CN102952162A - Organometallic compound and organic electroluminescence device and composition containing same - Google Patents
Organometallic compound and organic electroluminescence device and composition containing same Download PDFInfo
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Abstract
The invention provides an organometallic compound and an organic electroluminescence device and composition containing the same. The organometallic compound has the chemical formula shown by (I) or (II), wherein R is alkyl or naphthenic base.
Description
[technical field]
The present invention relates to a kind of organometallic compound and comprise its Organnic electroluminescent device, particularly a kind of organo-metallic phosphorescent compound and comprise its phosphorescent organic electroluminescent device.
[background technology]
Organnic electroluminescent device (organic electroluminescent device) also is called Organic Light Emitting Diode (organic light-emitting diode; OLED), be with a kind of photodiode (LED) of organic layer as active layer.Because Organnic electroluminescent device has the advantages such as low voltage operating, high brightness, lightweight, wide viewing angle and high correlative value, gradually is used in recent years on the flat panel display (flat panel display).Different from liquid-crystal display, the organic light emitting diode pixel array that display of organic electroluminescence comprises has self luminous characteristic, therefore need not add backlight.
Generally speaking, organic light-emitting diode element comprises electrode, and the organic light emitting medium layer between electrode.Luminous is to lead because of in following phenomenon.When electric field imposed on two electrodes, negative electrode penetrated electronics to the organic light emitting medium layer, and anode penetrates the hole to the organic light emitting medium layer.When electronics and hole in the organic light emitting medium layer in conjunction with the time, can produce exciton (excitons).The again combination in electronics and hole just is accompanied by luminous.
According to the spin state (spin state) of hole and electronics, the exciton that is produced by the again combination of hole and electronics can have the spin state of triplet state (triplet) or singlet state (singlet).By singlet state exciton (singlet exciton) produce luminous for fluorescence (fluorescence), and luminously be phosphorescence (phosphorescence) by what triplet exciton (triplet exciton) produced.The luminous efficiency of phosphorescence is three times of fluorescence.Therefore, developing high efficiency phosphor material is very important with the luminous efficiency of promoting organic light-emitting diode element.
At present organic light-emitting diode element luminescence unit material is take small molecule material as main, this be because the small molecules organic light-emitting diode element no matter all high than polymer organic light-emitting diode element (PLED) at aspects such as efficient, brightness and life-spans.Now small molecules organic light-emitting diode element processing procedure unlike PLED take rotary coating or ink jet printing (Inkjet printing) as main, but in the evaporation mode as main.Yet, be used for the employed mode vacuum process equipment cost of evaporation mode higher, only have in addition 5% luminous organic material can be plated on the substrate, 95% luminous organic material is wasted on the cavity wall, so that the manufacturing cost of organic light-emitting diode element is high.Therefore, wet process (comprising rotary coating (spin coating) or scraper for coating (blade coating)) is proposed on the processing procedure of small molecules organic light-emitting diode element, reduces equipment cost and reaches the rate of utilization that greatly promotes luminous organic material.
But, traditional organic phosphorescent light-emitting materials is because the relation of poor solubility, and is not suitable for wet process.Therefore, developing the dissolved organic phosphorus light luminescent material that is applicable to wet process is the most key (especially as orange photodopant), for the Organic Light Emitting Diode technology, is a very important problem.
[summary of the invention]
The present invention proposes a kind of organometallic compound, is alkyl or cycloalkyl is imported 4-phenyl thieno-[3,2-c] pyridine (4-phenylthieno[3,2-c] pyridine) structure, makes material have good solubleness.Short carbon chain (short-chain alkyl, for example methyl or ethyl) is imported in the organometallic compound structure of the present invention, and the organometallic compound of gained can form organic light-emitting diode element with evaporation and wet process; Import in the organometallic compound structure of the present invention if will grow carbochain (long alkyl, for example tertiary butyl or hexanaphthene), the organometallic compound of gained can form organic light-emitting diode element with wet process.In addition, organometallic compound of the present invention can be applicable to Organnic electroluminescent device, as the material of luminescence unit, promotes the efficiency of element of Organnic electroluminescent device.
According to one preferred embodiment of the present invention, this organometallic compound has suc as formula (I) or the chemical structure (II):
Wherein, R is alkyl or cycloalkyl.
Another preferred embodiment according to the present invention the invention provides a kind of Organnic electroluminescent device, and this device comprises electrode; And luminescence unit, be disposed at this between the electrode, wherein this luminescence unit comprises above-mentioned organometallic compound, can be used as orange smooth phosphorescence dopant material.
The another preferred embodiment according to the present invention the invention provides a kind of composition, comprising: the Organic Light Emitting Diode material of main part; And above-mentioned organometallic compound, be dispersed in the organic solvent.The material of main part of this Organic Light Emitting Diode can for example be macromolecular material (for example: PVK (Polyvinyl carbazole (poly (vinylcarbazole))), and said composition can further comprise more than one carrier promotor (carrier promoter), for example electronics promotor (for example: PBD, 2-xenyl-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole)) or hole promotor (for example: TPD, N, N '-phenylbenzene-N, N '-(two (3-aminomethyl phenyls)-[1, the 1-xenyl]-4,4 '-diamines (N, N '-diphenyl-N, N '-(bis (3-methylphenyl)-[1,1-biphenyl]-4,4 ' diamine))).
Below illustrate further method of the present invention, feature and advantage by several embodiment and comparing embodiment, but they are not to limit the scope of the invention, scope of the present invention should be as the criterion with the scope of appending claims.
[description of drawings]
Fig. 1 is the sectional structure chart of the described Organnic electroluminescent device of one embodiment of the present invention.
[main description of reference numerals]
Organnic electroluminescent device～10;
Substrate～12;
Lower electrode～14;
Luminescence unit～16; And
Top electrode～18.
[embodiment]
Organometallic compound
The present invention discloses a kind of organometallic compound, its have formula (I) or (II) shown in structure:
Wherein, wherein, R is alkyl or cycloalkyl.For instance, R can be C
1-12Alkyl or C
4-12Cycloalkyl similarly is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.
Below by the following example the synthesis mode of organometallic compound of the present invention is described, in order to further to illustrate technical characterictic of the present invention.
Embodiment 1
Compound P O-01-M's is synthetic
Commercially available compound 1 (2-(2-amino-ethyl) thiophene (2-(2-aminoethyl) thiophene), 7.0g, 55.1mmol) is put into the single neck bottle of 500mL, add 200mL H
2O also connects feed hopper.Then in feed hopper, add commercial compound 2 (P-Toluoyl chloride (p-toluoyl chloride), 11.0mL, 82.7mmol), under ice water bath environment, splash in the reaction flask, produce gradually white solid.After dripping off, add the 20%NaOH aqueous solution, stirred overnight.Filter with the ceramic whiteware funnel, can get compound 3 (white solid product), productive rate is 93%).The reaction formula of above-mentioned reaction is as follows:
Compound 1 compound 2 compounds 3.
Then, compound 3 (5.0g, 20.4mmol) is put into the single neck round-bottomed bottle of 250mL, add toluene (toluene, 80mL).Under the ice-water bath, via feed hopper with POCl
3(5.7mL, 61.2mmol) splashes in the reaction flask.After dripping off, remove ice-water bath, change with oil bath and be heated to refluxing toluene, react after 2 hours, with saturated sodium bicarbonate (NaHC0
3) aqueous solution neutralization reaction, extract with toluene again.Collect toluene solution, dewater with anhydrous magnesium sulfate, after concentrating under reduced pressure is drained, leave standstill a few hours, can get crystallized product (compound 4), productive rate is 50%.The reaction formula of above-mentioned reaction is as follows:
Compound 3 compounds 4.
Then, compound 4 (3.0g, 13.2mmol) and 10%Pd/C (3.0g) are put into the single neck round-bottomed bottle of 250mL, add toluene (100mL), be heated to refluxing toluene.React after 18 hours, with diatomite (Celite 545) Pd/C is filtered, filtrate is drained with the concentrating under reduced pressure machine, can get product 5, and productive rate is 85%.The reaction formula of above-mentioned reaction is as follows:
Compound 4 compounds 5.
Then, with compound 5 (5.0g, 22.2mmol) and hydration iridium chloride compound (IrCl
3.xH
2O, 3.0g, 10mmol) put into the single neck round-bottomed bottle of 100mL, add respectively 2-methyl cellosolve (2-methoxy ethanol) (15mL) and water (5mL), be heated to 140 ℃.React after 24 hours, add a large amount of water, filter, can get orange solid product (compound 6), productive rate is 49%.The reaction formula of above-mentioned reaction is as follows:
Compound 5 compounds 6.
With compound 6 (3.3g, 4.0mmol), acac (Acetyl Acetone (acetyl acetone), 1.65g, 16mmol) and yellow soda ash solid (Na
2CO
3, 1.71g 16mmol) and put into the single neck round-bottomed bottle of 100mL, add 2-methyl cellosolve (40mL), be heated to backflow.React after 24 hours, wait to rise again to room temperature, add 40mL water, stirred for several hour is broken up solid.Filter, solid with the separation and purification of tubing string chromatography (take absolute dichloromethane as eluant), can be got orange powdered product PO-01-M, productive rate is 50%.The reaction formula of above-mentioned reaction is as follows:
Compound 6 PO-01-M.
Utilize nuclear magnetic resonance spectroscopy Compound P O-01-M, the spectroscopic data of gained is as follows:
1H?NMR(CDCl
3，200MHz)δ8.41(d，J＝3.4Hz，2H)，8.34(d，J＝5.6Hz，2H)，8.02(d，J＝8.0Hz，2H)，7.66(d，J＝5.6Hz，2H)，7.60(d，J＝6.2Hz，2H)，6.69(d，J＝7.6Hz，2H)，6.15(s，2H)，5.18(s，1H)，2.03(s，6H)，1.75(s，6H).
Embodiment 2
Compound P O-01-TB's is synthetic
Compound 1 (2-(2-amino-ethyl) thiophene, 7.0g, 55.1mmol) is put into the single neck bottle of 500mL, add 200mL H2O and connect feed hopper.Then in feed hopper, add commercial compound 7 (4-tert.-butylbenzene formyl chloride (4-t-butyl benzoyl chloride), 16.2g, 82.5mmol), under ice water bath environment, splash in the reaction flask, produce gradually white solid.After dripping off, add the 20%NaOH aqueous solution, stirred overnight.Filter with the ceramic whiteware funnel, can get white solid product (compound 8,15.4g), productive rate is 98%.The reaction formula of above-mentioned reaction is as follows:
Compound 1 compound 7 compounds 8.
Then, compound 8 (2.87g, 10mmol) is put into the single neck round-bottomed bottle of 250mL, add toluene (toluene, 80mL).Under the ice-water bath, via feed hopper with POCl
3(2.8mL, 30mmol) splashes in the reaction flask.After dripping off, remove ice-water bath, change with oil bath and be heated to refluxing toluene, react after 2 hours, with saturated sodium bicarbonate (NaHCO
3) aqueous solution neutralization reaction, extract with toluene again.Collect toluene solution, dewater with anhydrous magnesium sulfate, after concentrating under reduced pressure is drained, leave standstill a few hours, can get crystallized product (compound 9,1.6g), productive rate is 60%.The reaction formula of above-mentioned reaction is as follows:
Compound 8 compounds 9.
Compound 9 (2.7g, 10mmol) and 10%Pd/C (0.5g) are put into the single neck round-bottomed bottle of 250mL, add toluene (100mL), be heated to refluxing toluene.React after 18 hours, (Celite545) filters Pd/C with diatomite, and filtrate is drained with the concentrating under reduced pressure machine, with the separation and purification of tubing string chromatography (ethyl acetate/normal hexane=1/9), can get compound 10 again, and productive rate is 79%.The reaction formula of above-mentioned reaction is as follows:
Compound 9 compounds 10.
With compound 10 (5.0g, 18.7mmol) and hydration iridium chloride compound (IrCl
3.xH
2O, 2.9g, 8.5mmol) put into the single neck round-bottomed bottle of 100mL, add respectively 2-methyl cellosolve (15mL) and water (5mL), be heated to 140 ℃.React after 24 hours, add a large amount of water, filter, can get orange solid product (compound 11,4.1g), productive rate is 49%.The reaction formula of above-mentioned reaction is as follows:
Compound 10 compounds 11.
With compound 11 (1.48g, 1.5mmol), acac (Acetyl Acetone, 0.6g, 6mmol) and yellow soda ash solid (Na
2CO
3, 0.64g, 6mmol) and put into the single neck round-bottomed bottle of 100mL, add 2-methyl cellosolve (15mL), be heated to backflow.React after 24 hours, wait to rise again to room temperature, add 40mL water, stirred for several hour is broken up solid.Filter, solid with the separation and purification of tubing string chromatography (take absolute dichloromethane as eluant), can be got the orange powdered product, PO-01-TB, productive rate are 89%.The reaction formula of above-mentioned reaction is as follows:
Compound 11 PO-01-TB.
Utilize nuclear magnetic resonance spectroscopy Compound P O-01-M, the spectroscopic data of gained is as follows:
1H?NMR(CDCl
3，200MHz)δ8.45(d，J＝6.6Hz，2H)，8.30(d，J＝5.4Hz，2H)，7.99(d，J＝8.4Hz，2H)，7.64(d，J＝5.0Hz，4H)，6.88(dd，J＝8.6，1.8Hz，2H)，6.22(d，J＝1.8Hz，2H)，5.22(s，1H)，1.79(s，6H)，0.98(s，18H).
Embodiment 3
Compound P O-01-HEX's is synthetic
In the single neck bottle of compound 1 (2-(2-amino-ethyl) thiophene, 9.4g, 74.1mmol) 500mL, add 200mL H
2O also connects feed hopper.Then in feed hopper, add commercial compound 12 (4-positive hexyl phenenyl formyl chloride, 25.0g, 111.2mmol), under ice water bath environment, splash in the reaction flask, produce gradually white solid.After dripping off, add the 20%NaOH aqueous solution, stirred overnight.Filter with the ceramic whiteware funnel, can get white solid product (compound 13,20.6g), productive rate is 88%.The reaction formula of above-mentioned reaction is as follows:
Compound 1 compound 12 compounds 13.
Compound 13 (5.0g, 15.9mmol) is put into the single neck round-bottomed bottle of 250mL, add toluene (80mL).Under the ice-water bath, via feed hopper with POCl
3(4.4mL, 47.6mmol) splashes in the reaction flask.After dripping off, remove ice-water bath, change with oil bath and be heated to refluxing toluene, react after 2 hours, with saturated sodium bicarbonate (NaHCO
3) aqueous solution neutralization reaction, extract with toluene again.Collect toluene solution, dewater with anhydrous magnesium sulfate, after concentrating under reduced pressure is drained, leave standstill a few hours, can get crystallized product (compound 14,2.6g), productive rate is 55%.The reaction formula of above-mentioned reaction is as follows:
Compound 13 compounds 14.
Compound 14 (3.0g, 13.2mmol) and 10%Pd/C (3.0g) are put into the single neck round-bottomed bottle of 250mL, add toluene (100mL), be heated to refluxing toluene.React after 18 hours, (Celite545) filters Pd/C with diatomite, and filtrate is drained with the concentrating under reduced pressure machine, with the separation and purification of tubing string chromatography (ethyl acetate/normal hexane=1/9), can get compound 15 again, and productive rate is 75%.The reaction formula of above-mentioned reaction is as follows:
Compound 14 compounds 15.
With compound 15 (3.8g, 12.88mmol) and hydration iridium chloride compound (IrCl
3.xH
2O, 1.7g, 5.85mmol) put into the single neck round-bottomed bottle of 100mL, add respectively 2-methyl cellosolve (15mL) and water (5mL), be heated to 140 ℃.React after 24 hours, add a large amount of water, filter, can get orange solid product (compound 16), productive rate is 40%.The reaction formula of above-mentioned reaction is as follows:
Compound 15 compounds 16.
With compound 16 (5.0g, 4.0mmol), acac (Acetyl Acetone, 1.23g, 12.26mmol) and yellow soda ash solid (Na
2CO
3, 1.30g, 12.26mmol) and put into the single neck round-bottomed bottle of 100mL, add 2-methyl cellosolve (30mL), be heated to backflow.React after 24 hours, wait to rise again to room temperature, add 40mL water, stirred for several hour is broken up solid.Filter, solid with the separation and purification of tubing string chromatography (take methylene dichloride/normal hexane=1/3 as eluant), can be got orange powdered product (PO-01-HEX), productive rate is 63%.The reaction formula of above-mentioned reaction is as follows:
Utilize nuclear magnetic resonance spectroscopy Compound P O-01-M, the spectroscopic data of gained is as follows:
1H?NMR(CDCl
3，200MHz)δ8.42(d，J＝3.4Hz，2H)，8.32(d，J＝5.0Hz，2H)，8.01(d，J＝5.0Hz，2H)，7.65(d，J＝5.4Hz，2H)，7.42(d，J＝4.8Hz，2H)，6.69(d，J＝7.6Hz，2H)，6.10(s，2H)，5.19(s，1H)，2.26(t，J＝6.6Hz，4H)，1.76(s，6H)，1.55(s，4H)，1.10(br，12H)，0.80(t，J＝7.2Hz，6H).
Embodiment 4
The solubleness test
Respectively with PO-01-TB and the PO-01-HEX material of embodiment 2-3 gained, and PO-01 (structure is
Group in contrast), with 0.5%, 0.8%, 1%, 1.5%, 2%, and the ratio of 3% (weight ratio of material and solvent) be dissolved in the chlorobenzene, carry out the test of solubleness.The result is as shown in table 1:
Table 1
Insoluble or the dissolving of (*: expression not exclusively, zero: expression mixes fully)
As shown in Table 1, by alkyl or cycloalkyl being imported 4-phenyl thieno-[3,2-c] PO-01-TB of pyridine structure gained and PO-01-HEX material have good solubleness, in chlorobenzene solvent solubleness can reach 1.5% or more than, and the PO-01 of non-modified only has 0.5%.
Organnic electroluminescent device
Please refer to Fig. 1, this figure shows a cross-sectional view according to Organnic electroluminescent device 10 of the present invention, and this Organnic electroluminescent device 10 comprises substrate 12, lower electrode 14, luminescence unit 16 and top electrode 18.This Organnic electroluminescent device 10 can be luminous, lower luminous or double-sided light emitting organic electroluminescence device.This substrate can for example be glass, plastic substrate or semiconductor substrate.The material of this lower electrode 14 and top electrode 18 can for example be lithium, magnesium, calcium, aluminium, silver, indium, gold, tungsten, nickel, platinum, copper, indium tin oxide (ITO), indium-zinc oxide (IZO), Zinc-aluminium (AZO), zinc oxide (ZnO) or its combination, and its generation type can be hot evaporation, sputter or plasma reinforced chemical vapour deposition mode.In addition, this lower electrode 14 and top electrode 18 one of at least need to have light transmission.
This luminescence unit 16 comprises luminescent layer at least, can further comprise hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer or other retes.It should be noted that according to a preferred embodiment of the invention, this luminescence unit 16 must comprise the organometallic compound with formula (I) of the present invention.In other words, in this luminescence unit 16, have at least a rete to comprise this organometallic compound.
Another preferred embodiment according to the present invention, this Organnic electroluminescent device can be the phosphorescent organic electroluminescent device, and the luminescence unit of this phosphorescence luminescence unit comprises main body (host) material and phosphorescence dopant material, and this phosphorescence dopant material comprise of the present invention have formula (I) or (II) shown in the organometallic compound of structure.The visual employed electroluminescent organic material of those skilled in the art and required element characteristic mix organometallic compound of the present invention and required phosphorescence dopant material, and change the doping of the hotchpotch of arranging in pairs or groups.Therefore, the doping of hotchpotch how much be not feature of the present invention, be not the restriction scope of the invention foundation.
For further specifying Organnic electroluminescent device of the present invention, following examples will be by the organometallic compound of embodiment 1-3 gained as dopant material, the embodiment (forming with evaporation (dry process) or coating (wet process) mode respectively) of a plurality of Organnic electroluminescent devices is provided, come to compare with comparing embodiment (with PO-01 as hotchpotch), verify that organometallic compound of the present invention compares with current material and really have higher photoelectric characteristic.
Dry process
Comparing embodiment 1:
Use mild detergent, acetone, and ethanol clean with the ultra-sonic oscillation ITO of patterning (thickness is as 120nm) substrate of glass.With nitrogen base material is dried up, then processed 30 minutes with UV-ozone (UV-OZONE), then in 10
-6Sequentially deposit NPB (N under the pressure of holder, N '-two (naphthalene-1-yl)-N, N '-diphenylbenzidine (N, N '-di (naphthalene-l-yl)-N, N '-diphenyl-benzidine), thickness are 30nm), CBP (4,4 '-N, N '-two carbazole biphenyl (4,4 '-N, N '-dicarbazole-biphenyl)) doping PO-01 (
) (ratio of CBP and PO-01 is that 100: 6, thickness are 30nm), BCP (2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthrolene (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), thickness is 10nm), Alq
3(three (oxine) aluminium (tris (8-hydroxyquinoline) aluminum), thickness are 20nm), LiF (thickness is 0.5nm), and Al (thickness is 120nm) obtain this el light emitting device (1) after the encapsulation.The structure of this el light emitting device (1) can be expressed as: ITO/NPB/CBP:PO-01 (6%)/BCP/Alq
3/ LiF/Al.
Then, measure the optical characteristics of this el light emitting device (1), its measuring result please refer to table 2.
Embodiment 5:
Use mild detergent, acetone, and ethanol clean with the ultra-sonic oscillation ITO of patterning (thickness is as 120nm) substrate of glass.With nitrogen base material is dried up, then with UV-ozonize 30 minutes, then in 10
-6Sequentially deposit NPB (N under the pressure of holder, N '-two (naphthalene-1-yl)-N, N '-diphenylbenzidine, thickness are 30nm), CBP (4,4 '-N, N '-two carbazole biphenyl) doping PO-01-TB (ratio of CBP and PO-01-TB is that 100: 6, thickness are 30nm), BCP (2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthrolene, thickness are 10nm), Alq
3(three (oxine) aluminium, thickness are 20nm), LiF (thickness is 0.5nm), and Al (thickness is 120nm) obtain this el light emitting device (2) after the encapsulation.The structure of this el light emitting device (2) can be expressed as: ITO/NPB/CBP:PO-01-TB (6%)/BCP/Alq
3/ LiF/Al.
Then, measure the optical characteristics of this el light emitting device (2), its measuring result please refer to table 2.
Table 2
As shown in table 2, under the condition of collocation same body material, organometallic compound PO-01-TB of the present invention compares with PO-01, can reduce driving voltage and have preferably efficiency of element.
Wet process
Comparing embodiment 2:
Use mild detergent, acetone, and ethanol clean with the ultra-sonic oscillation ITO of patterning (thickness is as 120nm) substrate of glass.With nitrogen base material is dried up, then with UV-ozonize 30 minutes.Then, select PEDOT (poly-(3,4)-(poly (3 for ethylidene dioxy base thiophene, 4)-ethylendioxythiophen)): PS S (e-PSS (e-polystyrenesulfonate)) is used as hole injection layer (hole-inject layer), form rete (thickness is as 50nm) take scraper and rotary coating mode (rotating speed 4000rpm), then heat 100 ℃ and continue 40 minutes.Then, on the PEDOT:PSS layer, form TFB (poly-[99 in the scraper for coating mode, 9-dioctyl fluorenyl-2,7-two bases)-copolymerization-(4,4 '-(N-(4-secondary butyl phenenyl)) diphenylamine (poly[99,9-dioctylfluorenyl-2,7-diyl)-co-(4,4 '-(N-(4-s-butylphenyl)) diphenylamine))]) layer (thickness is 20nm), then be heated to 180 ℃ and continue 40 minutes under vacuum, hole transport layer (hole-transport layer) material is used as by TFB system.Then, on the TFB layer, form luminescent layer (thickness is about 30nm) with coating method, the coating composition that is used for forming luminescent layer comprises: PVK (Polyvinyl carbazole (poly (vinylcarbazole))), PBD (2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole)), TPD (N, N '-phenylbenzene-N, N '-(two (3-aminomethyl phenyls)-[1, the 1-xenyl]-4,4 '-diamines (N, N '-diphenyl-N, N '-(bis (3-methylphenyl)-[1,1-biphenyl]-4,4 ' diamine))), and PO-01, (PVK: PBD: TPD: PO-01 is (55: 34: 9: 6), be dissolved in the chlorobenzene solvent to part by weight.Then, on luminescent layer, form hole barrier layer electron transfer layer (hole-block/electron-transport layer) TPBI (1 that holds concurrently with scraper and rotary coating mode, 3,5-three (phenyl-2-benzimidazolyl-)-benzene (1,3,5-tris (phenyl-2-benzimidazolyl)-benzene)), thickness is about 20nm.Then, deposit LiF (thickness is 0.5nm), reach Al (thickness is 120nm), obtain this el light emitting device (3) after the encapsulation.The structure of this el light emitting device (3) can be expressed as: ITO/PEDOT (CH8000)/TFB/PVK:PBD:TPD:PO-01/TPBI/LiF/Al.
Then, measure the optical characteristics of this el light emitting device (3), its measuring result please refer to table 3.
Embodiment 6:
Use mild detergent, acetone, and ethanol clean with the ultra-sonic oscillation ITO of patterning (thickness is as 120nm) substrate of glass.With nitrogen base material is dried up, then with UV-ozonize 30 minutes.Then, select PEDOT (poly-(3,4)-and ethylidene dioxy base thiophene): PSS (e-PSS) is used as hole injection layer, form rete (thickness is as 50nm) take scraper and rotary coating mode (rotating speed 4000rpm), then heat 100 ℃ and continue 40 minutes.Then, on the PEDOT:PSS layer, form TFB (poly-[99 in the scraper for coating mode, 9-dioctyl fluorenyl-2,7-two bases)-copolymerization-(4,4 '-(N-(4-secondary butyl phenenyl)) diphenylamine) layer (thickness is 20nm), then be heated to 180 ℃ and continue 40 minutes under vacuum, the hole-transfer layer material is used as by TFB system.Then, on the TFB layer, form luminescent layer (thickness is about 30nm) with coating method, the coating composition that is used for forming luminescent layer comprises: PVK (Polyvinyl carbazole), PBD (2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3, the 4-oxadiazole), TPD (N, N '-phenylbenzene-N, N '-(two (3-aminomethyl phenyls)-[1, the 1-xenyl]-4,4 '-diamines), reach PO-01-TB, (PVK: PBD: TPD: PO-01-TB is (61: 24: 9: 6), be dissolved in the chlorobenzene solvent to part by weight.Then, on luminescent layer, form hole barrier layer electron transfer layer (hole-block/electron-transport layer) TPBI (1 that holds concurrently with scraper and rotary coating mode, 3,5-three (phenyl-2-benzimidazolyl-)-benzene), thickness is about 20nm.Then, deposit LiF (thickness is 0.5nm), reach Al (thickness is 120nm), obtain this el light emitting device (4) after the encapsulation.The structure of this el light emitting device (4) can be expressed as: ITO/PEDOT (CH8000)/TFB/PVK:PBD:TPD:PO-01-TB/TPBI/LiF/Al.
Then, measure the optical characteristics of this el light emitting device (4), its measuring result please refer to table 3.
Embodiment 7:
Use mild detergent, acetone, and ethanol clean with the ultra-sonic oscillation ITO of patterning (thickness is as 120nm) substrate of glass.With nitrogen base material is dried up, then with UV-ozonize 30 minutes.Then, select PEDOT (poly-(3,4)-and ethylidene dioxy base thiophene): PSS (e-PSS) is used as hole injection layer, form rete (thickness is as 50nm) take scraper and rotary coating mode (rotating speed 4000rpm), then heat 100 ℃ and continue 40 minutes.Then, on the PEDOT:PSS layer, form TFB (poly-[99 in the scraper for coating mode, 9-dioctyl fluorenyl-2,7-two bases)-copolymerization-(4,4 '-(N-(4-secondary butyl phenenyl)) diphenylamine) layer (thickness is 20nm), then be heated to 180 ℃ and continue 40 minutes under vacuum, the hole-transfer layer material is used as by TFB system.Then, on the TFB layer, form luminescent layer (thickness is about 30nm) with coating method, the coating composition that is used for forming luminescent layer comprises: PVK (Polyvinyl carbazole), PBD (2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3, the 4-oxadiazole), TPD (N, N '-phenylbenzene-N, N '-(two (3-aminomethyl phenyls)-[1, the 1-xenyl]-4,4 '-diamines), reach PO-01-HEX, (PVK: PBD: TPD: PO-01-HEX is (61: 24: 9: 6), be dissolved in the chlorobenzene solvent to part by weight.Then, on luminescent layer, form hole barrier layer electron transfer layer (hole-block/electron-transport layer) TPBI (1 that holds concurrently with scraper and rotary coating mode, 3,5-three (phenyl-2-benzimidazolyl-)-benzene), thickness is about 20nm.Then, deposit LiF (thickness is 0.5nm), reach Al (thickness is 120nm), obtain this el light emitting device (5) after the encapsulation.The structure of this el light emitting device (5) can be expressed as: ITO/PEDOT (CH8000)/TFB/PVK:PBD:TPD:PO-01-HEX/TPBI/LiF/Al.
Then, measure the optical characteristics of this el light emitting device (5), its measuring result please refer to table 3.
Table 3
As shown in table 3, under the condition of collocation same body material, the PO-01-TB after the modification and PO-01-HEX are owing to having better solubleness, so the wet process efficiency of element of gained exceeds respectively more than 12 times and 7 times than PO-01.
Although the present invention discloses as above with preferred embodiment, so it is not to limit the present invention.Any the technical staff in the technical field of the invention, without departing from the spirit and scope of the present invention, Ying Kezuo is change and retouching arbitrarily.Therefore, protection scope of the present invention should be as the criterion with the appended claims restricted portion.
Claims (10)
1. organometallic compound, it has suc as formula the chemical formula shown in (I) or the formula (II):
Wherein, R is alkyl or cycloalkyl.
2. organometallic compound as claimed in claim 1, wherein this R is C
1-12Alkyl or C
4-12Cycloalkyl.
3. organometallic compound as claimed in claim 1, wherein this R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.
4. Organnic electroluminescent device comprises:
To electrode; And
Luminescence unit is disposed at this between the electrode,
Wherein, this luminescence unit comprise have formula (I) or (II) shown in the organometallic compound of structure:
Wherein, R is alkyl or cycloalkyl.
5. Organnic electroluminescent device as claimed in claim 4, wherein this R is C
1-12Alkyl or C
4-12Cycloalkyl.
6. Organnic electroluminescent device as claimed in claim 4, wherein this R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.
7. Organnic electroluminescent device as claimed in claim 4, wherein this luminescence unit system prepares in the evaporation mode and gets.
8. Organnic electroluminescent device as claimed in claim 4, wherein this luminescence unit system prepares in the wet process mode and gets.
9. Organnic electroluminescent device as claimed in claim 4, wherein this luminescence unit system sends orange light.
10. composition comprises:
The Organic Light Emitting Diode material of main part; And
Organometallic compound, it has suc as formula the chemical formula shown in (I) or the formula (II):
Wherein, R is alkyl or cycloalkyl.
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