CN101874096A - Aorganic electroluminescent compounds and display device containing the same - Google Patents
Aorganic electroluminescent compounds and display device containing the same Download PDFInfo
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- CN101874096A CN101874096A CN200780101753A CN200780101753A CN101874096A CN 101874096 A CN101874096 A CN 101874096A CN 200780101753 A CN200780101753 A CN 200780101753A CN 200780101753 A CN200780101753 A CN 200780101753A CN 101874096 A CN101874096 A CN 101874096A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The present invention relates to an organic electroluminescent compound and a display device using the same. The electroluminescent compound according to the present invention has good luminous efficiency and excellent lifetime of the material, so that an OLED device having very good operation lifetime can be prepared.
Description
Technical field
The organic electroluminescent compounds of the novelty shown in the present invention relates to and the display device that comprises this compound.
Background technology
The most important factor that exploitation has high-level efficiency and long-life organic electroluminescent (EL) device is that exploitation has high performance electroluminescent material.
Under the blue light-emitting situation,, will be favourable aspect luminous efficiency if the light emission wavelength moves to long wavelength's direction.But, this material is applied to high-quality indicating meter and is not easy, reason is that pure blue can not be satisfactory.In addition, also there are some problems aspect purity of color, efficient and the thermostability.
For blue light material, since Idemitsu Kosen Co., Ltd. (Idemitsu-Kosan CompanyLimited) since European patent is openly announced the research and development that disclosed DPVBi (compound a) in No. 1063869, people have developed many materials, and commercialization.Up to now, the distyryl compound of known Idemitsu Kosen Co., Ltd. (distryl compound) system has top efficiency, and power efficiency is 6lm/W, and useful device lifetime was greater than 30,000 hours.But when being applied to full-color display, because purity of color descends with driving time, its life-span has only several thousand hours.
[compound a]
Meanwhile, Kodak (Kodak) is at United States Patent (USP) the 6th, 465, and the dinaphthyl anthracene compound (compound b) that discloses in No. 115 is the compound that is called as the HTL material, and this material also can be used as blue coloured electroluminous compound.But these compounds are having problem to be solved aspect luminous efficiency and the purity of color.
[compound b]
Recently, LG chemical company (LG Chem) has disclosed the electroluminescent derivative (compound c) in the similar scope of compound b in WO2006/25700.But also there is defective in compound c aspect luminous efficiency and the purity of color.
[compound c]
Meanwhile, people have developed following system and also have been extensive use of as green fluorescent material: in this system, with coumarin derivatives (compound d, C545T), quinacridone derivative (Verbindung), DPT (compound f) etc. extremely go among the AIq (main body) as doping agent greater than 20% doped in concentrations profiled with percentum.Although conventional electroluminescent material has good initial luminous efficiency performance at actual application level,, there is very big problem in these materials because starting efficiency significantly reduces aspect the life-span.Therefore, the application of these materials in the high-performance panel of large-size screen is restricted.
People have reported that this is short the causing of life-span owing to the cationic form of the AIq that is used as main body.In order to overcome this problem, people press for and develop the main body that has amphoteric properties, simultaneously cationic form and anionic form are had stability.
[compound d]
[Verbindung]
[compound f]
Summary of the invention
Technical problem
The objective of the invention is to overcome above-mentioned problem, electroluminescent compounds is provided, the character that wherein is used as the main body of solvent or energy carrier in electroluminescent material is compared with the material of routine and is obtained to significantly improve.In addition, purpose of the present invention comprises provides a kind of blueness or green electroluminescent material, obtains the luminous efficiency of this material and device lifetime to improve, and a kind of organic electroluminescence device that comprises described electroluminescent material also is provided.
Technical scheme
The present invention relates to the organic electroluminescent compounds that Chemical formula 1 is represented:
[Chemical formula 1]
R1 to R3 represents phenyl or C10-C20 fused polycycle aromatic ring independently in the formula, the phenyl of described R1 to R3 or C10-C20 fused polycycle aromatic ring can further be replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen, the C5-C7 cycloalkyl, phenyl or condensed polyaromatic; The invention still further relates to the display device that uses described compound.
From in broad terms, the electroluminescent material that the present invention mentioned comprises any material that can be used as the organic substance in the organic electroluminescence device, and described organic electroluminescence device is by forming with the lower section: first electrode, second electrode and the organic substance between described first electrode and second electrode; And from narrow sense, electroluminescent material comprises those materials that are applied to the electroluminescent main body, described electroluminescent main body in electroluminescence layer as electroluminescent medium.
In the represented compound of Formula I of the present invention, R1 to R3 is independently selected from phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, fluoranthene base (fluorancenyl), pyrenyl, perylene base or naphthacenyl; And phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, fluoranthene base (flurorancenyl), pyrenyl, perylene base and naphthacenyl are randomly replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen atom, C5-C7 cycloalkyl, phenyl, or condensed polyaromatic.The organic electroluminescent compounds that Chemical formula 1 of the present invention is represented can be represented with following structural formula, but scope of the present invention is not limited to these structural formulas:
The present invention also provides a kind of organic electroluminescence device, and this device is by first electrode; Second electrode; And the one or more organic layers compositions between described first electrode and second electrode, described organic layer comprises the compound that one or more Chemical formula 1s are represented:
[Chemical formula 1]
R1 to R3 represents phenyl or C10-C20 fused polycycle aromatic ring independently in the formula, the phenyl of described R1 to R3 or C10-C20 fused polycycle aromatic ring can further be replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen, C5-C7 cycloalkyl, phenyl or condensed polyaromatic.
The feature of organic electroluminescent of the present invention (EL) device is, described organic layer comprises the EL district, and described EL district comprises one or more compounds of one or more EL doping agents and chemical formula (1) expression as the EL main body.The EL doping agent that is applied to organic EL device of the present invention is had no particular limits, but one of Chemical formula 2-4 has been represented some examples of this compound:
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In chemical formula 3 and chemical formula 4, Ar1 and Ar2 are the indenofluorene of following chemical formulation independently, fluorenes or spiral shell fluorenes:
R11 to R16 is independently selected from the C1-C20 alkyl in the formula, and the phenyl or naphthyl with C1-C5 alkyl substituent, does not perhaps have the phenyl or naphthyl of C1-C5 alkyl substituent;
Ar3 to Ar6 is independently selected from C5-C20 aromatic ring or many cyclophanes ring; Prerequisite is that Ar1 is identical with Ar2, and Ar3 is identical with Ar5, and Ar4 is identical with Ar6.
A and B represent chemical bond independently, perhaps
Or
R17 and R18 represent aromatic ring or many cyclophanes ring independently, and wherein two or more aromatic rings condense;
R19 to R22 represents the C1-C20 alkyl that has halogenic substituent or do not have plain substituent straight or branched independently;
R23 to R26 represents hydrogen or aryl independently;
Ar7 to Ar10 represents aromatic ring or many cyclophanes ring independently, and wherein two or more aromatic rings condense.
The object lesson of the compound of chemical formula 3 or chemical formula 4 is the compounds shown in one of following formula:
R19 to R22 represents methyl or ethyl in the formula.The example of green EL compound can be the compound of one of following chemical formula 5-7 expression:
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
In chemical formula 6 and chemical formula 7, R27 and R28 represent many cyclophanes ring independently, and wherein two or more aromatic rings condense; R29 to R32 represents aromatic ring independently; Each aromatic ring of R27 to R32 can further be replaced by the C1-C20 alkyl.
The object lesson of the compound of chemical formula 6 and chemical formula 7 can be the compound shown in one of following formula:
[description of drawings]
Fig. 1 shows the luminous efficiency-current density character of comparative example 1;
Fig. 2 shows current density-voltage character of the blue OLED of embodiment 9;
Fig. 3 shows luminous efficiency-current density character of the blue OLED of embodiment 9;
Fig. 4 shows luminous efficiency-lightness properties of the green OLED of comparative example 2, and this green OLED uses conventional electroluminescent material;
Fig. 5 shows luminous efficiency-current density character of the green OLED of embodiment 22;
Fig. 6 shows luminous efficiency-current density character of the green OLED of embodiment 22, comparative example 3 and comparative example 4;
Fig. 7 is the curve of purity of color of the green OLED of comparing embodiment 22 and comparative example 2.
Embodiment
With reference to following examples, about the method for preparing novel organic EL compound of the present invention the present invention is further described, these embodiment only are used to illustrate, but are not used for limiting the scope of the invention.
The preparation of the compound that [preparation embodiment] Chemical formula 1 is represented
The preparation of compound 12
At toluene: dissolving 9-bromo anthracene (58.3 millis rub) in the mixing solutions of ethanol (2: 1 v/v), boric acid (boronic acid) derivative (compound 11,70.0 millis rub) and tetrakis triphenylphosphine palladium (0) (Pd (PPh3) 4) (5.8 rub in the least).After the aqueous sodium carbonate that wherein adds 2M, the mixture of gained 120 ℃, under refluxad stirred 5 hours.Cool the temperature to 25 ℃ then, by adding the feasible reaction of distilled water quencher.Use ethyl acetate extraction, dry under reduced pressure, use tetrahydrofuran (THF) and recrystallizing methanol then, make compound (12).
The preparation of compound (13)
Under nitrogen atmosphere, compound (12) (46.0 millis rub) and the N-bromosuccinimide (50.6 millis rub) that as above makes is dissolved in the methylene dichloride.The solution of gained stirred 5 hours down at 25 ℃ then.Make this reaction quencher by adding distilled water.Use dichloromethane extraction, dry under reduced pressure, with tetrahydrofuran (THF) and methane recrystallization, make compound (13).
The preparation of compound (2)
The compound (13) (39.0 millis rub) that as above makes is dissolved in the tetrahydrofuran (THF) of meticulous purifying.With the solution quenching of gained to-78 ℃, to wherein slowly adding n-Butyl Lithium (1.6M hexane solution) (46.8 millis rub).After this mixture stirring 1 hour, add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two oxa-boron pentamethylene (78.0 millis rub).Slowly be warming up to 25 ℃, this mixture stirred 1 day.By adding the feasible reaction of distilled water quencher, this mixture ethyl acetate extraction is dry under reduced pressure then.With tetrahydrofuran (THF) and recrystallizing methanol, make compound (2).
The preparation of compound (3)
With 2-chloro-9,10-anthraquinone (29.7 millis rub), compound (2) (35.5 millis rub), tetrakis triphenylphosphine palladium (0) (Pd (PPh3) 4) (3.0 millis rub) and aliquat 336 (Aliquat 336) (3.0 millis rub) are dissolved in the toluene.After the wet chemical that wherein adds 2M, the mixture of gained under refluxad stirred 3 hours.Temperature is reduced to 25 ℃ then, makes this reaction quencher by adding distilled water.Use ethyl acetate extraction, dry under reduced pressure, with methyl alcohol and tetrahydrofuran (THF) recrystallization, make compound (3).
The preparation of compound (6)
Add tetrahydrofuran (THF) in bromo compound (compound 4 or 5) (54.3 millis rub), this mixture stirred 10 minutes at 25 ℃, made and dissolved fully.Quenching extremely after-72 ℃, slowly drips n-Butyl Lithium (hexane solution of 2.5M) (65.1 millis rub).After 1 hour, to wherein adding compound (3) (21.7 millis rub), temperature slowly is elevated to 25 ℃.After this reaction mixture stirred 26 hours, to wherein adding saturated aqueous ammonium chloride solution, the mixture of gained stirred 1 hour.Under reduced pressure, filter, separate organic layer, evaporate, make compound (6).
The preparation of compound (1)
With the compound (6) (21.7 millis rub) that as above makes, potassiumiodide (KI) (86.8 millis rub) and a hypophosphite monohydrate sodium (NaH2PO2H2O) (130.2 millis rub) are dissolved in the acetate, and this solution under refluxad stirred 21 hours.Solution is cooled to after 25 ℃, under agitation adds water, the solid that produces is filtered.The solid that obtains with methyl alcohol, ethyl acetate and tetrahydrofuran (THF) washing, obtains shallow eburneous solid target compound (1) successively.
The preparation of [preparation embodiment 1] compound (101)
The preparation of compound (300)
With 9-bromo anthracene (15.0g, 58.3 milli rubs), phenyl-boron dihydroxide (compound 200) (8.5g, 70.0 millis rub) and tetrakis triphenylphosphine palladium (0) (Pd (PPh3) 4) (6.7g, 5. milli rubs) are dissolved in the mixing solutions of toluene (300 milliliters) and ethanol (150 milliliters).To the aqueous sodium carbonate that wherein adds 2M (145 milliliters) afterwards, the mixture of gained stirred 5 hours under 120 ℃ reflux conditions.Cool the temperature to 25 ℃ then, by adding the feasible reaction of distilled water (150 milliliters) quencher.With ethyl acetate (200 milliliters) extraction, dry under reduced pressure, use tetrahydrofuran (THF) (20 milliliters) and methyl alcohol (300 milliliters) recrystallization then, make compound (300) (12.0g, 47.2 millis rub).
The preparation of compound (400)
Under nitrogen atmosphere, compound (300) (11.7g, 46.0 millis rub) and N-bromosuccinimide (9.0g, 50.6 millis rub) are dissolved in the methylene dichloride (360 milliliters).The solution of gained stirred 5 hours at 25 ℃ then.By adding the feasible reaction of distilled water (300 milliliters) quencher.With methylene dichloride (200 milliliters) extraction, dry under reduced pressure, use tetrahydrofuran (THF) (20 milliliters) and methyl alcohol (200 milliliters) recrystallization then, make target compound (400) (13.0g, 39.0 millis rub).
The preparation of compound (500)
(13.0g, 39.0 millis rub) is dissolved in the tetrahydrofuran (THF) (200 milliliters) of meticulous purifying with compound (400).The solution quenching of gained is to-78 ℃, to wherein slowly adding n-Butyl Lithium (hexane solution of 1.6M) (29.3 milliliters, 46.8 millis rub).After this mixture stirring 1 hour, add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two oxa-boron pentamethylene (15.9 milliliters, 78.0 millis rub).Temperature slowly is elevated to 25 ℃, and this mixture stirred 1 day.Add after the feasible reaction of distilled water (200 milliliters) quencher, this mixture is with ethyl acetate (300 milliliters) extraction, and is dry under reduced pressure.With tetrahydrofuran (THF) (20 milliliters) and methyl alcohol (200 milliliters) recrystallization, make target compound (500) (13.5g, 35.5 millis rub).
The preparation of compound (600)
With 2-chloro-9,10-anthraquinone (7.2g, 29.7 millis rub), compound (500) (13.5g, 35.5 millis rub), tetrakis triphenylphosphine palladium (0) (Pd (PPh3) 4) (3.5g, 3.0 milli rubs) and aliquat 336 (336,1.4 milliliters of Aliquat, 3.0 rub in the least) be dissolved in the toluene (300 milliliters).To the wet chemical that wherein adds 2M (150 milliliters) afterwards, the mixture of gained under refluxad stirred 3 hours.Cool the temperature to 25 ℃ then, by adding the feasible reaction of distilled water (100 milliliters) quencher.With ethyl acetate (200 milliliters) extraction, dry under reduced pressure, use methyl alcohol (200 milliliters) and tetrahydrofuran (THF) (50 milliliters) recrystallization then, make target compound (600) (10.0g, 21.7 millis rub).
The preparation of compound (700)
Tetrahydrofuran (THF) (250 milliliters) is added 2-naphthalene bromide (11.2g, 54.3 millis rub), and this mixture stirred 10 minutes at 25 ℃, made and dissolved fully.Quenching extremely after-72 ℃, slowly drips n-Butyl Lithium (hexane solution of 2.5M) (26.0 milliliters, 65.1 millis rub).After 1 hour, to wherein adding compound (600) (10.0g, 21.7 millis rub), temperature slowly is elevated to 25 ℃.This reaction mixture stirred 26 hours, and to wherein adding ammonium chloride saturated aqueous solution, the gained mixture stirred 1 hour then.Filter under reduced pressure, separate organic layer, evaporation makes target compound (700) (15.6g, 21.7 millis rub).
The preparation of compound (101)
With compound (700) (15.6g, 21.7 milli rubs), a potassiumiodide (KI) (14.4g, 86.8 millis rub) and hypophosphite monohydrate sodium (NaH2PO2H2O) (13.8g, 130.2 milli rubs) be dissolved in the acetate (250 milliliters), this solution under refluxad stirred 21 hours then.Solution is cooled to 25 ℃, under agitation adds entry (400 milliliters) then, with the solid filtering that produces.The solid that obtains is used methyl alcohol (300 milliliters) successively, and ethyl acetate (100 milliliters) and tetrahydrofuran (THF) (50 milliliters) washing obtain shallow ivory white solid target compound (101) (10.0g, 68%).
1H?NMR(CDCl3，200MHz)δ＝7.22(m，IH)，7.32-7.35(m，12H)，7.48-7.54(m，5H)，7.67-7.73(m，13H)，7.89(m，3H)
MS/FAB:682 (measured value), 682.85 (calculated values)
[preparation embodiment 2-36]
Prepare the organic EL compound shown in the table 1 according to preparation embodiment 1 described step.The NMR numerical value of all cpds is listed in table 2.
[table 1]
[table 2]
| ??105 | ??δ7.22(m，1H)7.32-7.34(m，12H)，??7.48-7.54(m，9H)，7.65-7.73(m，13H)，??7.88(m，3H) | ??758 | ??758.94 |
| ??106 | ??δ7.21(m，1H)7.32-7.54(m，20H)，??7.67-7.73(m，14H)，7.90(m，3H) | ??759 | ??759.94 |
| ??107 | ??δ7.28-7.34(m，15H)，7.48-7.54(m，??7H)，7.68-7.74(m，13H)，7.87(m，3H) | ??758 | ??758.94 |
| ??108 | ??δ7.24(m，2H)7.33-7.34(m，14H)，??7.48-7.54(m，7H)，7.66-7.73(m，16H)，??7.89(m，3H) | ??834 | ??835.04 |
| ??109 | ??δ7.30-7.33(m，12H)，7.52-7.54(m，??8H)，7.67-7.74(m，16H)，7.86(m，3H) | ??808 | ??809.00 |
| ??110 | ??δ7.32-7.38(m，15H)，7.54(m，4H)，??7.67-7.75(m，17H)，7.88(m，4H) | ??810 | ??809.00 |
| ??111 | ??δ7.28-7.32(m，14H)，7.54-7.56(m，??6H)，7.67-7.74(m，16H)，7.91(m，4H) | ??808 | ??809.00 |
| ??112 | ??δ7.32-7.38(m，13H)，7.52-7.55(m，??8H)，7.65-7.75(m，16H)，7.87(m，3H) | ??810 | ??809.00 |
| ??113 | ??δ1.68(s，12H)7.28-7.38(m，13H)，??7.48-7.77(m，16H)，7.84-7.90(m，5H) | ??814 | ??815.05 |
| ??114 | ??δ1.67(s，12H)7.28-7.35(m，12H)，??7.54-7.77(m，18H)，7.84-7.90(m，6H) | ??864 | ??865.11 |
| ??115 | ??δ7.22-7.32(m，15H)，7.48-7.54(m，??7H)，7.65-7.75(m，7H)，7.89(s，1H) | ??582 | ??582.73 |
| ??116 | ??δ7.22(m，2H)7.32-7.35(m，12H)，??7.49-7.55(m，6H)，7.65-7.72(m，10H)，??7.88(s，2H) | ??633 | ??632.79 |
| ??105 | ??δ7.22(m，1H)7.32-7.34(m，12H)，??7.48-7.54(m，9H)，7.65-7.73(m，13H)，??7.88(m，3H) | ??758 | ??758.94 |
| ??117 | ??δ7.21(m，1H)7.32-7.40(m，14H)，??7.45-7.55(m，5H)，7.63-7.67(m，13H)，??7.87(s，1H) | ??683 | ??682.85 |
| ??118 | ??δ7.30-7.38(m，14H)，7.54(m，4H)，??7.63-7.73(m，16H)，7.89(s，2H) | ??732 | ??732.91 |
| ??119 | ??δ7.22-7.32(m，15H)，7.48-7.54(m，??15H)，7.67-7.73(m，7H)，7.86(s，1H) | ??734 | ??734.92 |
| ??120 | ??δ7.20(m，2H)7.32(m，12H)，7.46-??7.56(m，14H)，7.65-7.74(m，10H)，??7.89(m，2H) | ??784 | ??784.98 |
| ??121 | ??δ7.20-7.38(m，17H)，7.44-7.54(m，??11H)，7.67-7.70(m，9H)，7.89(s，1H) | ??735 | ??734.92 |
| ??122 | ??δ7.22-7.34(m，21H)，7.46-7.53(m，??11H)，7.66-7.74(m，13H)，7.85(s，1H) | ??886 | ??887.11 |
| ??123 | ??δ7.28-7.32(m，19H)，7.50-7.54(m，??11H)，7.65-7.67(m，7H)，7.88(s，1H) | ??734 | ??734.92 |
| ??124 | ??δ7.20(m，1H)7.32-7.35(m，12H)，??7.46-7.54(m，13H)，7.65-7.72(m，13H)， | ??834 | ??835.04 |
| ??7.90(m，3H) | |||
| ??125 | ??δ7.32-7.44(m，18H)，7.54(m，4H)，??7.67-7.70(m，18H)，7.88(s，4H) | ??886 | ??885.10 |
| ??105 | ??δ7.22(m，1H)7.32-7.34(m，12H)，??7.48-7.54(m，9H)，7.65-7.73(m，13H)，??7.88(m，3H) | ??758 | ??758.94 |
| ??126 | ??δ7.28-7.32(m，17H)，7.48-7.54(m，??9H)，7.67-7.73(m，13H)，7.87(m，3H) | ??834 | ??835.04 |
| ??127 | ??δ1.67(s，6H)7.22-7.33(m，13H)，??7.48-7.73(m，17H)，7.84-7.90(m，4H) | ??748 | ??748.95 |
| ??128 | ??δ1.68(s，6H)，7.28-7.38(m，12H)，??7.55-7.73(m，19H)，7.84-7.90(m，5H) | ??798 | ??799.01 |
| ??129 | ??δ1.67(s，12H)7.21-7.38(m，12H)，??7.55-7.73(m，18H)，7.85-7.91(m，6H) | ??864 | ??865.11 |
| ??130 | ??δ1.67(s，6H)，7.32-7.38(m，13H)，??7.54-7.74(m，19H)，7.84-7.93(m，4H) | ??798 | ??799.01 |
| ??131 | ??δ1.68(s，6H)7.23-7.40(m，13H)，??7.48-7.60(m，10H)，7.67-7.77(m，11H)，??7.85-7.90(m，4H) | ??824 | ??825.04 |
| ??132 | ??δ1.67(s，6H)7.22-7.33(m，13H)，??7.48-7.73(m，17H)，7.84-7.90(m，4H) | ??748 | ??748.95 |
| ??133 | ??δ1.68(s，6H)，7.28-7.38(m，12H)，??7.55-7.73(m，19H)，7.84-7.90(m，5H) | ??798 | ??799.01 |
| ??134 | ??δ1.67(s，12H)7.21-7.38(m，12H)，??7.55-7.73(m，18H)，7.85-7.91(m，6H) | ??864 | ??865.11 |
| ??135 | ??δ1.67(s，6H)，7.32-7.38(m，13H)，??7.54-7.74(m，19H)，7.84-7.93(m，4H) | ??798 | ??799.01 |
| ??136 | ??δ1.68(s，6H)7.23-7.40(m，13H)，??7.48-7.60(m，10H)，7.67-7.77(m，11H)，??7.85-7.90(m，4H) | ??824 | ??825.04 |
[embodiment 1～13] uses compound of the present invention to make the OLED device
Use electroluminescent material of the present invention to make the OLED device.
At first, the transparency electrode ito thin film that is used for OLED that will get by glass (15 Ω/) carry out ultrasonic cleaning with trieline, acetone, ethanol and distilled water successively, and before using, be stored in the Virahol.
Then, the ITO substrate is contained in the substrate folder (folder) of vacuum vapor deposition equipment, will be by 4 of following chemical formulation, 4 ', 4 " three (N, N-(2-naphthyl)-phenyl amino) triphenylamine (2-TNATA) places the cell (cell) of vacuum vapor deposition equipment, then; exhaust, makes indoor vacuum be up to 10
-6Holder.On cell, apply electric current, make the 2-TNATA evaporation, the hole injection layer of vapour deposition 60 nano thickness on the ITO substrate.
The N that in another cell of this vacuum vapor deposition equipment, adds following chemical formulation then, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines (NPB), this cell is applied electric current, make NPB evaporate, thereby vapour deposition thickness is the hole transport layer of 20 nanometers on described hole injection layer.
After forming hole injection layer and hole transport layer, vapour deposition electroluminescence layer (5) is specific as follows in the above.Add compound of the present invention (for example compound 121) in a cell of described vacuum vapor deposition equipment, adding has the perylene of following structure as dopant material in another cell.Make these two kinds of materials with the evaporation of different speed, on hole transport layer vapour deposition the electroluminescence layer of 35 nanometer thickness, the concentration of having mixed in described electroluminescence layer is the perylene of 2-5 mole %.
Then, with three (oxine) aluminium (III) of following chemical formulation (Alq) vapour deposition be the electron transport layer of 20 nano thickness, will by the oxine lithium (lithiumquinolate) of following chemical formulation (Liq) vapour deposition be the electron injecting layer of 1-2 nanometer thickness.Then, adopt another vapor deposition apparatus, the Al negative electrode of vapour deposition 150 nanometer thickness is made OLED.
Each material that uses in this OLED device is 10
-6Use behind the vacuum-sublimation purifying of holder.
[embodiment 14-26]
Use compound of the present invention to make the OLED device
Form hole injection layer and hole transport layer, the EL of vapour deposition thereon layer as mentioned below according to the mode identical with embodiment 1.In a cell of described vacuum vapor deposition equipment, add compound of the present invention (for example compound 121), in another cell, add have structure shown below tonka bean camphor 545T (Coumarin 545T) (C545T).Make these two kinds of materials with the evaporation of different speed, on hole transport layer vapour deposition thickness be the EL layer of 35 nanometers, the concentration of having mixed in described EL layer is the tonka bean camphor 545T (C545T) of 2-5 mole %.
According to the method identical with embodiment 1, vapour deposition electron transport layer and electron injecting layer use another vapor deposition apparatus to deposit the Al negative electrode of 150 nanometer thickness, make OLED.
[comparative example 1] uses conventional EL material to make the OLED device
According to embodiment 1 described hole injection layer and the hole transport layer of having formed.In a cell of vacuum vapor deposition device, add dinaphthyl anthracene (DNA) as the blue EL material, in another cell, add perylene as another kind of blue EL material.Adopt 100: 1 vapour deposition ratio, the electroluminescence layer of thick 35 nanometers of vapour deposition on hole transport layer.
According to embodiment 1 described identical step, vapour deposition electron transport layer and electron injecting layer, the Al negative electrode of thick 150 nanometers that used another vapor deposition apparatus vapour deposition is made OLED.
[comparative example 2] uses conventional EL material to make the OLED device
According to embodiment 1 described hole injection layer and the hole transport layer of having formed.In another cell of described vapor deposition apparatus, add three (oxine) aluminium (III) (AIq) as the EL material of main part, in another cell, add tonka bean camphor 545T (C545T).Make these two kinds of materials with the evaporation of different speed, EL layer by thick 30 nanometers of doping vapour deposition on hole transport layer.In Alq is benchmark, and doping content is preferably 2-5 mole %.
According to the method identical with embodiment 1, vapour deposition electron transport layer and electron injecting layer use another vapor deposition apparatus to deposit the Al negative electrode of 150 nanometer thickness, make OLED.
[comparative example 1] uses conventional EL material to make the OLED device
According to embodiment 1 described hole injection layer and the hole transport layer of having formed.In another cell of described vapor deposition apparatus, add dinaphthyl anthracene (DNA) as the blue EL material, in another cell, add tonka bean camphor 545T (C545T).Make these two kinds of materials with the evaporation of different speed, EL layer by thick 30 nanometers of doping vapour deposition on hole transport layer.In Alq is benchmark, and doping content is preferably 2-5 mole %.
[comparative example 4] uses conventional EL material to make the OLED device
According to embodiment 1 described hole injection layer and the hole transport layer of having formed.The compound (A) that the adding U.S. Patent Publication is disclosed for 20060046097A1 number in another cell of described vapor deposition apparatus is as the blue EL material, and it has structure shown below, adds tonka bean camphor 545T (C545T) in another cell.Make these two kinds of materials with the evaporation of different speed, EL layer by thick 30 nanometers of doping vapour deposition on hole transport layer.In Alq is benchmark, and doping content is preferably 2-5 mole %.
According to the method identical with embodiment 1, vapour deposition electron transport layer and electron injecting layer use another vapor deposition apparatus to deposit the Al negative electrode of 150 nanometer thickness, make OLED.
The blue EL character of the OLED device that [experimental example 1] made
In 500cd/m2 and 2, measured the blue-light-emitting efficient of the OLED that comprises organic EL compound of the present invention and conventional electroluminescent compounds of embodiment 1-13 and comparative example 1 manufacturing under the condition of 000cd/m2 respectively independently, it the results are shown in table 3.
[table 3]
Table 3 shows the result who material of the present invention is used for the blue EL device.As can be seen from Table 3, the luminous efficiency of EL material of the present invention under low-light level is 5.26-6.30cd/A, luminous efficiency under high brightness is 4.80-5.88cd/A, and the luminous efficiency of El material under low-light level and high brightness of comparative example 1 is respectively 4.45cd/A and 3.6cd/A.Therefore, compare, use the high 1.5cd/A of luminous efficiency of El element of organic EL compound of the present invention or more with comparative example.Particularly, confirm that the luminous efficiency of every kind of compound under high brightness conditions improves 2cd/A or more.
In addition, when using material of main part of the present invention, observing purity of color has improvement slightly.More than shown in purity of color and luminous efficiency obtain improved result simultaneously and prove that EL material of the present invention has splendid character.
Fig. 1 has shown use DNA: perylene is as the luminous efficiency-current density character of the comparative example 1 of conventional EL material, and Fig. 2 and Fig. 3 show current density-voltage character and the luminous efficiency-current density character of use compound of the present invention (121) as the embodiment 9 of EL material.Result shown in the figure confirms that performance obtains significant the raising.
The green EL character of the OLED device that [experimental example 2] made
In 500cd/m2 and 2, measured the green emitting efficient of the OLED that comprises organic EL compound of the present invention and conventional electroluminescent compounds of embodiment 14-26 and comparative example 1 manufacturing under the condition of 000cd/m2 respectively independently, it the results are shown in table 4.
[table 4]
Table 4 has shown the character result of the green El element that uses material of the present invention.Similar with the blue EL device of experimental example 1, confirm to compare with the EL material of routine, the device of this embodiment has splendid character under low-light level and high brightness.
Its efficient is compared with the Alq main body of comparative example 2 and has been improved 70% or more, compares with the conventional body of comparative example 3 and has improved 40% or more.This result shows the defective that has significantly overcome conventional green EL material.Especially, estimate that its splendid improvement of performance under high brightness makes this compound can be used for the practical application of giant-screen OLED, perhaps be used for manual (manual) OLED of 2 inches levels (level) of the demanding character of needs.
Aspect chromaticity coordinates, there is not significant difference.Therefore EL material of the present invention has improved luminous efficiency, has kept purity of color simultaneously, therefore can be called and surmount the conventional material epoch-making invention in a period.
Fig. 4 has shown that using the luminous efficiency-luminosity of Alq:C545T as the comparative example 2 of the green EL material of routine, Fig. 5 to show uses the luminous efficiency-current density character of compound of the present invention (121) as the green El element of EL material.Fig. 6 has shown the comparative example 3 that uses conventional EL material and 4 and use the luminous efficiency-current density character of compound of the present invention (121) as the green El element of the embodiment 22 of EL material.
EL material of the present invention can be used for blue OLED and green OLED, demonstrate splendid results of property.These results show the excellent properties of splendid EL material.Material of the present invention with these characteristics makes the designs simplification of oled panel, causes reducing the less important result of OLED production cost.Because these splendid features can obtain the novelty result in the exploitation in OLED field.
Fig. 7 shows and will use the comparison of compound of the present invention (121) as the purity of color of the green El element of the purity of color of the green El element of the embodiment 22 of EL material and comparative example 2.EL material of the present invention shows good EL color property, does not have significant difference because its color property is compared with the pure green EL material of routine.In the EL spectrum of the El element of embodiment 22, confirm the conventional green EL peak of 520 nanometers.This shows that the organic EL compound with blue EL character of the present invention has good electrical property, can make the characteristic of EL doping agent reach maximum horizontal.
The splendid life properties that material of the present invention is compared with conventional EL material and other character have obtained material of the present invention with respect to the benefit of the maximum with the conductive conventional material of good electronics.
Link to each other with the 2-position of anthracene by the 10-position with 9-aryl anthryl, the eclipsing effect of intermolecular orbit obtains to improve, and the relation between enabled stage and the doping agent is more favourable, thereby solves simple routine 9, the defective of 10-diaryl anthracene structure.
Commercial Application
Electroluminescent compounds of the present invention has good luminous efficiency and splendid material lifetime, therefore can make the good OLED device of working life.
Claims (9)
1. the electroluminescent organic material that following Chemical formula 1 is represented:
[Chemical formula 1]
R1 to R3 represents phenyl or many cyclophanes of C10-C20 condensed ring independently in the formula, the phenyl of described R1 to R3 or many cyclophanes of C10 to C20 condensed ring can further be replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen, C5-C7 cycloalkyl, phenyl or condensed polyaromatic.
2. electroluminescent organic material as claimed in claim 1 is characterized in that, the R1 to R3 of chemical formula (1) is independently selected from: phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, fluoranthene base, pyrenyl, perylene base or naphthacenyl; And phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, the fluoranthene base, pyrenyl, perylene base and naphthacenyl are randomly replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen atom, C5-C7 cycloalkyl, phenyl or condensed polyaromatic.
3. electroluminescent organic material as claimed in claim 2, this material is selected from the compound of following chemical formulation:
4. organic electroluminescence device, this device comprises first electrode, second electrode and the one or more organic layers between described first electrode and second electrode, wherein, described organic layer comprises the compound of one or more chemical formulas (1) expression:
[Chemical formula 1]
R1 to R3 represents phenyl or many cyclophanes of C10-C20 condensed ring independently in the formula, and the phenyl of described R1 to R3 or many cyclophanes of C10-C20 condensed ring can further be replaced by following group: C1-C20 alkyl, C1-C20 alkoxyl group, halogen, C5-C7 cycloalkyl.
5. organic electroluminescence device as claimed in claim 4 is characterized in that described organic layer comprises electro-luminescent zones, and described electro-luminescent zones comprises compound and one or more electroluminescent doping agents of one or more chemical formulas (1) expression.
6. organic electroluminescence device as claimed in claim 5 is characterized in that, described electroluminescent doping agent is selected from the compound shown in one of following chemical formula (2)-(4):
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In the formula, Ar1 and Ar2 are selected from the indenofluorene of following chemical formulation, fluorenes and spiral shell fluorenes:
R11 to R16 is independently selected from the C1-C20 alkyl in the formula, and has the C1-C5 alkyl substituent or do not have the phenyl or naphthyl of C1-C5 alkyl substituent;
Ar3 to Ar6 is independently selected from C5-C20 aromatic ring or many cyclophanes ring; Prerequisite is that Ar1 is identical with Ar2, and Ar3 is identical with Ar5, and Ar4 is identical with Ar6;
A and B represent chemical bond, perhaps group independently
R17 and R18 represent aromatic ring or many cyclophanes ring independently, and wherein two or more aromatic rings condense;
R19 to R22 represents the C1-C20 alkyl of the straight or branched that has halogenic substituent or do not have halogenic substituent independently;
R23-R26 represents hydrogen or aryl independently;
Ar7 to Ar10 represents aromatic ring or many cyclophanes ring independently, and wherein two or more aromatic rings condense.
7. organic electroluminescence device as claimed in claim 6 is characterized in that, described electroluminescent doping agent is selected from the compound of one of following formula expression:
R19 to R22 represents methyl or ethyl in the formula.
8. organic electroluminescence device as claimed in claim 5 is characterized in that, described electroluminescent doping agent is selected from the compound of chemical formula (5) to one of (7) expression:
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
In the formula, R27 and R28 represent many cyclophanes ring independently, and wherein two or more aromatic rings condense; R29 to R32 represents aromatic ring independently; Each aromatic ring of R27 to R32 can further be replaced by the C1-C20 alkyl.
9. organic electroluminescence device as claimed in claim 8 is characterized in that, described electroluminescent doping agent is selected from the compound of one of following formula expression:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2007/005942 WO2009066814A1 (en) | 2007-11-23 | 2007-11-23 | Organic electroluminescent compounds and display device containing the same |
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|---|---|
| EP (1) | EP2217677A1 (en) |
| JP (1) | JP2011504493A (en) |
| CN (1) | CN101874096A (en) |
| WO (1) | WO2009066814A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795983A (en) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | Anthraquinone derivative material and preparation method and application thereof |
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| JP5723127B2 (en) * | 2009-09-28 | 2015-05-27 | 双葉電子工業株式会社 | COMPOUND FOR ORGANIC EL ELEMENT AND ORGANIC EL ELEMENT |
| CN109678645A (en) * | 2018-12-28 | 2019-04-26 | 陕西师范大学 | A kind of organic blue fluorescent material and its preparation method and application based on dianthracene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004231563A (en) * | 2003-01-30 | 2004-08-19 | Idemitsu Kosan Co Ltd | Bianthryl derivative, luminescent coating film forming material containing the same, and organic electroluminescent element |
| US8053762B2 (en) * | 2005-12-13 | 2011-11-08 | Lg Chem, Ltd. | Imidazoquinazoline derivative, process for preparing the same, and organic electronic device using the same |
| TWI348463B (en) * | 2006-03-06 | 2011-09-11 | Lg Chemical Ltd | Novel anthracene derivative and organic electronic device using the same |
| DE102006013802A1 (en) * | 2006-03-24 | 2007-09-27 | Merck Patent Gmbh | New anthracene compounds useful in organic electronic devices, preferably organic electroluminescent device e.g. integrated organic electroluminescent devices and organic field-effect-transistors |
| JP5417702B2 (en) * | 2006-11-02 | 2014-02-19 | 三菱化学株式会社 | Organic electroluminescent device, organic electroluminescent layer coating solution, color display device |
| KR100858816B1 (en) * | 2007-03-14 | 2008-09-17 | 삼성에스디아이 주식회사 | Organic light emitting device comprising anthracene derivative compound |
-
2007
- 2007-11-23 WO PCT/KR2007/005942 patent/WO2009066814A1/en active Application Filing
- 2007-11-23 EP EP07851144A patent/EP2217677A1/en not_active Withdrawn
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795983A (en) * | 2011-05-25 | 2012-11-28 | 海洋王照明科技股份有限公司 | Anthraquinone derivative material and preparation method and application thereof |
| CN102795983B (en) * | 2011-05-25 | 2016-01-20 | 海洋王照明科技股份有限公司 | Anthraquinone derivative material and its preparation method and application |
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|---|---|
| EP2217677A1 (en) | 2010-08-18 |
| WO2009066814A1 (en) | 2009-05-28 |
| JP2011504493A (en) | 2011-02-10 |
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Application publication date: 20101027 |