphen), double (2-methyl-8-hydroxyindole) _4_(phenylbenzene) jgaiq) and so on. 27 200911018 2,3,6,7-tetrahydro-1,1,7,7-tetramethylval 5H11H Lu (2_benzopolizine-[9,9a,lgh]coumarin (C545T) widely The ground is used as a green light object to co-evaporate with the main body (Butter 3) as a green light emitting layer. 4_(dicyan〇_ methylene)-2-t-butyl-6-(l , , ? , 7.tetramethyl. Jul_lidyl.9. 5 Vi_-4H-Pyran (DOTB) is widely used as a red light object to co-evaporate with the main body (Alw) as a red light-emitting layer. Other luminescent materials for fluorescent OLEDs (main / guest) can be, for example, 9,10-di(naphthalen-2-yl)anthracene (AND), 3-tert-butyl-9,10-mono(qin-2-yl)indole (TBAND), 10 4 , 4-bis(2,2-mono-ethyl-ethen-1-yl)-phenyl (DpvBi), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), 2, 7-Bis[9,9-bis(4-methylphenyl)- 2nd-yl]-9,9-bis(4-methylphenyl)fluoride (TDFA), 2,2 —_yl-9 , 9-spiral bismuth (2,2'-Spiro-Pye), 15 2,7-di-youji-9,9-spiral bismuth (Spiro-Pye), 1,4-two (you-1 -Phenyl (p-Bpye), 1,3-bis(you-1-yl)benzene (p-Bpye), 1,3,5-di(you-1-yl)benzene (TPB3), 2, 2,-bis(9,10-diphenyl)indole (TPBA), 20 3 , (2-benzopyrene)-7-(diethylamino)coumarin (Coumarin 6 ), Ν,Ν'-dimethyl-quinacridone (DMQA), 9.10- double [team Yiji O-Phenylphenyl)-amino] onion (1' D??), 9.10-bis[phenyl(m-methylphenyl)-amino]indole (ΤΡΑ), 4,4,-Bis(9-ethyl-3) -carbazovinylene)-l,r-biphenyl ( BCzVBi) 28 200911018 2,5,8,11-tetra-tert-butyl hydrazine (TBPe), 4,4'-bis[4_(di-fluorenyl-tolylamino)benzene Vinyl]biphenyl (DPAVBi), 4_(di-P-tolylamino)-4'-[(di-P-nonylphenylamino) stupid vinyl]diphenylethylene (DPAVB), 5 4,4'- Bis[4-(diphenylamino)styryl]biphenyl (BDAVB), N,N,-Bis(naphthale-2-yl)-N,N,-bis(phenyl)-tris-(9,9- Dimethy lfluorenylene) (BNP3FL), N-(4-(E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalene-2-yl)benzyl)-N -Phenylaniline (N-BDAVBi), 10 2,7-bis[4·(diphenylamino)styryl]-9,9-spiral double (Spiro-BDAVBi), 6-methyl-2- (4-(9-(4-(6-methylbenzo[d]thiazol-2-yl)phenyl)indole-10-yl)phenyl)benzo[d]thiazole (DBzA), (5, 6,11,12)-Tetraphenylnaphthophthalene (Rubrene), 15 2,8-II -tert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene (TBRb) or the like. € Other examples of luminescent materials (master/guest) for phosphorescent OLEDs are bis(2-methyl-8-quinoline)-4-(phenylphenolate)aluminum (BAlq), 1,3-double (carbazol-9-yl)benzene (MCP), 20 1,3,5_tris(carbazol-9-yl)benzene (TCP), 4,4',4''-tris(carbazole-9- Triphenylamine (TcTa), 4,4'-bis(carbazol-9-yl)biphenyl (CBP), 4,4'-bis(carbazol-9-yl)-2,2'-dioxin Base benzene (CDBP), 2,2',7,7,-tetrakis(carbazol-9-yl)-9,9'-spiral bismuth (Spin)-CBP), 29 200911018 9,9-double [4-(carbazol-9-yl)-phenyl]fluoro^[-208?), 1,4-bis(triphenylmethyl)benzene (UGH2), 1,3-bis(triphenylfluorenyl) Benzene (UGH3), bis(4-N,N-diethylamino-2-methylphenyl)-4-mercaptophenylmethane 5 (MPMP), tris(2-phenylacridine)indole (III (lr(ppy)3), bis(2-phenylpyridinium) (acetamidine) ruthenium (III) (lr(ppy)2(acac)), three [2-(p-toluene) 0] Silver(III) (Ir(mppy)3), bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxyacridinyl)phosphonium(III) 10 ( FIrpic ), bis(2,4-difluorophenyl "bipyridine)tetrakis (bobazole) bismuth borate (m) (FIr6), (Iridium(III) Bis(4 ,6'-difluorophenylpyridinato)tetrakis(l-pyrazolyl)borate), tris(diphenylmercaptomethane)morpholinoline (m) (Eu(dbm)3(phen)), 15 pairs (2_benzene) And [b] ° thiophene · ° pyridine) (acetamidine) ruthenium (III) (Ir (btp) 2 (acac)), bis [H9,9-dimethyl-9H-葙_2_ group ) _isoquine] (acetamidine) ruthenium (III) - (Ir(fliq)2(acac)), bis[3-(9,9-dimethyl-9H-_2-yl)-iso啥琳](乙醯丙嗣)表(hi) 20 ( Ir(flq)2(acac)), tris(2·phenylphosphonium)silver (nI)(Ir(2_phq)3), biguanide phenyl (4) (: Ethylacetone) 铱 (10) (Ir (2 · (4) 2 (acac), etc. A typical 〇LED contains a cathode formed by thermal evaporation of a low work function metal such as A, Mg, Ca, Li, and K. The low work function metal can assist 30 200911018 electron injection into the electron transport layer from the cathode. In addition, in order to reduce the electron injection barrier and improve the performance of the OLED, a film-like electron injection layer is interposed between the cathode and the electron transport layer. Conventional electron injecting layer materials are metal halides or metal oxides having a low work function such as LiF, MgO, or Li2. 5 On the other hand, after the OLEDs were fabricated, the electroluminescence EL spectrum and the CIE chromaticity coordinates were measured using a PR650 spectral scanning photometer. In addition, current/voltage, fluorescence/voltage, and luminescence/voltage characteristics were obtained using a Keithley 2400 programmable-voltage-current source (Keityley 2400 programmalbe voltage-current source). The various instruments 10 described above are operated at room temperature (about 20 ° C) and atmospheric pressure. Example 6 A red organic light-emitting element (OLED) was fabricated and tested according to the above general method. The structure of the OLED (please refer to FIG. 2) is as follows: ITO glass substrate / compound number 2 (80〇A) / NPB (15 〇A)/Balq+l〇% 15 Ir(2-phq)3 ( 350A ) /Bfpy-OXD ( 350A ) /LiF ( 5A ) /A1 ( 1600 A). It has an emission intensity of 14100 cd/m2 at an applied voltage of 9 V, and an energy use efficiency of 1.88 lm/W is obtained. The CIE chromaticity coordinates (x, yH 〇.57, 0.43) have a half-life of 430 hours at an initial intensity of 3000 cd/m2. Example 7 20 An OLED having the same structure and thickness as that of Example 6 was produced by substituting Compound No. 6 for Compound No. 2. It has an emission intensity of 16000 cd/m2 at an applied voltage of 9 V, and an energy use efficiency of 1.69 lm/W is obtained. The CIE chromaticity coordinate (x, y) = (0.56, 0.44), and the half-life is 480 hours at an initial intensity of 3000 cd/m2. 31 200911018 Example 8 An OLED having the same structure and thickness as that of Example 6 was produced by substituting Compound No. 22 for Compound No. 2. It has an emission intensity of 13500 cd/m2 at an applied voltage of 9 V, and an energy use efficiency of 2·12 lm/W is obtained. The CIE chromaticity coordinate (x, y) = (〇.57, 0.43), and the half-life is 390 hours at an initial intensity of 3000 cd/m2. Comparative Example 1 A ruthenium LED having the same structure and thickness as that of Example 6 was produced by dividing 2T-NATA (hole injection material) in place of the compound No. 2. It has an emission intensity of 3400 cd/m 2 at a voltage of 10 of 9 V, and an energy use efficiency of 2. 〇 1 lm/W is obtained. The CIE chromaticity coordinates (x, y) = (〇.53, 0.46), and the half-life is 125 hours at an initial intensity of 3000 cd/m2. Example 9 A red organic light-emitting element 15 (OLED) was fabricated and tested according to the above general method. The structure of the OLED (please refer to FIG. 1) is as follows: ITO glass substrate / compound number 2 (80 A) / NPB ( 15〇A)/Alq3+2% Compound No. 16 (40〇A) /Alq3(30〇A) /LiF(5A) /Al(1600 A). It has an emission intensity of 2260 cd/m2 at an applied voltage of 9 V, and an energy use efficiency of 1.29 lm/W is obtained. The CIE chromaticity coordinate (x, y) = (〇.53, 20 0.44), in the case of an initial intensity of 1000 cd/m2, the half-life is 360 hours. Example 10 An OLED having the same structure and thickness as that of Example 9 was prepared by substituting Compound No. 11 for Compound No. 16. It has an emission intensity of 1100 cd/m2 at an applied voltage of 9 V, and an energy of 1.25 lm/W is used. 32 200911018 Efficiency. The CIE chromaticity coordinate (x, y) = (0 50, 0.48), and the half-life is 42 〇 hours in the case of an initial intensity of 100 cd/m 2 . Comparative Example 2 An OLED having the same structure and thickness as that of Example 9 was produced by dividing DCJTB (-red light guest) with compound No. 16. It has an emission intensity of 2400 cd/m2 at an applied voltage of 9 V, and an energy use efficiency of 1.45 lm/W is obtained. The CIE chromaticity coordinates (x, y) = (〇.57, 0.41), and the half-life is 165 hours at an initial intensity of 1000 cd/m2. The above preferred examples show that the arylamine compound has good hole-injection and luminescent properties, high thermal stability, and practical operational durability. Good performance can be obtained by using the arylamine compound of the present invention to produce a red light-emitting organic electroluminescent device. In particular, the arylamine compound can be used as a red light guest of the light-emitting layer because its photoluminescence (PL spectrum) is above 6 〇〇 nm of the photoluminescence spectrum (see Fig. 4). Further, the arylamine compound of the present invention 15 shows a high 1^/1111! (see Fig. 5 and Fig. 0), and remains solid under the sublimation/deposition procedure. This makes the arylamine compound of the present invention suitable for industrial implementation. In summary, the present invention discloses a 20 arylamine compound which can be used as an electron beam implantation or/and a hole transporting material or/and an illuminating host/guest in an organic electroluminescent device. The arylamine compound is represented by the following formula (I) or / and formula (II) 33 (I) 200911018 (I) /

R2

Re (II) jc, from a substituted or unsubstituted sulfhydryl group and eight A each being the same or different, selected (anthryn, 10 y) - substituted or unsubstituted pyrypy (pyreny), and 〆 substituted: Substituted perkylenyl; 2 each identical or different, selected from substituted or unsubstituted phenyl, substituted filamentary naphthyl, substituted or unsubstituted onion, and - substituted or Unsubstituted Yuji. ～Rn are each independently selected from a hydrogen atom, a functional atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group. An alkyl group, a substituted or unsubstituted heterocyclic group. 34 200911018 [Simple Description of the Drawings] Fig. 1 is an embodiment of the organic light-emitting element of the present invention. Fig. 2 is another embodiment of the organic light-emitting element of the present invention. Figure 3 is the absorption and luminescence spectra of Example Compound No. 2. 5 Figure 4 is an absorption and luminescence spectrum of Example Compound No. 16. Figure 5 is a graph showing the thermal degradation temperature (Td) and melting point (Tm) of Example Compound No. 2. Figure 6 is the thermal degradation temperature (Td) and melting point (Tm) of Example Compound No. 16. 10 [Description of main component symbols] 1 ..............Transparent electrode 2 ..............Cell transport layer 3 ... ........ luminescent layer 4 ..............electron transport layer 5 ..............metal electrode 6 .... .......... hole injection layer 35

Claims (1)

200911018 X. Patent Application Range: 1. An arylamine compound represented by the following general formula (I) or formula (II): Wherein, each A is the same or different, and is selected from a substituted or unsubstituted 5 fluorenyl group, a substituted or unsubstituted thiol group, and a substituted or unsubstituted thiol group; Z is the same or different, and is selected a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted fluorenyl group; each of which is independently selected from the group consisting of hydrogen Atom, a halogen atom, a substituted or unsubstituted amino group 10, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a monosubstituted or unsubstituted aralkyl group, a substituted or unsubstituted Heterocyclic group. 2. The compound according to claim 1, wherein the naphthyl group is represented by the following formula (III): 36 200911018 Wherein R" is selected from a hydrogen atom, a - atom, a substituted or unsubstituted amino group, a substituted or unsubstituted filament, a substituted or unsubstituted aryl group, a substituted or unsubstituted branch, A substituted or unsubstituted heterocyclic group. 3. For example, Shenqing Patent System No. 1 is a slave compound, and its ‘I base is expressed by the following formula (IV): 10 VIII, R14 is selected from the group consisting of a hydrogen atom, a (tetra), a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group or an unsubstituted base group, a substituted group. Or unsubstituted heterocyclic group. 4. The scope of the patent application formula (V) represents: a compound according to item 1, wherein the oxime group is below R15 (V) wherein 'R14 is selected from a hydrogen atom minus, a substituted or unsubstituted, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted 37 15 200911018 aryl' Heterocyclic group. 5. If the aralkyl group is substituted or unsubstituted, once substituted or not mentioned, the compound described in Item 1 Shot, W«, once substituted or unsubstituted from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic earth, a 'substituted or unsubstituted aryl 7 group, a substituted or unsubstituted heterocyclic group. 10 6. If you apply for the patent scope, item 1 is printed ##. A compound which has been planted, wherein Ri to Rn are selected from alkyl groups having 1 to 8 carbon atoms. 7. The compound described in Item 1 of (4) is a methyl group which is independently or independently dependent on each other. 8. A compound as claimed in claim 1 wherein R, to Rn are each independently or independently dependent n-butyl. An organic light-emitting element comprising: an electrode pair consisting of a cathode and a tantalum anode and a layer comprising at least one compound (4) represented by the lower or/and formula (U) between the pair of electrodes, 38 200911018 Wherein, each A is the same or different, and is selected from a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted fluorenyl group; Z is the same or different, and is selected A substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted thiol group; each of which is independently selected from the group consisting of a hydrogen atom, an atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl 10 group, a monosubstituted or unsubstituted aralkyl group, a substituted or unsubstituted Heterocyclic group. 10. The organic light-emitting device according to claim 9, wherein the naphthyl group is represented by the following formula (III): 39 (III) 200911018 Wherein R13 is selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted gas group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group. , / substituted or unsubstituted heterocyclic group. For example, there are nine organic light-emitting elements recorded in the patent scope, wherein the 蒽-based system is represented by the following general formula (IV): (IV) 10 wherein 'Rm is selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted heterocyclic group. The organic light-emitting element according to claim 9, wherein the base system is represented by the following general formula (V) (V) The complex φ Rl4 is selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group of 40 15 200911018, once substituted or unsubstituted An aralkyl group, a substituted or unsubstituted heterocyclic group. 13. The organic light-emitting device of claim 9, wherein the fluorene group is represented by the following formula (VI): Wherein Rm is selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted heterocyclic group. The organic light-emitting device according to claim 9, wherein the one to Ru is selected from the group consisting of an alkyl group having 1 to 8 carbon atoms. 15. The organic light-emitting element of the invention of claim 9 wherein each of & to Rii is independently or independently dependent. 16. The organic light-emitting device according to claim 9, wherein the center to 15 Rl1 is independently or independently a n-butyl group. 17. The organic light-emitting device according to claim 9, wherein the arylamine compound is used as a hole injection layer or/and a hole transport layer or/and a light-emitting layer. 18. The organic light-emitting device according to claim 9, wherein the aryl 20-amine compound is used as a hole injection layer. The organic light-emitting device according to claim 9, wherein the arylamine compound is used as a hole transport layer. 20. The organic light-emitting device according to claim 9, wherein the arylamine compound is used as a light-emitting layer. The organic light-emitting device according to claim 9, wherein the arylamine compound is used as a light-emitting layer guest. 22. The organic light-emitting device according to claim 9, wherein the arylamine compound emits a fluorescence wavelength of from 500 nm to 650 nm. 42