CN101747374A - Compound containing phosphorus-oxygen groups and organic electroluminescent device comprising compound containing phosphorus-oxygen groups and preparation method thereof - Google Patents
Compound containing phosphorus-oxygen groups and organic electroluminescent device comprising compound containing phosphorus-oxygen groups and preparation method thereof Download PDFInfo
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- CN101747374A CN101747374A CN201010002646A CN201010002646A CN101747374A CN 101747374 A CN101747374 A CN 101747374A CN 201010002646 A CN201010002646 A CN 201010002646A CN 201010002646 A CN201010002646 A CN 201010002646A CN 101747374 A CN101747374 A CN 101747374A
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Abstract
The invention provides a compound containing phosphorus-oxygen groups, at least comprising two phosphorus-oxygen groups and a bridging unit. The invention also provides an organic electroluminescent device comprising a substrate, a first electrode layer is arranged on the substrate, at least one or a plurality of organic electroluminescent layers are arranged on the first electrode layer, an electron transport layer is arranged on the organic electroluminescent layer, a second electrode layer is arranged on the electron transport layer, and the organic electroluminescent layer and/or the electron transport layer comprise the compound containing the phosphorus-oxygen groups. The invention further provides a preparation method of the organic electroluminescent device, comprising the following steps: a first electrode is formed on the substrate, one or a plurality of organic electroluminescent layers are formed on the first electrode, the electron transport layer is formed on the organic electroluminescent layer, a second electrode is formed on the electron transport layer, and the organic electroluminescent layer and/or the electron transport layer comprise the compound containing the phosphorus-oxygen groups.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, relate in particular to a kind of compound that contains phosphorus-oxygen groups, contain organic electroluminescence device of phosphorus-oxygen groups compound and preparation method thereof.
Background technology
Organic electroluminescence device is a kind of selfluminous element, has characteristics such as voltage is low, brightness is high, the visual angle is wide, response is fast, thermal adaptability is good, is widely used in electronic product indicating meters such as digital camera, mobile phone, MP3.
The principle of luminosity of organic electroluminescence device is as follows: under effect of electric field, hole and electronics inject from anode and negative electrode respectively, are compounded to form exciton at luminescent layer, and the exciton attenuation is luminous.In order to improve the performance of device, prior art generally increases one deck electron transfer layer between luminescent layer and negative electrode, in order to injection and the transmission situation of improving electronics.Electron transport material must satisfy following requirement: have higher electronic mobility, be easy to transmission electronic; Has stronger electronics receiving capability; Have higher electron affinity, be easy to inject electronics etc. by negative electrode.Prior art discloses multiple material as the electric transmission layer material, as 8-hydroxyquinoline aluminum (Alq
3) wait a metal-organic complex or 2-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD), 1,3,5-three (2-N-phenyl benzimidazolyl-) benzene (TPBI), 3-(4-phenylbenzene)-5-(tert-butyl-phenyl)-4-(4-ethylphenyl)-1,2,4-triazole aromatic series organic molecules such as (TAZ).
But the electron transfer rate of existing electron transport material is about 10
-5Cm
2V
-1s
-1-10
-6Cm
2V
-1s
-1, and the hole mobile material commonly used such as the hole migration speed of tri-arylamine group material can reach 10
-2Cm
2V
-1s
-1-10
-3Cm
2V
-1s
-1, the difference of electron transport material and hole mobile material transfer rate causes electronics and the hole concentration imbalance in the luminescent layer, thus the performance of restriction organic electroluminescence device makes device efficiency lower.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of compound that contains phosphorus-oxygen groups, contains organic electroluminescence device of phosphorus-oxygen groups compound and preparation method thereof, improves the efficient of organic electroluminescence device.
The invention provides a kind of formula (I) compound:
Wherein,
Bridge is the bridging unit, is selected from any one structure of following (1)-(126):
Ar
1-Ar
8Be selected from any one structure of following (1001)-(1057) respectively:
Ar
9Be selected from any one structure of following A-G:
R
1Alkyl for C1-C8.
Preferably, described compound has formula (I-a) structure:
Preferably, described compound has formula (I-b) structure:
Preferably, described compound has formula (I-c) structure:
Preferably, described compound has formula (I-d) structure:
Preferably, described compound has formula (I-e) structure:
Preferably, described compound has formula (I-f) structure:
Preferably, described compound has formula (I-g) structure:
The present invention also provides a kind of organic electroluminescence device, comprising:
Substrate;
First electrode layer is arranged on substrate;
On described first electrode layer, has one or more layers organic electro luminescent layer at least;
On described organic electro luminescent layer, electron transfer layer is arranged;
On described electron transfer layer, the second electrode lay is arranged;
Described organic electro luminescent layer and/or electron transfer layer comprise the described compound that contains phosphorus-oxygen groups of technique scheme.
Preferably, described organic electro luminescent layer comprises material of main part and the singlet fluorescence dye or the triplet state phosphorescent coloring that are entrained in the described material of main part, and described material of main part is the described compound that contains phosphorus-oxygen groups of technique scheme.
The present invention also provides a kind of preparation method of organic electroluminescence device, comprising:
On substrate, form first electrode;
On described first electrode, form one or more layers organic electro luminescent layer;
On described organic electro luminescent layer, form electron transfer layer;
On described electron transfer layer, form second electrode;
Described organic electro luminescent layer and/or electron transfer layer comprise the described compound that contains phosphorus-oxygen groups of above-mentioned technological method.
Preferably, described organic electro luminescent layer comprises material of main part and the singlet fluorescence dye or the triplet state phosphorescent coloring that are entrained in the described material of main part, and described material of main part is the described compound that contains phosphorus-oxygen groups of technique scheme.
Compared with prior art, the present invention has introduced phosphorus-oxygen groups in the organic compound periphery, by making up line style, star-like or X type molecule, obtains containing the compound of phosphorus-oxygen groups.Phosphorus-oxygen groups is an electron acceptor(EA) class group, can improve the electron transport ability of organic compound, makes the organic compound that contains phosphorus-oxygen groups have the good electron transmittability.Contain electron transport material or the material of main part of the compound of phosphorus-oxygen groups, can improve electron transfer rate, the concentration in electronics and hole in the balance luminescent layer, thereby the performance and the efficient of raising device as organic electroluminescence device.Experiment shows, is material of main part with the compound that contains phosphorus-oxygen groups provided by the invention, is that the maximum luminous efficiency of the device of dopant material preparation can reach 36.4cd/A with FIrpic, and maximum power efficiency can reach 29.3ml/W, and high-high brightness can reach 11300cd/m
2With the compound that contains phosphorus-oxygen groups provided by the invention is electron transport material, and the maximum luminous efficiency that is entrained in the device for preparing among the PVK with FIrpic can reach 34.4cd/A, and maximum power efficiency can reach 16.9ml/W, and high-high brightness can reach 7750cd/m
2
Description of drawings
The structural representation of the organic electroluminescence device that Fig. 1 provides for the embodiment of the invention;
What Fig. 2 provided for the embodiment of the invention is the luminous efficiency-current density graphic representation of the organic electroluminescence device of electron transfer layer with TPCz;
That Fig. 3 provides for the embodiment of the invention is the current density-voltage-brightness curve figure of the organic electroluminescence device of electron transfer layer with TPCz;
What Fig. 4 provided for the embodiment of the invention is the electroluminescent spectrum of the organic electroluminescence device of electron transfer layer with TPCz;
What Fig. 5 provided for the embodiment of the invention is the luminous efficiency-current density graphic representation of the organic electroluminescence device of material of main part with TPCz;
That Fig. 6 provides for the embodiment of the invention is the current density-voltage-brightness curve figure of the organic electroluminescence device of material of main part with TPCz;
What Fig. 7 provided for the embodiment of the invention is the electroluminescent spectrum of the organic electroluminescence device of material of main part with TPCz.
Embodiment
The invention provides a kind of organic compound that contains phosphorus-oxygen groups, have formula (I) structure:
Wherein, Bridge is the bridging unit, and its effective conjugate length is 1 aromatic ring, 2 aromatic rings or 3 aromatic rings; Its connection site can be 2,3 or 4.When Bridge had 2 connection site, its structure was any described structures in above-mentioned (1)-(68); When Bridge had 3 connection site, its structure was any described structures in above-mentioned (69)-(96); When Bridge had 4 connection site, its structure was any described structures in above-mentioned (97)-(126).Ar
1-Ar
4Be aromatic substituent, be selected from any described structure in above-mentioned (1001)-(1057) respectively, Ar
1-Ar
4Can be identical, also can be different, the present invention does not have particular restriction.
According to the present invention, when Bridge is preferably above-mentioned (14) described structure and R
1Be preferably-H and Ar
1-Ar
4When all being preferably phenyl, described compound has formula (I-a) structure, called after DPCz:
The present invention does not have particular restriction to the preparation method of DPCz, preferably includes following steps:
With N-ethyl-2,7-dibromo carbazole and diphenyl phosphorus chloride are raw material, are reaction medium with THF, are protection gas with the argon gas, are catalyzer with n-BuLi, and reaction obtains reaction product at ambient temperature;
With described reaction product H
2O
2Oxidation obtains final product.
Described final product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product DPCz for having formula (I-a) structure really.
According to the present invention, when Bridge is preferably above-mentioned (57) described structure and Ar
1-Ar
4When all being preferably phenyl, described compound has formula (I-b) structure, called after DPSF:
The present invention does not have particular restriction to the preparation method of DPSF, preferably includes following steps:
With lithium, diphenyl phosphorus chloride and 2,7-dibromo spiral shell fluorenes is a raw material, is reaction medium with THF, is protection gas with the argon gas, reacts under 0 ℃-100 ℃ condition, obtains reaction product;
With described reaction product H
2O
2Oxidation obtains product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product DPSF for having formula (I-b) structure really.
According to the present invention, when Bridge is preferably above-mentioned (71) described structure and Ar
1-Ar
6When all being preferably phenyl, described compound has formula (I-c) structure, called after TPTA:
The present invention does not have particular restriction to the preparation method of TPTA, preferably includes following steps:
With triphenylamine and bromine is raw material, with CHCl
3Being reaction medium, reaction obtains 4,4 ', 4 " tribromo triphenylamines;
With 4,4 ', 4 " tribromo triphenylamine and diphenyl phosphorus chloride are raw material, are reaction medium with THF, are protection gas with the argon gas, are catalyzer with n-BuLi, and reaction at room temperature is with reaction product H
2O
2Oxidation obtains final product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product TPTA for having formula (I-c) structure really.
According to the present invention, when Bridge is preferably above-mentioned (69) described structure and Ar
1-Ar
6When all being preferably phenyl, described compound has formula (I-d) structure, called after TPCz:
The present invention does not have particular restriction to the preparation method of TPCz, preferably includes following steps:
To be raw material to bromine hexichol, carbazole, be catalyzer with salt of wormwood and CuI, with 1,3-dimethyl-2-imidazolidone (DMI) is a reaction medium, is protection gas with the argon gas, under 100 ℃-200 ℃ condition reaction obtain 4 '-bromo-N-phenyl carbazole;
With 4 '-bromo-N-phenyl carbazole and NBS are raw material, are reaction medium with DMF, reaction obtains 3,6,4 '-three bromo-N-phenyl carbazoles under the condition of ice-water bath;
With 3,6,4 '-three bromo-N-phenyl carbazoles and diphenyl phosphorus chloride are raw material, are reaction medium with THF, are protection gas with the argon gas, are catalyzer with n-BuLi, and reaction at room temperature is with reaction product H
2O
2Oxidation obtains final product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product TPCz for having formula (I-d) structure really.
According to the present invention, when Bridge is preferably above-mentioned (72) described structure and Ar
1-Ar
6When all being preferably phenyl, described compound is for having formula (I-e) structure, called after TPTP:
The present invention does not have particular restriction to the preparation method of TPTP, preferably includes following steps:
With paradibromobenzene, phosphorus trichloride is raw material, is reaction medium with THF, is protection gas with the argon gas, under 0 ℃-100 ℃ condition reaction obtain 4,4 ', 4 " tribromo triphenyl phosphorus;
With 4,4 ', 4 " tribromo triphenyl phosphorus and diphenyl phosphorus chloride are raw material, are reaction medium with THF, are protection gas with the argon gas, are catalyzer with n-BuLi, reaction at room temperature; Then with reaction product H
2O
2Oxidation obtains final product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product TPTP for having formula (I-e) structure really.
According to the present invention, when Bridge is preferably above-mentioned (86) described structure and Ar
1-Ar
6When all being preferably phenyl, described compound has formula (I-f) structure, called after TPTB:
The present invention does not have particular restriction to the preparation method of TPTB, preferably includes following steps:
With parabromoacetophenone and silicon tetrachloride is raw material, is reaction medium with ethanol, is protection gas with the argon gas, three pairs of bromophenyl benzene between room temperature condition reacts down and obtains;
With three pairs bromophenyl benzene and diphenyl phosphorus chloride is raw material, is reaction medium with THF, is protection gas with the argon gas, reacts under the effect of n-BuLi; Then with reaction product H
2O
2Oxidation obtains final product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product TPTB for having formula (I-f) structure really.
According to the present invention, when Bridge is preferably above-mentioned (97) described structure and Ar
1-Ar
8When all being preferably phenyl, described compound has formula (I-g) structure, called after TePSF:
The present invention does not have particular restriction to the preparation method of TePSF, preferably includes following steps:
With lithium, diphenyl phosphorus chloride and 2,2 ', 7,7 '-dibromo spiral shell fluorenes is a raw material, is reaction medium with THF, is protection gas with the argon gas, reacts under 0 ℃-100 ℃ the condition, obtains reaction product;
With described reaction product H
2O
2Oxidation obtains final product.
Described product is carried out nuclear magnetic resonance spectroscopy, and its proton nmr spectra proves the described product TePSF for having formula (I-g) structure really.
Compared with prior art, the present invention has introduced phosphorus-oxygen groups in the organic compound periphery, by making up line style, star-like or X type molecule, obtains containing the compound of phosphorus-oxygen groups.Phosphorus-oxygen groups is an electron acceptor(EA) class group, can improve the electron transport ability of organic compound, makes the organic compound that contains phosphorus-oxygen groups have the good electron transmittability.
The present invention also provides a kind of organic electroluminescence device, comprising:
Substrate;
First electrode layer is arranged on substrate;
On described first electrode layer, has one or more layers organic electro luminescent layer at least;
On described organic electro luminescent layer, electron transfer layer is arranged;
On described electron transfer layer, the second electrode lay is arranged;
Described organic electro luminescent layer and/or electron transfer layer comprise the described compound that contains phosphorus-oxygen groups of technique scheme.
The present invention does not have particular requirement to described substrate, is preferably glass or plastics, and the thickness of described substrate is preferably 0.3mm-0.7mm.According to the present invention, described first electrode is an anode, for being easy to the material that the hole is injected, is preferably conducting metal or conducting metal oxide, includes but not limited to nickel, platinum, gold, indium tin oxide (ITO) and indium-zinc oxide (IZO).According to the present invention, the compound that contains phosphorus-oxygen groups or 4 that described organic electro luminescent layer (EML) is described by technique scheme, have formula (I) structure, 4 '-N, N '-two carbazole biphenyl (CBP), Polyvinyl carbazole carbazoles derivatives such as (PVK) are that material of main part, fluorescence dye or phosphorescent coloring are that doping agent is formed.According to the present invention, the thickness of described luminescent layer is preferably
According to the present invention, described electron transfer layer is compound that contains phosphorus-oxygen groups or the Alq that technique scheme is described, have formula (I) structure
3, material such as PBD, TPBI, TAZ, the thickness of electron transfer layer is preferably
According to the present invention, described second electrode is a negative electrode, is preferably the metal of low work content, includes but not limited to calcium, barium, aluminium, magnesium and silver, and the thickness of described second electrode is preferably
In order to improve device performance and efficient, between described first electrode and described luminescent layer, preferably include hole transmission layer (HTL).The present invention does not have particular restriction to the material of hole transmission layer, be preferably N, N '-two (3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (TPD) or N, N '-two (1-naphthyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (NPB), the thickness of described hole transmission layer is preferably
According to the present invention, between described first electrode and described hole transmission layer, preferably include hole injection layer (HIL).Hole injection layer can reduce the contact resistance between first electrode and the hole transmission layer, increases the injectability in hole.The present invention does not have particular restriction to the material of hole injection layer, be preferably poly-(3, the 4-Ethylenedioxy Thiophene) (PEDOT), poly styrene sulfonate (PSS) or molybdic oxide, the thickness of described hole injection layer is preferably
According to the present invention, between described luminescent layer and hole transmission layer, preferably include electronic barrier layer (EBL), described EBL can stop that exciton or electronic migration are to hole transmission layer.The present invention does not have particular restriction to electronic barrier layer, and material is preferably 1,3-two carbazyl benzene (mCP), and thickness is preferably
According to the present invention, between described luminescent layer and electron transfer layer, preferably include electron injecting layer (EIL), the present invention does not have particular restriction to the material of electron injecting layer, is preferably LiF, NaCl, NaOH, CsF, Cs
2CO
3, Ca (acac)
3, the thickness of described electron injecting layer is preferably
Below in conjunction with accompanying drawing the organic electroluminescence device that the embodiment of the invention provides is described, referring to Fig. 1, the structural representation of the organic electroluminescence device that Fig. 1 provides for the embodiment of the invention, as seen from the figure, described organic electroluminescence device is connected to form successively by substrate (101), first electrode (102), HIL (103), HTL (104), EBL (105), EML (106), ETL (107), EIL (108) and second electrode (109).
The present invention also provides a kind of preparation method of organic electroluminescence device, comprising:
On substrate, form first electrode;
On described first electrode, form one or more layers organic electro luminescent layer;
On described organic electro luminescent layer, form electron transfer layer;
On described electron transfer layer, form second electrode;
Described organic electro luminescent layer and/or electron transfer layer comprise the described compound that contains phosphorus-oxygen groups of above-mentioned technological method.
According to the present invention, at first on substrate, form first electrode, the present invention does not have particular restriction to described formation method, is preferably method well known to those skilled in the art.The present invention does not have particular requirement to described substrate, is preferably glass or plastics, and the thickness of described substrate is preferably 0.3mm-0.7mm.According to the present invention, described first electrode is an anode, for being easy to the material that the hole is injected, is preferably conducting metal or conducting metal oxide, includes but not limited to nickel, platinum, gold, indium tin oxide (ITO) and indium-zinc oxide (IZO).
According to the present invention, on first electrode, be formed with organic electroluminescent layer.The present invention does not have particular restriction to the formation method, is preferably method well known to those skilled in the art, includes but not limited to methods such as vacuum codeposition, solution spin coating.According to the present invention, the compound that contains phosphorus-oxygen groups or 4 that described organic electro luminescent layer (EML) is described by technique scheme, have formula (I) structure, 4 '-N, N '-two carbazole biphenyl (CBP), Polyvinyl carbazole carbazoles derivatives such as (PVK) are that material of main part, fluorescence dye or phosphorescent coloring are that doping agent is formed.According to the present invention, in the described luminescent layer, the doping ratio of described singlet fluorescence dye or triplet state phosphorescent coloring is preferably 0-30wt%, and more preferably 1%-20% most preferably is 5%-10%.According to the present invention, the thickness of described luminescent layer is preferably
According to the present invention, before forming luminescent layer, preferred cleaning has the substrate of first electrode, and the substrate after cleaning is carried out ultraviolet ray, ozone or Cement Composite Treated by Plasma.
According to the present invention, on described organic electro luminescent layer, form electron transfer layer.The present invention does not have particular restriction to the formation method, is preferably method well known to those skilled in the art, includes but not limited to methods such as vacuum moulding machine.According to the present invention, described electron transfer layer is compound that contains phosphorus-oxygen groups or the Alq that technique scheme is described, have formula (I) structure
3, material such as PBD, TPBI, TAZ, the thickness of electron transfer layer is preferably
According to the present invention, on described electron transfer layer, form second electrode, the present invention does not have particular restriction to the formation method, is preferably method well known to those skilled in the art, includes but not limited to deposition.Described second electrode is a negative electrode, is preferably the metal of low work content, includes but not limited to calcium, barium, aluminium, magnesium and silver.
In order to improve device performance and efficient, before forming luminescent layer, preferably on described first electrode, form hole transmission layer (HTL), the present invention does not have particular restriction to described formation method, is preferably vacuum moulding machine.The present invention does not have particular restriction to the material of hole transmission layer, be preferably N, N '-two (3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (TPD) or N, N '-two (1-naphthyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (NPB), the thickness of described hole transmission layer is preferably
According to the present invention, before forming hole transmission layer, preferably on first electrode, form hole injection layer (HIL), hole injection layer can reduce the contact resistance between first electrode and the hole transmission layer, increases the injectability in hole.The present invention does not have particular restriction to described formation method, is preferably vacuum moulding machine or vacuum evaporation or spin coating.Can the present invention the material of hole injection layer not be had particular restriction, be preferably poly-(3, the 4-Ethylenedioxy Thiophene) (PEDOT), poly styrene sulfonate (PSS) or molybdic oxide, the thickness of described hole injection layer is preferably
According to the present invention, after forming hole transmission layer, before forming luminescent layer, preferably on hole transmission layer, form electronic barrier layer, described EBL can stop that exciton or electronic migration are to hole transmission layer.The present invention does not have particular restriction to the formation method, is preferably vacuum moulding machine.The present invention does not have particular restriction to electronic barrier layer, and material is preferably 1,3-two carbazyl benzene (mCP), and thickness is preferably
According to the present invention, form before second electrode, be preferably included in and form electron injecting layer (EIL) on the electron transfer layer, the present invention does not have particular restriction to described formation method, is preferably vacuum moulding machine.The present invention does not have particular restriction to the material of electron injecting layer, is preferably LiF, NaCl, NaOH, CsF, Cs
2CO
3, Ca (acac)
3, the thickness of described electron injecting layer is preferably
The preparation method of the organic electroluminescence device that the embodiment of the invention is provided below in conjunction with accompanying drawing is described, referring to Fig. 1, the structural representation of the organic electroluminescence device that Fig. 1 provides for the embodiment of the invention, its preparation method may further comprise the steps: form first electrode (102) at substrate (101); Clean described sinking to the bottom with Virahol, acetone and other organic solvent then; Go up the HIL (103) that forms the molybdic oxide material by the mode of vacuum evaporation at first electrode (102); On HIL, form HTL (104) in vacuum-deposited mode; Mode with the vacuum codeposition on HTL forms EBL (105), method with vacuum moulding machine or solution spin coating on EML forms EML (106), on EML, form ETL (107) with vacuum-deposited method, on ETL, form EIL (108), on EIL, form second electrode (109) at last, obtain organic electroluminescence device as shown in Figure 1.
Compared with prior art, the present invention has introduced phosphorus-oxygen groups in the organic compound periphery, by making up line style, star-like or X type molecule, obtains containing the compound of phosphorus-oxygen groups.Phosphorus-oxygen groups is an electron acceptor(EA) class group, can improve the electron transport ability of organic compound, makes the organic compound that contains phosphorus-oxygen groups have the good electron transmittability.Contain electron transport material or the material of main part of the compound of phosphorus-oxygen groups, can improve electron transfer rate, the concentration in electronics and hole in the balance luminescent layer, thereby the performance and the efficient of raising device as organic electroluminescence device.Experiment shows, is material of main part with the compound that contains phosphorus-oxygen groups provided by the invention, is that the maximum luminous efficiency of the device of dopant material preparation can reach 36.4cd/A with FIrpic, and maximum power efficiency can reach 29.3ml/W, and high-high brightness can reach 11300cd/m
2With the compound that contains phosphorus-oxygen groups provided by the invention is electron transport material, and the maximum luminous efficiency that is entrained in the device for preparing among the PVK with FIrpic can reach 34.4cd/A, and maximum power efficiency can reach 16.9ml/W, and high-high brightness can reach 7750cd/m
2
In order further to understand the present invention, organic electroluminescence device that contains the phosphorus-oxygen groups compound, contains the phosphorus-oxygen groups compound provided by the invention and preparation method thereof is described below in conjunction with embodiment.
The DPCz that preparation according to the following steps has formula (I-a) structure:
In the exsiccant reaction flask, add 5.67mmol (2.0g) N-ethyl-2; 7-dibromo carbazole and 40mL exsiccant tetrahydrofuran (THF) (THF); under the argon shield; dry ice acetone bath is cooled to-78 ℃; in reaction flask, add 13.6mmoln-BuLi (8.5mL1.6M hexane solution) then, react and add 14.73mmol (2.64mL) diphenyl phosphorus chloride (Ph after 1 hour
2PCl), slowly rise to room temperature, reacted 24 hours.Slowly add 5mLH
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 1.13gDPCz after separating, productive rate 33.5% through phenetic analysis, confirms the DPCz of this product for having formula (I-a) structure.
1HNMR(300MHz，DMSO)[ppm]：δ8.39(dd，J＝8.1，2.7Hz，2H)，8.04(s，1H)，8.00(s，1H)，7.62-7.73(m，12H)，7.54-7.59(m，8H)，7.43(d，J＝8.7Hz，1H)，7.40(d，J＝8.1Hz，1H)，4.48(q，J＝6.9Hz，2H)，1.23(t，J＝7.2Hz，3H)。
31PNMR[ppm]：δ26.29。
Reaction formula is as follows:
Embodiment 2
The DPSF that preparation according to the following steps has formula (I-b) structure:
Add 30mmol (0.2g) Li in the exsiccant reaction flask, argon shield adds 50mL exsiccant THF down, slowly adds 15mmol (3.31g) diphenyl phosphorus chloride (Ph
2PCl), 50 ℃ were reacted 10 hours, obtained the THF solution of diphenylphosphine lithium salts.In another exsiccant reaction flask, add 5mmol (2.37g) 2,7-dibromo spiral shell fluorenes, argon shield adds the 20mL dry THF down, imports the THF solution of described diphenylphosphine lithium salts, and 50 ℃ were reacted 12 hours.Slowly add 5mLH
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 2.1gDPSF after separating, productive rate 58.6% through phenetic analysis, confirms the DPSF of this product for having formula (I-b) structure.
1H?NMR(300MHz，DMSO)[ppm]：δ8.27(dd，J＝8.1，2.4Hz，2H)，8.02(d，J＝7.5Hz，2H)，7.56-7.63(m，6H)，7.40-7.53(m，18H)，7.16(t，J＝7.2Hz，2H)，7.06(d，J＝11.4Hz，2H)，6.68(d，J＝7.8Hz，2H)。
31P?NMR[ppm]：δ25.06。
Reaction formula is as follows:
The TPTA that preparation according to the following steps has formula (I-c) structure:
In the 250mL round-bottomed flask, add 86mmol (21.6g) triphenylamine and 86mLCHCl
3, slowly drip 266.6mmol (42.6g) Br
2, drip the back and continue reaction 3 hours.Add 100mL water and 200mL ethanol in flask, suction filtration obtains white solid, uses CHCl
3And ethyl alcohol recrystallization, obtain 37.8g4,4 ', 4 " the tribromo triphenylamine, productive rate 90.7%, through phenetic analysis, confirm this product be 4,4 ', 4 " tribromo triphenylamines;
1H NMR (300MHz, CDCl
3) [ppm]: δ 7.35 (d, J=8.7Hz, 6H), 6.92 (d, J=8.7Hz, 6H);
In the exsiccant reaction flask, add 4mmol (1.93g) 4; 4 '; 4 " tribromo triphenylamine and 50mL exsiccant THF; under the argon shield; dry ice acetone bath is cooled to-78 ℃; add 13.2mmoln-BuLi (5.28mL2.5M hexane solution) then in reaction flask react and add 14mmol (2.5mL) diphenyl phosphorus chloride (Ph after 1 hour
2PCl), slowly rise to room temperature, reacted 24 hours, slowly add 5mL H
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 3.38gTPTA after separating, productive rate 89.0% through phenetic analysis, confirms the TPTA of this product for having formula (I-c) structure.
1H?NMR(300MHz，DMSO)[ppm]：δ7.54-7.67(m，36H)，7.22(d，J＝8.4Hz，6H)。
31P?NMR[ppm]：δ24.66。
Reaction formula is as follows:
The TPCz that preparation according to the following steps has formula (I-d) structure:
In reaction flask, add 200mmol (47.2g) paradibromobenzene, 100mmol (16.7g) carbazole, 150mmol (20.7g) salt of wormwood, 15mmol (2.9g) CuI and 15mL1; 3-dimethyl-2-imidazolidone (DMI); under the argon shield, be heated to 190 ℃ of reactions 20 hours.After the cooling, reaction mixture is dissolved with methylene dichloride, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 17.2g4 '-bromo-N-phenyl carbazole, productive rate 54.0% after separating, through phenetic analysis, confirm this product be 4 '-bromo-N-phenyl carbazole.
1H?NMR(300MHz，CDCl
3)[ppm]：δ8.13(d，J＝7.5Hz，2H)，7.72(d，J＝8.4Hz，2H)，7.45(d，J＝8.4Hz，2H)，7.35-7.41(m，4H)，7.29(t，J＝7.8Hz，2H)；
In the 250mL round-bottomed flask, add 40mmol (12.8g) 4 '-bromo-N-phenyl carbazole and 100mL2,5-dihydrofuran (DMF), reaction flask is placed ice-water bath, slowly drip 100mL and contain 88mmol (15.6g) 1-bromo-2, the DMF solution of 5-pyrroledione (NBS), drip the back and continue to stir, reacted 24 hours.Suction filtration obtains solid, with the gained solid dispersed at NaHSO
3Suction filtration in the aqueous solution is washed three times, obtains 15.0g3,6,4 '-three bromo-N-phenyl carbazoles, and productive rate 91.0% through phenetic analysis, confirms that this product is 3,6,4 '-three bromo-N-phenyl carbazoles.
1H?NMR(300MHz，CDCl
3)[ppm]：δ8.19(d，J＝1.8Hz，2H)，7.74(d，J＝8.7Hz，2H)，7.51(dd，J＝8.7，1.8Hz，2H)，7.38(d，J＝8.4Hz，2H)，7.22(d，J＝8.7Hz，2H)；
In the exsiccant reaction flask, add 15mmol (7.2g) 3; 6; 4 '-three bromo-N-phenyl carbazoles and 150mL exsiccant THF; under the argon shield; dry ice acetone bath is cooled to-78 ℃; in reaction flask, add 49.5mmoln-BuLi (19.8mL2.5M hexane solution) then, react and add 52.5mmol (9.44mL) diphenyl phosphorus chloride (Ph after 1 hour
2PCl), slowly rise to room temperature, reacted 24 hours.Slowly add 10mLH
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 8.5gTPCz after separating, productive rate 66.7% through phenetic analysis, confirms the TPCz of this product for having formula (I-d) structure.
1H?NMR(300MHz，DMSO)[ppm]：δ8.74(d，J＝12.3Hz，2H)，7.91-7.97(m，4H)，7.52-7.77(m，34H)。
31P?NMR[ppm]：δ24.77，25.88。
Reaction formula is as follows:
The TPTP that preparation according to the following steps has formula (I-e) structure:
In the exsiccant reaction flask, add 100mmol (2.4g) magnesium chips and a small amount of iodine; argon shield adds 10mL exsiccant THF down; slowly drip the THF solution that 100mL contains 100mmol (23.6g) paradibromobenzene, 50 ℃ of reactions added 100mmol (4.12g) phosphorus trichloride (PCl after 4 hours
3), continue reaction 24 hours.Reaction mixture is poured in the water, and dichloromethane extraction is washed anhydrous sodium sulfate drying three times, filter, concentrate, silicagel column obtains 8.3g4 after separating, 4 ', 4 " the tribromo triphenyl phosphorus, productive rate 56.7%; through phenetic analysis, confirm this product be 4,4 ', 4 " tribromo triphenyl phosphorus.
1H?NMR(300MHz，CDCl
3)[ppm]：δ7.48(d，J＝8.1Hz，6H)，7.12(t，J＝7.8Hz，6H)。
In the exsiccant reaction flask, add 15mmol (7.4g) 4; 4 '; 4 " tribromo triphenyl phosphorus and 50mL exsiccant THF; under argon shield; dry ice acetone bath is cooled to-78 ℃; in reaction flask, add 49.5mmol n-BuLi (18.9mL2.5M hexane solution) then, react after 1 hour, add Ph
2PCl slowly rises to room temperature, reacts after 24 hours, slowly adds 10mLH
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 11.0gTPTP after separating, productive rate 83.5% through phenetic analysis, confirms the TPTP of this product for having formula (I-e) structure.
1H?NMR(300MHz，DMSO)[ppm]：δ7.80-7.87(m，12H)，7.61-7.67(m，18H)，7.52-7.58(m，12H)。
31P?NMR[ppm]：δ23.78，24.69。
Reaction formula is as follows:
Embodiment 6
The TPTB that preparation according to the following steps has formula (I-f) structure:
In the exsiccant reaction flask, add 60.0mmol (11.9g) parabromoacetophenone and 1200mL exsiccant ethanol; under the argon shield; ice-water bath is cooled to 0 ℃; in reaction flask, add 120.0mmol (13.7mL) silicon tetrachloride then; 0 ℃ was reacted 1 hour; rose to room temperature reaction 24 hours; reaction mixture is poured in the water, and dichloromethane extraction is washed three times; anhydrous sodium sulfate drying; filter, concentrate, obtain three pairs of bromophenyl benzene between 4.2g, productive rate 38.7% with THF and normal hexane recrystallization; through phenetic analysis, confirm this product be between three pairs of bromophenyl benzene.
1H?NMR(300MHz，CDCl
3)[ppm]：δ7.69(s，3H)，7.60(d，J＝8.7Hz，6H)，7.53(d，J＝8.7Hz，6H)。
In the exsiccant reaction flask, add between 3.68mmol (2.0g) three pairs of bromophenyl benzene and 40mL exsiccant THF; under the argon shield; dry ice acetone bath is cooled to-78 ℃; in reaction flask, add 13.26mmoln-BuLi (5.3mL2.5M hexane solution) then, react and add 14.36mmol (2.6mL) Ph after 1 hour
2PCl slowly rises to room temperature, reacts after 24 hours, slowly adds 5mL H
2O
2Stirred 2 hours, with reaction mixture greatly once in a while in the water, dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 0.96gTPTB after separating, productive rate 29.1% through phenetic analysis, confirms this product TPTB for having formula (I-f) structure really.
1H?NMR(300MHz，DMSO)[ppm]：δ8.01-8.07(m，9H)，7.55-7.76(m，34H)，7.43(m，1H)，7.30-7.35(m，1H)。
31PNMR[ppm]：δ25.09。
Reaction formula is as follows:
Embodiment 7
The TePSF that preparation according to the following steps has formula (I-g) structure:
Add 16mmol (0.11g) lithium bar in the exsiccant reaction flask, argon shield adds the 20mL dry THF down, slowly adds 8mmol (1.77g) Ph
2PCl, 50 ℃ were reacted 10 hours, obtained the THF solution of diphenylphosphine lithium salts;
Add 1mmol (0.63g) 2,2 ' in another dry reaction bottle, 7,7 '-tetrabromo spiral shell fluorenes, argon shield adds the 20mL dry THF down, imports the THF solution of described diphenylphosphine lithium salts then, and 50 ℃ were reacted 12 hours, and slowly added 5mLH
2O
2Stirred 2 hours, and reaction mixture was poured in the water into dichloromethane extraction, wash three times, anhydrous sodium sulfate drying filters, concentrates, silicagel column obtains 0.84gTePSF after separating, productive rate 75.0% through phenetic analysis, confirms the TsPSF of this product for having formula (I-g) structure.HNMR(300MHz，DMSO)[ppm]：δ8.26(dd，J＝7.8，2.1Hz，4H)，7.64(d，J＝8.1Hz，2H)，7.61(d，J＝7.8Hz，2H)，7.55-7.59(m，8H)，7.40-7.47(m，32H)，7.05(d，J＝11.4Hz，4H)。
31P?NMR[ppm]：δ25.24。
Reaction formula is as follows:
Prepare organic electroluminescence device according to following steps:
With plastics as substrate; On plastic, form first electrode of indium tin oxide (ITO) material; On first electrode, form the PEDOT material, thickness is the hole injection layer of 50nm; Method formation thickness with the solution spin-coating method on hole injection layer is the organic electro luminescent layer of 50nm, and described luminescent layer is entrained among the PVK by blue light phosphorescent coloring (FIrpic) to be formed, and the doping ratio of FIrpic is 10wt%; On luminescent layer by vacuum-deposited method form embodiment 4 preparations the TPZc material, thickness is the electron transfer layer of 40nm; On electron transfer layer, form the LiF material, thickness is the electron injecting layer of 1nm; Second electrode of depositing Al material on electron injecting layer, thickness is 150nm, obtains having the organic electroluminescence device of following structure:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TPCz(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result is referring to Fig. 2, Fig. 3 and Fig. 4, and what Fig. 2 provided for the embodiment of the invention is the luminous efficiency-current density graphic representation of the organic electroluminescence device of electron transfer layer with TPCz; That Fig. 3 provides for the embodiment of the invention is the current density-voltage-brightness curve figure of the organic electroluminescence device of electron transfer layer with TPCz; What Fig. 4 provided for the embodiment of the invention is the electroluminescent spectrum of the organic electroluminescence device of electron transfer layer with TPCz.The result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 34.4cd/A, and maximum power efficiency is 16.9lm/W, and high-high brightness is 7750cd/m
2
Embodiment 9
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the DPZc material of embodiment 1 preparation, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/DPCz(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 21.7cd/A, and maximum power efficiency is 9.5lm/W, and high-high brightness is 4380cd/m
2
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the DPSF material of embodiment 2 preparations, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/DPSF(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 26.3cd/A, and maximum power efficiency is 12.8lm/W, and high-high brightness is 5640cd/m
2
Embodiment 11
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the TPTA material of embodiment 3 preparations, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TPTA(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 29.4cd/A, and maximum power efficiency is 14.1lm/W, and high-high brightness is 6800cd/m
2
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the TPTP material of embodiment 5 preparations, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TPTP(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 31.9cd/A, and maximum power efficiency is 15.5lm/W, and high-high brightness is 7110cd/m
2
Embodiment 13
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the TPTB material of embodiment 6 preparations, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TPTB(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 17.5cd/A, and maximum power efficiency is 8.4lm/W, and high-high brightness is 3890cd/m
2
Embodiment 14
Step according to embodiment 8 prepares organic electroluminescence device, and except electron transfer layer is the TePSF material of embodiment 7 preparations, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TePSF(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 27.2cd/A, and maximum power efficiency is 13.4lm/W, and high-high brightness is 5700cd/m
2
Prepare organic electroluminescence device according to following steps:
With plastics as substrate; On plastic, form first electrode of indium tin oxide (ITO) material; On first electrode, form molybdic oxide (MoO
3) material, thickness is the hole injection layer of 8nm; On hole injection layer, form N with vacuum-deposited method, N '-two (1-naphthyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (NPB) material, thickness is the hole transmission layer of 65nm; On hole transmission layer with vacuum-deposited method form the mCP material, thickness is the electronic barrier layer of 10nm; On electronic barrier layer with vacuum altogether the method for evaporation to form thickness be the organic electro luminescent layer of 20nm, described luminescent layer is entrained in by blue light phosphorescent coloring (FIrpic) among the TPCz of embodiment 4 preparations to be formed, the doping ratio of FIrpic is 8wt%; On luminescent layer, form 3-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-1,2 by vacuum-deposited method, 4-triazole (TAZ) material, thickness is the electron transfer layer of 40nm; On electron transfer layer, form the LiF material, thickness is the electron injecting layer of 1nm; Second electrode of depositing Al material on electron injecting layer, thickness is 150nm, obtains having the organic electroluminescence device of following structure:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TPCz：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result participates in Fig. 5, Fig. 6 and Fig. 7, and what Fig. 5 provided for the embodiment of the invention is the luminous efficiency-current density graphic representation of the organic electroluminescence device of material of main part with TPCz; That Fig. 6 provides for the embodiment of the invention is the current density-voltage-brightness curve figure of the organic electroluminescence device of material of main part with TPCz; What Fig. 7 provided for the embodiment of the invention is the electroluminescent spectrum of the organic electroluminescence device of material of main part with TPCz.The result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 36.4cd/A, and maximum power efficiency is 29.3lm/W, and high-high brightness is 11300cd/m
2
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the DPCz of embodiment 1 preparation, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/DPCz：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 25.7cd/A, and maximum power efficiency is 23.0lm/W, and high-high brightness is 9870cd/m
2
Embodiment 17
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the DPSF of embodiment 2 preparations, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/DPSF：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 29.9cd/A, and maximum power efficiency is 26.6lm/W, and high-high brightness is 10500cd/m
2
Embodiment 18
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the TPTA of embodiment 3 preparations, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TPTA：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 32.4cd/A, and maximum power efficiency is 27.6lm/W, and high-high brightness is 11000cd/m
2
Embodiment 19
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the TPTP of embodiment 5 preparations, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TPTP：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 35.2cd/A, and maximum power efficiency is 28.7lm/W, and high-high brightness is 10900cd/m
2
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the TPTB of embodiment 6 preparations, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TPTB：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 22.0cd/A, and maximum power efficiency is 19.2lm/W, and high-high brightness is 8760cd/m
2
Embodiment 21
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is the TePSF of embodiment 7 preparations, other materials, thickness are all identical with the organic electroluminescence device that embodiment 15 prepares, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TePSF：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 30.3cd/A, and maximum power efficiency is 27.8lm/W, and high-high brightness is 10400cd/m
2
Comparative example 1
Step according to embodiment 8 prepares organic electroluminescence device, and except the material of electron transfer layer is traditional TPBI, other materials, the thickness all organic electroluminescence device with embodiment 8 preparations are identical, and structure is as follows:
ITO/PEDOT(50nm)/PVK：FIrpic(50nm)/TPBI(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 12.2cd/A, and maximum power efficiency is 5.5lm/W, and high-high brightness is 1800cd/m
2
Comparative example 2
Step according to embodiment 15 prepares organic electroluminescence device, and except the material of main part of luminescent layer is traditional TPBI, other materials, the thickness all organic electroluminescence device with embodiment 15 preparations are identical, and structure is as follows:
ITO/MoO
3(8nm)/NBP(65nm)/mCP(10nm)/TPBI：FIrpic(20nm)/TAZ(40nm)/LiF(1nm)/Al(150nm)
Described organic electroluminescence device is carried out performance test, and the result shows that the maximum luminous efficiency of the organic electroluminescence device that present embodiment provides is 14.7cd/A, and maximum power efficiency is 7.0lm/W, and high-high brightness is 3300cd/m
2
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (12)
1. a formula (I) compound:
Wherein,
Bridge is the bridging unit, is selected from any one structure of following (1)-(126):
Ar
1-Ar
8Be selected from any one structure of following (1001)-(1057) respectively:
Ar
9Be selected from any one structure of following A-G:
R
1Alkyl for C1-C8.
2. compound according to claim 1 has formula (I-a) structure:
3. compound according to claim 1 has formula (I-b) structure:
4. compound according to claim 1 has formula (I-c) structure:
5. compound according to claim 1 has formula (I-d) structure:
6. compound according to claim 1 has formula (I-e) structure:
7. compound according to claim 1 has formula (I-f) structure:
8. compound according to claim 1 has formula (I-g) structure:
9. an organic electroluminescence device is characterized in that, comprising:
Substrate;
First electrode layer is arranged on substrate;
On described first electrode layer, has one or more layers organic electro luminescent layer at least;
On described organic electro luminescent layer, electron transfer layer is arranged;
On described electron transfer layer, the second electrode lay is arranged;
Described organic electro luminescent layer and/or electron transfer layer comprise any described compound of claim 1-8.
10. organic electroluminescence device according to claim 9, it is characterized in that, described organic electro luminescent layer comprises material of main part and the singlet fluorescence dye or the triplet state phosphorescent coloring that are entrained in the described material of main part, and described material of main part is any described compound of claim 1-8.
11. the preparation method of an organic electroluminescence device is characterized in that, comprising:
On substrate, form first electrode;
On described first electrode, form one or more layers organic electro luminescent layer;
On described organic electro luminescent layer, form electron transfer layer;
On described electron transfer layer, form second electrode;
Described organic electro luminescent layer and/or electron transfer layer comprise any described compound of claim 1-8.
12. method according to claim 11, it is characterized in that, described organic electro luminescent layer comprises material of main part and the singlet fluorescence dye or the triplet state phosphorescent coloring that are entrained in the described material of main part, and described material of main part is any described compound of claim 1-8.
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| JP2012224626A (en) * | 2011-04-08 | 2012-11-15 | Showa Denko Kk | Phosphine oxide-based compound, organic electroluminescent element, production method therefor, and application of the same |
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