CN1534024A - Terbium compound electroluminous material and device - Google Patents
Terbium compound electroluminous material and device Download PDFInfo
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- CN1534024A CN1534024A CNA031077153A CN03107715A CN1534024A CN 1534024 A CN1534024 A CN 1534024A CN A031077153 A CNA031077153 A CN A031077153A CN 03107715 A CN03107715 A CN 03107715A CN 1534024 A CN1534024 A CN 1534024A
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- pyrazolin
- pmp
- isophthalic acid
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Abstract
An electroluminescent material Tb(L1)3(L2)n is disclosed, where Tb is three-valence positive ion of Tb, Li is the organic chelating negative ion of pyrazolinone and L2 is neutral ligand. The device prepared from it is also disclosed. Their advantages are high brightness and high efficiency.
Description
Technical field
The present invention relates to the organic electroluminescent of field of light emitting materials, the title complex, this title complex that relates in particular to a series of pyrazolone parts, this part and rare earth element terbium is as the application of electroluminescent material and with the device of this title complex as luminescent materials.Compare with device with existing rare earth compounding electroluminescent material, electroluminescent material of the present invention and device have the excellent characteristics of brightness height, excellent in efficiency.
Technical background
At present, the used color monitor of people mostly is teletron and shows or liquid-crystal display, the former volume is big, response speed is slow, efficient is low, the latter compares volume-diminished with the former, can realize flat pannel display, but is the passive type light source because of it, the visual angle is little, low-response, complex process still can not satisfy people's needs.1987, the Deng Qingyun (C.W.Tang) and the VanSlyke (Appl.Phys.Lett.1987 of U.S. Eastman Kodak company, 51,913) organic electroluminescent has been done to start new research, they are clipped in double-deck organic membrane and have made organic electroluminescence device (OLED) between two electrodes.Since then, organic electroluminescent becomes the research focus in luminous field.Organic electroluminescent exists huge magnetism to be that it has following characteristics:
1) adopt organism, the material range of choice is wide, can realize the demonstration of any color from the blue light to ruddiness.
2) driving voltage is low, only needs the volts DS of 3-10 volt.
3) luminosity and luminous efficiency height.
4) full solidified active illuminating.
5) visual angle is wide, and response speed is fast.
6) preparation process is simple, and expense is low.
7) ultrathin membrane, in light weight.
8) can be produced on the softish substrate, device is expected bending fold.
Electroluminescent organic material can be divided into organic polymer and small molecule material.Organic polymer is used for electroluminescent, but is difficult to obtain pure color owing to spectral range is wide.Rare earth compounding belongs to organic small molecule material.For the luminous rare earth compounding of central ion (the especially title complex of europium and terbium), because its luminous mechanism is to be excited to singlet state behind the part absorption energy, give excited triplet state with transmission ofenergy more through leaping up between system then, give central ion with transmission ofenergy again, it is excited, the radiative transition process of rare earth central ion excited state to ground state takes place at last.Compare with other organic molecules, it is narrow that rare earth compounding has emission band, the purity of color height, modified ligand does not influence the emission of central ion, be used for do not spinned restriction, the internal quantum efficiency of choosing rule of electroluminescent and can reach advantage such as 100% in theory, make it become one of the research focus in electroluminescent field.
The title complex of terbium is a green luminescent material, people such as Gao Xicun, Cao Hong in 1998, Huang Chunhui reported a terbium coordination compound promptly three (3-methyl isophthalic acid-phenyl-4-isobutyryl pyrazolin-5-one), two (triphenylphosphine oxides) close terbium (III) and [abbreviate Tb (PMIP) as
3(TPPO)
2, the structural formula See Figure] electroluminescent properties, device architecture is: ITO/TPD (42nm)/Tb (PMIP)
3(TPPO)
2(42nm)/[wherein TPD is N to AlQ (42nm)/Al (50nm), N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-phenylbenzene-4,4 '-diamines, AlQ are oxine aluminium], at 18 volts to six voltages, high-high brightness reaches every square metre of 920 Kan Tela, but some light spreads out of material TPD from the hole, and, TPD luminous ratio increase along with the increase of voltage, the light that device is sent is not pure green, but is greyish-green.Every watt of power efficiency 0.51 lumen of this device (X.C.Gao, H.Cao, C.H.Huang, B.G.Li, S.Umitani, Appl.Phys.Lett.1998,72,2217).
Tb (PMIP)
3(TPPO)
2, TPD structural formula
S.Capecchi in 2000, O.Renault, people such as D-G.Moon disclose with i.e. three (3-methyl isophthalic acid-phenyl-4-pivaloyl) pyrazolin-5-one of terbium coordination compound) (triphenylphosphine oxide) close terbium (III) and [abbreviate Tb (tb-PMP) as
3TPPO, the structural formula See Figure] make device as luminescent layer.Single layer device ITO/Tb (tb-PMP) wherein
3The bright voltage that rises of TPPO (85nm)/Mg:Al is 23 volts, and maximum brightness is every square metre of (23 volts time) 6 Kan Tela, and power efficiency is every watt of 0.05 lumen.Introducing hole mobile material TPD, behind hole-injecting material MTDATA and the hole barrier materials TAZ (the wherein structural formula See Figure of MTDATA and TAZ), made following device: ITO/MTDATA (7.5nm)/TPD (40nm)/[Tb (tb-PMP)
3TPPO] (34nm)/TAZ (60nm)/Mg:Al, its maximum brightness is every square metre of (cd/m of 2000 Kan Tela
2), maximum power efficient is every watt of 2.4 lumen when 16 volts of voltages, but the brightness of this moment has only every square metre of [S.Capecchi of 70 Kan Tela, O.Renault, people such as D-G.Moon, Advanced Materials, Vol.12 (21), 1591-1594,2000], its performance is also far away less than other small molecules.
Tb (tb-PMP)
3The structural formula of TPPO
The structural formula of the structural formula TAZ of MTDATA
The factor that influences the terbium coordination compound electroluminescent properties mainly contains: the luminescent properties of material itself, the carrier transmission performance of material, and the problems such as concentration quenching in the luminescence process.The photoluminescence efficiency of material itself is high more, and electroluminescent efficiency is just good more; Current carrier (hole and (or) electronics) transmission performance is good more, and it is compound in the luminous zone to help current carrier more, helps the raising of brightness and efficient; And change the chemical structure of title complex, and increase sterically hinderedly, can reduce concentration quenching, also help improving the performance of device.Therefore, synthetic terbium coordination compound with These characteristics just becomes the key that improves its luminescent properties.We are on working foundation for many years, rare earth compounding electroluminescent material and device have been invented with These characteristics, the high-high brightness of some terbium coordination compound electroluminescent material and device has reached 12000 Kan Tela more than every square metre, thereby has finished the present invention.
Description of drawings
Fig. 1 device architecture synoptic diagram
A. single layer device,
B. bi-layer devices,
C. three layer devices,
D. four-layer device;
Wherein each layer is 1:ITO, 2: metallic cathode, 3: terbium coordination compound layer, 4: electron transfer layer, 5: hole transmission layer, 6: hole blocking layer.
Fig. 2 three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (triphenylphosphine oxide) closes terbium [Tb (eb-PMP)
3TPPO] photoluminescence spectra;
Fig. 3 three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (2,2 '-Lian pyridine) closes terbium [Tb (eb-PMP)
3Bipy] photoluminescence spectra;
Fig. 4 three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (o-phenanthroline) closes terbium [Tb (eb-PMP)
3Phen] photoluminescence spectra;
Fig. 5 three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (triphenylphosphine oxide) closes terbium [Tb (te-PMP)
3TPPO] photoluminescence spectra;
Fig. 6 three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (o-phenanthroline) closes terbium [Tb (te-PMP)
3Phen] photoluminescence spectra;
Fig. 7 three (3-methyl isophthalic acid-phenyl-4-(ethyl hexanoyl base) pyrazolin-5-one) (o-phenanthroline) closes terbium [Tb (eh-PMP)
3Phen] photoluminescence spectra;
The electroluminescent spectrum of Fig. 8 device one;
The electroluminescent spectrum of Fig. 9 device two;
The electroluminescent spectrum of Figure 10 device three;
The electroluminescent spectrum of Figure 11 device four;
The voltage-to-current curve of Figure 12 device two;
Voltage-the brightness curve of Figure 13 device two.
Summary of the invention
The purpose of this invention is to provide the following a series of pyrazolone ligand L of structural formula
1:
Wherein
R is a carbonatoms greater than 4 straight or branched alkyl, and preferred carbonatoms is the branched-chain alkyl of 5-9, particularly-and CH (CH
2CH
3)
2,-CH
2C (CH
3)
3With-CH (CH
2CH
3) CH
2CH
2CH
2CH
3With
R
1For hydrogen, carbonatoms is the straight or branched alkyl of 1-5.
Above-mentioned carbonatoms is that the straight or branched alkyl of 1-5 for example is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl etc.
Above-mentioned carbonatoms is greater than 4 straight or branched alkyl, for example be amyl group, 1-ethyl propyl, 2-ethyl-butyl, 2,2-dimethyl propyl, 1-propyl group butyl, 1-ethyl pentyl group, 2,2-dimethyl amyl group, 2,2-diethyl amyl group etc., preferred carbonatoms is the branched-chain alkyl of 5-9, particularly 1-ethyl propyl-CH (CH
2CH
3)
2, 2,2-dimethyl propyl-CH
2C (CH
3)
3With 1-ethyl pentyl group-CH (CH
2CH
3) CH
2CH
2CH
2CH
3
Compare with part openly, substituent sterically hindered by increasing, when making it with the title complex of terbium formation, can only with a triphenyl oxygen see (TPPO) combine, balance the transmission performance of current carrier, improved the brightness and the efficient of device.
The example of part is: 3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one (eb-PMP); 3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one (te-PMP) and 3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one (eh-PMP).
Another object of the present invention has provided the preparation method of above-mentioned part, and above-mentioned part can be according to technology preparation known in the art.For example press Xi-Cun Gao etc., Synthetic Metals, 99, p27-132 (1999) disclosed method is synthetic.Concrete grammar is with 3-methyl isophthalic acid-(R
1-substituted-phenyl)-and the 4-pyrazolin-5-one is dissolved in the exsiccant dioxane, adds calcium hydroxide and hydrated barta powder, is added dropwise to corresponding acyl chlorides R-COX again, and wherein X is a halogen.The stirring and refluxing regular hour, after reaction finishes, reaction mixture neutralizes with acid, directly obtain head product, perhaps use organic solvent such as chloroform extraction, organic phase after drying, remove after desolvating head product, this head product can be with conventional purification process such as method purifying such as recrystallization, column chromatography.
Another object of the present invention has provided a series of with pyrazolone part (L
1) be the center part, with the terbium coordination compound that the rare earth element terbium forms, the general formula of this title complex is:
Tb(L
1)
3(L
2)
n
Wherein Tb is the trivalent positive ion of terbium;
L
1Organic ligand for above-mentioned pyrazolone;
L
2Be neutral ligand, preferred L
2For the triphenyl oxygen of following formula is seen (TPPO), 2,2 '-dipyridyl (Bipy) or o-phenanthroline (Phen):
R ' wherein, R " identical or different, independently be hydrogen, C separately
1-4The alkyl or the nitrogen heterocycle of straight or branched; With
N is 1 or 2.
Term " C wherein
1-4The straight or branched alkyl " for containing the alkyl of straight or branched of 1-4 carbon atom, specifically define referring to C mentioned above
1-5The straight or branched alkyl.
Term wherein " nitrogen heterocycle " can be 5 or 6 yuan of aromatic heterocyclic groups that contain 1 or 2 nitrogen-atoms, for example pyrryl, pyridyl, pyrazolyl, pyrimidyl etc.
The example of described terbium coordination compound comprises: (a) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (triphenylphosphine oxides) close terbium [Tb (eb-PMP)
3TPPO], (b) terbium [Tb (eb-PMP) is closed in three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (2,2 '-dipyridyl)
3Bipy], (c) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (eb-PMP)
3Phen], (d) three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (triphenylphosphine oxides) close terbium [Tb (te-PMP)
3TPPO], (e) terbium [Tb (te-PMP) is closed in three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (2,2 '-dipyridyl)
3Bipy], (f) three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (te-PMP)
3Phen] and (g) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (eh-PMP)
3Phen].
Preferably be the terbium coordination compound of part with (eb-PMP), particularly three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (triphenylphosphine oxides) close terbium [Tb (eb-PMP)
3TPPO].
Another object of the present invention has provided the synthetic method of above-mentioned title complex, and this title complex can be synthetic by methods known in the art, as press Xi-Cun Gao etc., Synthetic Metals, and 99, p27-132 (1999) disclosed method is synthetic.
Terbium coordination compound of the present invention has excellent electroluminescent properties, can be used as electroluminescent material.In addition, this title complex also has good electronic transmission performance, therefore can also be used as electron transport material.With it during as electron transfer layer, can improve blue-light-emitting material N greatly, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-phenylbenzene-4,4 '-diamines (TPD) and N, N '-phenylbenzene-N, N '-two (1-naphthyl)-1,1 '-phenylbenzene-4, the luminosity and the efficient of 4 '-diamines (NPB).Therefore, terbium coordination compound of the present invention can be used as luminescent layer and/or electron transfer layer making device.
Therefore, another object of the present invention is to provide a series of new be part (L with the pyrazolone
1) terbium coordination compound that forms with the rare earth ion terbium is as the application of luminescent material, and provide with the device of this luminescent material as luminescent layer and/or electron transfer layer.This device can be single layer device, bi-layer devices or multilayer device, for example three layers, four layers or more multi-layered device.
For example, can comprise conductive glass (ITO) substrate layer, terbium coordination compound layer and cathode layer as the device of luminescent layer and/or electron transfer layer, form so-called single layer device with the new pyrazolone terbium coordination compound of the present invention.
In the embodiment of element manufacturing, for strengthening the injection of electronics, sometimes need to add one deck electron transfer layer between negative electrode and luminescent layer, this electron transfer layer is generally a kind of title complex oxine aluminium (AlQ) or other material with electron-transporting type system such as TAZ (see before and state the background technology partial structural formula) etc. of aluminium.The device that comprises conductive glass (ITO) substrate layer, terbium coordination compound layer, cathode layer and electron transfer layer is a bi-layer devices.
For strengthening the injection in hole, need sometimes between ITO and luminescent layer, to add one deck hole transmission layer, this hole transmission layer plays the effect of transporting holes and block electrons, hole transmission layer can be by arylamine family title complex, as Polyvinyl carbazole (PVK), N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-phenylbenzene-4,4 '-diamines (TPD), N, N '-phenylbenzene-N, N '-two (1-naphthyl)-1,1 '-phenylbenzene-4,4 '-diamines (NPB) etc.Thisly comprise that the device of conductive glass (ITO) substrate layer, terbium coordination compound layer, cathode layer, electron transfer layer and hole transmission layer is so-called three layer devices.
Pass luminescent layer and enter electron transfer layer for preventing the hole, reduce the illumination effect of luminescent layer, on conductive glass (ITO) substrate between luminescent layer and the electron transfer layer, deposit one deck hole barrier materials as 2,9-dimethyl-4,7-phenylbenzene-1,10-Fei Luolin (BCP).Thisly comprise that the device of conductive glass (ITO) substrate layer, terbium coordination compound layer, cathode layer, electron transfer layer, hole transmission layer and hole blocking layer is a four-layer device.
Similarly, can also make device more than four layers as required.
Structural representation with device of one～four layer is seen Fig. 1.
Therefore, another object of the present invention also is to provide making with the method for above-mentioned materials as the device of luminescent layer and/or electron transfer layer.
The making of electroluminescent device can be synthetic by methods known in the art, as press reference (Appl.Phys.Lett.1987,51,913) C.W.Tang and S.A.VanSlyke disclosed method and make.Concrete grammar is: in high vacuum (less than 8 * 10
-4Pa) under the condition, depositing light-emitting material on conductive glass (ITO) substrate that process is cleaned, negative electrode on deposition on the luminescent material, negative electrode is generally the alloy of a kind of metal or two kinds of metals.
For strengthening hole transmission layer that being infused in of hole add between ITO and the luminescent layer usually with the method film forming of spin coating or vacuum evaporation.
Below by specific embodiment product of the present invention and method are further described, but the protection domain that these specific embodiments do not limit the present invention in any way.
Specific embodiments
Raw materials used is known compound, can buy on market, or available methods known in the art is synthetic.
The mensuration of electroluminescent spectrum is on PR650 spectrograph or Hitachi F4500 fluorescence spectrophotometer, apply a constant voltage (usually 3-30 volt between) to device in, write down its emmission spectrum.
Voltage-to-current (I-V) curve and voltage-brightness (L-V) curve are by measuring on the computer-controlled Keithley 2400 Sourcemeter Unit, and brightness is corrected (referring to accompanying drawing 12 and 13) by silicon photoelectric diode.
Embodiment 1: part 3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one (eb-PMP) synthetic
In the exsiccant there-necked flask, add 7.5 gram (0.05mol) 3-methyl isophthalic acid-phenylpyrrazolin-5-ketone and anhydrous 1,100 milliliters of 4-dioxane, heated and stirred is to dissolving, the powder that adds 9 gram (0.18mol) calcium hydroxides and 1 gram (0.03mol) hydrated barta, be cooled to room temperature, be added dropwise to 8 milliliters of 2-ethyl butyryl chlorides (0.058mol), stirring and refluxing reaction 18 hours.The reaction mixture impouring is contained in 350 ml deionized water of 15 milliliters of concentrated hydrochloric acids, separate out red oil, chloroform extraction, be washed till nearly neutrality with deionized water, anhydrous sodium sulfate drying 24 hours is evaporated to the liquid in rotation that obtains dried, with sherwood oil: ethyl acetate (20: 1) is an eluent, separate purification with silicagel column, get pink colour oily matter 9.6g, yield 70%.
1H-NMR(400Hz，CDCl
3)δ：7.87(2H)；7.45(2H)；7.28(1H)；2.82(1H)；2.48(3H)；1.86(4H)；0.94(6H).
Embodiment 2: part 3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one (eh-PMP) synthetic
Synthetic method is with embodiment 1, but replaces 2-ethyl butyryl chloride with the 2-ethyl hexanoyl chloro.
1H-NMR(400Hz，CDCl
3)δ：7.87(2H)；7.45(2H)；7.28(1H)；2.90(1H)；2.48(3H)；1.63(4H)；1.50(4H)；0.94(6H).
Embodiment 3: part 3-methyl isophthalic acid-phenyl-4-(2-tertiary butyl ethanoyl) pyrazolin-5-one (te-PMP) synthetic
According to the method identical with embodiment 1, but with 3, the 3-dimethyl-butyrylchlorine replaces 2-ethyl butyryl chloride, with preparation 3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one (te-PMP).The crude product of this product can be by purifying with ethyl alcohol recrystallization.Fusing point 89-90 ℃.
1H-NMR(400Hz，CDCl
3)δ：7.87(2H)；7.45(2H)；7.28(1H)；2.62(2H)；2.48(3H)；1.86(4H)；1.12(9H).
Embodiment 4: title complex three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (triphenylphosphine oxide) closes terbium (Tb (eb-PMP)
3Synthesizing TPPO)
A certain amount of part [3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one] and triphenylphosphine oxide are dissolved in dehydrated alcohol, add the aqueous solution of a certain amount of terbium trichloride, the feed ratio of raw material: TbCl
3: eb-PMP: NaOH: TPPO=1: 3: 3: 2).In 70 ℃, under agitation condition, be added dropwise to 1.0 normal aqueous sodium hydroxide solutions, reacted 10 hours.With reacting liquid filtering, leave standstill the back by separating out colourless crystal in the mother liquor, use the dehydrated alcohol recrystallization, yield is greater than 80%.Fusing point: 156-157 ℃.The photoluminescence spectra of this title complex is seen Fig. 2.
Embodiment 5: three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (o-phenanthroline) closes terbium (Tb (eb-PMP)
3Synthesizing Phen)
With a certain amount of part [3-methyl isophthalic acid-phenyl-4-(2-ethyl) butyryl radicals] pyrazolin-5-one] and o-phenanthroline be dissolved in dehydrated alcohol, add the aqueous solution of a certain amount of terbium trichloride, feed ratio: TbCl
3P: eb-PM: NaOH: Phen=1: 3: 3: 1.In 70 ℃, under the agitation condition, be added dropwise to 1.0 normal aqueous sodium hydroxide solutions, reacted 10 hours, with reacting liquid filtering, separate out the Powdered crystal of white in the mother liquor, use the trichloromethane recrystallization, yield is greater than 80%.Fusing point: 206-207 ℃.The photoluminescence spectra of this title complex is seen Fig. 4.
Embodiment 6: three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (2,2 '-Lian pyridine) closes terbium [Tb (eb-PMP)
3Bipy] synthetic
According to embodiment 4 or 5 identical methods,, 2 '-dipyridyl reaction replacement triphenylphosphine oxide or o-phenanthroline and 3-methyl isophthalic acid-phenyl-4-[(2-ethyl just with 2) butyryl radicals] pyrazolin-5-one reacts, and obtains the purpose product.Accompanying drawing 3 is the photoluminescence spectra of this title complex.
Embodiment 7: title complex three (3-methyl isophthalic acid-phenyl)-4-(2-tertiary butyl ethanoyl) pyrazolin-5-one) (triphenylphosphine oxide) closes terbium (Tb (te-PMP)
3TPPO), terbium [Tb (te-PMP) is closed in three (3-methyl isophthalic acid-phenyl-4-(2-tertiary butyl ethanoyl) pyrazolin-5-one) (2,2 '-dipyridyl)
3Bipy] and three (3-methyl isophthalic acid phenyl-4-(2-tertiary butyl ethanoyl) pyrazolin-5-one) (o-phenanthrolines) close terbium (Tb (te-PMP)
3Synthesizing Phen)
According to the method identical with embodiment 4,5 and 6; replace 3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one with 3-methyl isophthalic acid-phenyl-4-(2-tertiary butyl ethanoyl) pyrazolin-5-one; respectively with triphenylphosphine oxide, 2; 2 '-dipyridyl and o-phenanthroline reaction; the crude product that obtains with corresponding method purifying after, obtain the above-mentioned purpose product.
Tb (te-PMP)
3TPPO fusing point: 215-216 ℃; The photoluminescence spectra of this title complex is seen Fig. 5.
Tb (te-PMP)
3Phen fusing point: 304-305 ℃; The photoluminescence spectra of this title complex is seen Fig. 6.
Embodiment 8: three (3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one) (o-phenanthroline) closes terbium [Tb (eh-PMP)
3Phen] synthetic
According to the method identical, just with (3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one) replacement 3-methyl isophthalic acid-phenyl-4-[(2-ethyl with embodiment 5) butyryl radicals] pyrazolin-5-one and o-phenanthroline react, and obtains the purpose product.Accompanying drawing 7 is the photoluminescence spectra of this title complex.
Embodiment 9: the making of device and performance test
Ito glass sheet (2.1 * 2.1 millimeter 2) removes 1/3rd ITO with concentrated hydrochloric acid corrosion, with its with the ultrasonic cleaning of detergent based organic solvent clean after, oven dry places in the vacuum plating unit, less than 8 * 10
-4Under the high vacuum condition of Pa, monitor the thickness of each layer with quartz resonator spare, with title complex, hole barrier materials, electron transport material and the metallic cathode [magnesium silver alloys (Mg of hole mobile material, terbium
0.9Ag
0.1) or aluminium or calcium or other metals] deposit on the conductive glass successively.The thickness of each organic layer can change so that device sends the feature green glow of title complex, or cooperate material only as electron transfer layer so that device sends the blue light of TPD or NPB.
Make four-layer device as Fig. 1 with this method, the structure of the various devices that make is as follows:
Device one: ITO/TPD/Tb (eb-PMP)
3TPPO/BCP/AlQ/Mg
0.9Ag
0.1/ Ag
Device two: ITO/NPB/Tb (eb-PMP)
3TPPO/BCP/AlQ/Mg
0.9Ag
0.1/ Ag
Device three: ITO/NPB/Tb (eb-PMP)
3TPPO/BCP/Mg
0.9Ag
0.1/ Ag
Device four: ITO/TPD/Tb (eb-PMP)
3Phen/BCP/AlQ/Mg
0.9Ag
0.1/ Ag
Wherein TPD is N, N '-phenylbenzene-N, and N '-two (3-aminomethyl phenyl)-1,1 '-phenylbenzene-4,4 '-diamines BCP are 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline; AIQ is an oxine aluminium; And NPB is N, N '-phenylbenzene-N, N '-dinaphthyl-1,1 '-phenylbenzene-4,4 '-diamines.
The research of electric current relative voltage is carried out on computer-controlled Keithly 2400 source instrument.
With F4500 luminoscope or PR650 spectrograph record photoluminescence and electroluminescence spectrum.When measuring element performance and electroluminescent spectrum, the ITO electrode always links to each other with positive pole.The emmission spectrum of device one～four is seen accompanying drawing 8～Figure 11.
The performance data of device one～four sees the following form:
Device maximum brightness maximum power efficient has flowed bright voltage glow color luminescent spectrum
Kan Tela/m
2Bright/watt volt
Device one 8,000 11.3 4V green glows are seen figure 11
Last table data declaration, above-mentioned device one and four has used title complex Tb of the present invention (eb-PMP) respectively
3TPPO and Tb (eb-PMP)
3Phen has obtained the feature green glow of terbium as luminescent material, and with document Appl.Phys.Lett.1998,72,2217 compare, and brightness and efficient all are significantly improved.On this basis, replace TPD as hole transmission layer,, make device two thus to have strengthened the injection in hole with NPB.Its brightness is increased to every square metre of 12000 Kan Tela, and efficient can reach every watt of 14 lumen.
For device three, because title complex Tb (tb-PMP)
3TPPO has good electric transmission character, sends N, N '-phenylbenzene-N, and N '-dinaphthyl-1,1 '-phenylbenzene-4, the blue light of 4 '-diamines, device brightness are every square metre of 7000 Kan Tela.In contrast to this, close terbium (III) and [abbreviate Tb (PMIP) as by known title complex three (3-methyl isophthalic acid-phenyl-4-isobutyryl pyrazolin-5-one) two (triphenylphosphine oxides)
3(TPPO)
2Tb (tb-PMP)
3TPPO] electroluminescent device ITO/TPD (42nm)/Tb (PMIP) of forming
3(TPPO)
2(42nm)/AlQ (42nm)/Al (50nm) launch blue light high-high brightness have only every square metre of 900 Kan Tela (X.C.Gao, H.Cao, C.H.Huang, B.G.Li, S.Umitani, Appl.Phys.Lett.1998,72,2217).Therefore, title complex Tb of the present invention (tb-PMP)
3TPPO has better luminous and/or electric transmission character than known other rare earth compounding.
Compare with device with other rare earth compounding electroluminescent material, terbium coordination compound of the present invention has higher brightness and better electroluminescent efficiency, and the high-high brightness of the electroluminescent device of gained of the present invention is the highest in the present rare earth compounding electroluminescent device.
Good effect
The inventor has found to have high light photoluminescence efficient and can produce high efficiency electroluminous Green terbium coordination compound. The electroluminescent properties of these complexs obviously is better than published terbium and cooperates Thing Tb (tb-PMP)3TPPO. As electroluminescent material, can obtain pure with these complexs Green light, brightness are all above every square metre of 2000 Kan Tela. Wherein maximum brightness can reach 12000 Every square metre of Kan Tela, power efficiency can reach every watt of 14 lumen, than the highest published numerical value 2000 Every square metre of Kan Tela and the every watt-minute of 2.6 lumens be you can well imagine high 9 and 7 times, and, in brightness 4000 Power efficiency still is higher than every watt of 2.0 lumen during every square metre of Kan Tela. In addition, these complexs Can also make blue emitting material obtain better illumination effect as electron transport material, make N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-diphenyl-4, the luminosity of 4 '-diamines (NPB) Surpass every square metre of 6000 Kan Tela, every watt of power efficiency 1.82 lumen. These terbium coordination compounds As the electroluminescent material of excellence, will become the colored industry that shows, such as colour TV, mobile phone, And the new material in the industry such as illumination.
Claims (11)
1. the following pyrazolone ligand L of structural formula
1:
Wherein
R is a carbonatoms greater than four straight or branched alkyl; With
R
1For hydrogen, carbonatoms is the straight or branched alkyl of 1-5.
2. the pyrazolone part of claim 1, R group wherein is the branched-chain alkyl of 5-9.
3. the pyrazolone part of claim 2, R group wherein is-CH (CH
2CH
3)
2,-CH
2C (CH
3)
3With-CH (CH
2CH
3) CH
2CH
2CH
2CH
3
4. the pyrazolone part of claim 3, R group wherein is 1-ethyl propyl-CH (CH
2CH
3)
2
5. the pyrazolone part of claim 1; wherein said part is 3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one (eb-PMP); 3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one (te-PMP) and 3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one (eh-PMP).
6. the preparation method of any pyrazolone part of claim 1-5, this method comprises makes 3-methyl isophthalic acid-(R
1-substituted-phenyl) pyrazolin-5-one in the presence of calcium hydroxide and hydrated barta, reacts with corresponding acyl chlorides R-COX in organic solvent, and wherein X is a halogen.
7. be the terbium coordination compound of part with any one pyrazolone of claim 1-5, this title complex has following general formula:
Tb(L
1)
3(L
2)
n
Wherein Tb is the trivalent positive ion of terbium;
L
1Pyrazolone part for any definition of claim 1-5;
L
2Be neutral ligand, be selected from the triphenylphosphine oxide (TPPO), 2 of following formula, 2 '-dipyridyl (Bipy) and o-phenanthroline (Phen):
R ' wherein, R " identical or different, independently be hydrogen, C separately
1-4Straight or branched alkyl or nitrogen heterocycle; And
N is 1 or 2.
8. the title complex of claim 7, wherein said part is that (a) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (triphenylphosphine oxide) closes terbium [Tb (eb-PMP)
3TPPO], (b) terbium [Tb (eb-PMP) is closed in three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (2,2 '-dipyridyl)
3Bipy], (c) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl butyryl radicals) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (eb-PMP)
3Phen], (d) three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (triphenylphosphine oxides) close terbium [Tb (te-PMP)
3TPPO], (e) terbium [Tb (te-PMP) is closed in three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (2,2 '-dipyridyl)
3Bipy], (f) three (3-methyl isophthalic acid-phenyl-4-(tertiary butyl ethanoyl) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (te-PMP)
3Phen] and (g) three (3-methyl isophthalic acid-phenyl-4-(2-ethyl hexanoyl base) pyrazolin-5-one) (o-phenanthrolines) close terbium [Tb (eh-PMP)
3Phen].
9. claim 7 or 8 title complex are as the application of electroluminescent material.
10. electroluminescent device, it is characterized in that this device with the title complex of claim 7 or 8 as electroluminescent material.
11. the electroluminescent device of claim 10, wherein this device can be single layer device, bi-layer devices or multilayer device.
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|---|---|---|---|
| CNA031077153A CN1534024A (en) | 2003-04-02 | 2003-04-02 | Terbium compound electroluminous material and device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031077153A CN1534024A (en) | 2003-04-02 | 2003-04-02 | Terbium compound electroluminous material and device |
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ID=34283007
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100505965C (en) * | 2004-11-25 | 2009-06-24 | 新日铁化学株式会社 | Organic electroluminescence device |
-
2003
- 2003-04-02 CN CNA031077153A patent/CN1534024A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100505965C (en) * | 2004-11-25 | 2009-06-24 | 新日铁化学株式会社 | Organic electroluminescence device |
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