CN104513662A - Organic light-emitting material and application thereof - Google Patents
Organic light-emitting material and application thereof Download PDFInfo
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- OYCBSPHIEICKIU-UHFFFAOYSA-N [O-][N+](c(c(-c1cccc2c1cccc2-c1cc(Br)ccc1[N+]([O-])=O)c1)ccc1Br)=O Chemical compound [O-][N+](c(c(-c1cccc2c1cccc2-c1cc(Br)ccc1[N+]([O-])=O)c1)ccc1Br)=O OYCBSPHIEICKIU-UHFFFAOYSA-N 0.000 description 2
- 0 *c1cccc2c1cccc2C1*=CC1 Chemical compound *c1cccc2c1cccc2C1*=CC1 0.000 description 1
- BZBAYMUKLAYQEO-UHFFFAOYSA-N Bc1ccccc1 Chemical compound Bc1ccccc1 BZBAYMUKLAYQEO-UHFFFAOYSA-N 0.000 description 1
- COYBLZMDBBKMOP-UHFFFAOYSA-N C(C1)C=C(C2C=CC(N(c3ccccc3)c(cc3)ccc3-c(cc3)ccc3N(c3ccccc3)c(cc3)ccc3-c3cccc4c3[s]c3c4cccc3)=CC2)c2c1c1ccccc1[s]2 Chemical compound C(C1)C=C(C2C=CC(N(c3ccccc3)c(cc3)ccc3-c(cc3)ccc3N(c3ccccc3)c(cc3)ccc3-c3cccc4c3[s]c3c4cccc3)=CC2)c2c1c1ccccc1[s]2 COYBLZMDBBKMOP-UHFFFAOYSA-N 0.000 description 1
- FXZPEFOSFYURDN-UHFFFAOYSA-N C(C1)C=CC=C1[n]1c2ccc(c(c3cc(-c4ccccc4)ccc33)c(cc4)[n]3-c3ccccc3)c4c2c2c1ccc(-c1ccccc1)c2 Chemical compound C(C1)C=CC=C1[n]1c2ccc(c(c3cc(-c4ccccc4)ccc33)c(cc4)[n]3-c3ccccc3)c4c2c2c1ccc(-c1ccccc1)c2 FXZPEFOSFYURDN-UHFFFAOYSA-N 0.000 description 1
- BMFRJUJQVCZJRG-UHFFFAOYSA-N C=[Br]c(cc1)cc(Br)c1[N+]([O-])=O Chemical compound C=[Br]c(cc1)cc(Br)c1[N+]([O-])=O BMFRJUJQVCZJRG-UHFFFAOYSA-N 0.000 description 1
- WHBLKYFROOXUPI-UHFFFAOYSA-N C=[Br]c(cc1c2c(ccc3c4c(cc(cc5)Br)c5[n]3-c3ccccc3)c4ccc22)ccc1[n]2-c1ccccc1 Chemical compound C=[Br]c(cc1c2c(ccc3c4c(cc(cc5)Br)c5[n]3-c3ccccc3)c4ccc22)ccc1[n]2-c1ccccc1 WHBLKYFROOXUPI-UHFFFAOYSA-N 0.000 description 1
- PUIGAFXFSIGZHY-UHFFFAOYSA-N c1c(-c2ccccc2)[s]c(-c(cc2)ccc2N(c2ccccc2)c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c(cc2)ccc2-c2ccc(-c3ccccc3)[s]2)c1 Chemical compound c1c(-c2ccccc2)[s]c(-c(cc2)ccc2N(c2ccccc2)c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c(cc2)ccc2-c2ccc(-c3ccccc3)[s]2)c1 PUIGAFXFSIGZHY-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to an organic light-emitting material represented as the formula I, wherein Ar1-A8 are individually selected from one of a group including hydrogen, a substituted or non-substituted aromatic hydrocarbon group with carbon number being 6-30, a substituted or non-substituted polycyclic aromatic hydrocarbon group with the carbon number being 6-30, a substituted or non-substituted polycyclic heterocyclic group with the carbon number being 6-30, a five-membered or six-membered heterocyclic group or substituted heterocyclic group, a triarylamine group, and a substituted or non-substituted fatty alkyl group with the carbon number being 1-12. The invention also relates to an application of the compound in organic light-emitting devices (OLED), especially as a hole injection material, a hole transport layer material, a fluorescent main material or a luminescent material in the OLED.
Description
Technical field
The present invention relates to a kind of novel organic luminescent material, particularly relate to a kind of for the compound of organic electroluminescence device and the application in organic electroluminescence device.
Background technology
Display of organic electroluminescence (hereinafter referred to as OLED) has, composition wide, lightweight from main light emission, low-voltage direct-current driving, all solidstate, visual angle and a series of advantage such as technique is simple, compared with liquid-crystal display, display of organic electroluminescence does not need backlight, visual angle is large, power is low, and its response speed can reach 1000 times of liquid-crystal display, and its manufacturing cost is but lower than the liquid-crystal display of equal resolving power, therefore, organic electroluminescence device has broad application prospects.
The restructuring of what the generation of organic electroluminescent was leaned on the is current carrier (electronics and hole) transmitted in organic electroluminescence material, as everyone knows, the electroconductibility of organic materials is very poor, with inorganic semiconductor unlike, do not have being with of continuity in organic semiconductor, the transmission of current carrier is commonly used jump theory to describe, namely under the driving of an electric field, electronics is being excited or is being injected in the lumo energy of molecule, via jumping to the lumo energy of another molecule to reach the object of transferring charge.In order to organic electroluminescence device can be made to reach breakthrough in application aspect, the difficulty of organic materials charge injection and transmittability difference must be overcome.Scientists is by the adjustment of device architecture, such as increase the number of device organic material layer, and make different organic layers play the part of different roles, the functional materials such as had helps electronics to inject from negative electrode and hole from anode, some materials help the transmission of electric charge, some materials then play the effect of block electrons and hole transport, certainly in organic electroluminescent, the luminescent material of most important shades of colour also will reach the object matched with adjacent functional material, the result of excellent in efficiency life-span long organic electroluminescence device normally optimization collocation of device architecture and various organic materials, this functionalization material just designing and developing various structure for chemists provides great opportunities and challenges.
The hole always used in organic electroluminescent device is injected and transport material is generally derivative of tri-arylamine group (such as bright dipping patent: publication number CN1152607C, publication date 2004,6,2), its general constructional feature is, as injecting material, in a molecule, its tertiary aromatic amine structure unit is at least more than three, and separate with a phenyl ring between two N, see Fig. 1; As transport material, in a molecule, its tertiary aromatic amine structure unit is generally two, and separates with biphenyl between two N, and in this kind of material, typical example is NPB, and its structure is shown in Fig. 2.
In recent years, the research of this kind of material has had some new progresses, introduce one or more thienyl in the molecule, or introduce one or more benzothienyl, see Fig. 3 and Fig. 4 (bright dipping patent: publication number CN101506191A, publication date 2009,8,12), result is the Hole injection capacity considerably increasing material; As transport material, when the tertiary aromatic amine structure unit carbazole of in material or diphenylene-oxide being replaced, the transmittability of material all has a more substantial increase.See Fig. 5 and Fig. 6 (bright dipping patent: publication number CN102334210A, the applying date 2012,1,25; Publication number: WO2010/114017A1, publication date 2010,10,7).
Summary of the invention
The object of the present invention is to provide a class novel organic luminescent material, such luminous organic material may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
For this reason, the technical scheme that the present invention takes is:
A kind of luminous organic material, has structure as shown in the formula (I):
Wherein:
Ar1-Ar8 be independently selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6 ~ C30, the condensed-nuclei aromatics group of the substituted or non-substituted of C6 ~ C30, the substituted or non-substituted of C6 ~ C30 fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle, triarylamine group, aryl oxide group base group, C1 ~ C12 substituted or non-substituted aliphatic alkyl group in one.
Further, described Ar4, Ar8, be H simultaneously.
Further, described Ar1 and Ar5 is separately phenyl, xenyl, naphthyl, anthryl, phenanthryl, perylene base, pyrenyl.
Further, described Ar2, Ar3, A6, Ar7 are separately selected from phenyl, naphthyl, anthryl, phenanthryl, perylene base, pyrenyl, carbazyl, the carbazyl of replacement, hexichol amido, N-phenylnaphthalene amino, dibenzothiophene base, dibenzofuran group.
In order to more clearly demonstrate content of the present invention, lower mask body describes the preferred structure of the compound that the present invention relates to:
Present invention also offers a kind of luminous organic material, be applied in organic electroluminescence device.
Further, described luminous organic material can be used as hole-injecting material, hole mobile material or material of main part.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer,
The substrate material of described hole transmission layer contains described luminous organic material.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole-injecting material, hole transmission layer, organic luminous layer and electron transfer layer,
The substrate material of described hole injection layer contains described luminous organic material.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer,
The substrate material of described organic luminous layer contains described luminous organic material.
For convenience of description, in the application's subsequent content, the hole mobile material of indication is the substrate material of hole transmission layer, and hole-injecting material is the substrate material of hole injection layer, and material of main part is the substrate material of organic luminous layer.
Compared with prior art, tool of the present invention has the following advantages:
In the present invention, we have proposed a class type material, connect with key on parent nucleus naphthyl a series of compounds that two carbazoles are general formula, this novel material is not only fitted collaborative agent material but also is made hole mobile material, when parent nucleus only connecting condensed-nuclei aromatics, such material is suitable as light emitting host material, is applied on device, can improve a lot to luminous efficiency, device lifetime is longer.When parent nucleus being connected with triaryl amine or fused heterocycle aromatic hydrocarbons, such as carbazole group, dibenzothiophene group, diphenylene-oxide group etc., such material is suitable as hole mobile material.In red device as hole mobile material application better, the use of material of the present invention, what reduce device opens bright voltage to this novel material, improves the luminous efficiency of device, adds the work-ing life of device.
(2) preparation is simple for the compounds of this invention, and these compounds have good thermostability, high hole mobility, with the electroluminescent device that this material makes, the bright voltage that opens of device reduces greatly, luminous efficiency increases, and significantly increases the work-ing life of device simultaneously, can be used as the material of main part in hole mobile material or organic luminous layer in organic electroluminescence device.
Accompanying drawing explanation
In order to make content of the present invention more easily be understood, with Gaussian03B3LYP/6-31G(d in the present invention) method tries to achieve the highest occupied molecular orbital(HOMO) (HOMO) of compound, lowest unoccupied molecular orbital (LUMO) and triplet (T1) respectively.
Fig. 1 is the highest occupied molecular orbital(HOMO) of organic compound 4 of the present invention, and HOMO energy level is-4.626ev, triplet T1=2.4351ev;
Fig. 2 is the lowest unoccupied molecular orbital of organic compound 4 of the present invention, and lumo energy is-1.294ev;
Fig. 3 is that organic compound 4 of the present invention is through Gaussian03B3LYP/6-31G(d) method optimize after each atom and the three-dimensional distribution map of group, anyway and ring carbazole carbazole parent as seen from the figure, has good coplanarity.
Embodiment
Basic raw material used in the present invention, 1,5-dibromine naphthalene, 2,6-dibromine naphthalene, 2,4-bis-bromo nitrobenzene, 2,5-bis-bromo nitrobenzene, and bromo carbazole derivative, bromo diphenylene-oxide, bromo dibenzothiophene, bromo Chrysene, bromo triphenylene, bromo pyrene etc., can buy in each large industrial chemicals market at home.
Embodiment 1
Preparation embodiment for intermediate of the present invention:
The diborated synthesis of main intermediate naphthalene-2,6-
Be dissolved in the THF of 100ml drying by 1, the 5-dibromine naphthalene (molecular weight 284,0.02mol) of 5.7g ,-80 DEG C drip normal-butyl reason 20ml(2.5M, 0.05mol), stir 15min, then drip triisopropyl boric acid ester 30ml.Hydrolysis, regulate pH to separate out white boric acid derivatives 4.35g to neutral, productive rate is close to 100%.
Embodiment 2
The synthesis of compound 1
(1) the first step
1000 milliliters of a bite bottles, join magnetic agitation, add naphthalene-1,5 hypoboric acid 4.35g(molecular weight 216,0.02mol), 2,4-bis-bromo nitrobenzene 11.4g(molecular weight 278,0.041mol), Pd (PPh
3)
4usage quantity 2.6g(molecular weight 1154,0.00253mol), sodium carbonate 150ml(2M), toluene 150ml, ethanol 150ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 3 hours, cooling, has separated basic unit, evaporate to dryness, has carried out post separation by ethyl acetate/petroleum ether, obtained 9.9g product, molecular weight 526, productive rate 94%.
(2) second step
50 milliliters of a bite bottles, join magnetic agitation, add the final product 9.9g(molecular weight 526,0.0188mol of the first step), triphenylphosphine 10.5g(molecular weight 262,0.04mol), orthodichlorobenzene 200ml.Mixture is heated to 175 DEG C, stirs, by TCL board monitoring reaction process, reacts and complete for 15 hours.Cooling, solvent evaporation in vacuo, washing, dry, with pillar layer separation, ethyl acetate and petroleum ether mixtures drip washing, obtain target molecule 7.9g, molecular weight 464, productive rate 90.5%
(3) the 3rd steps
500 milliliters of a bite bottles, join magnetic agitation, add second step final product 7.9g(molecular weight 464,0.017mol), iodobenzene 12.7g(molecular weight 254,0.05mol), cuprous iodide 1.0g(molecular weight 190,0.00526mol), salt of wormwood 13.8g(138,0.1mol), DMPU solvent 180ml.Mixture is heated to 1750C, stirs, by TCL board monitoring reaction process, reacts and complete for 13 hours.Cooling, in impouring water, leaches, and dry, with pillar layer separation, ethyl acetate and petroleum ether mixtures drip washing, obtain target molecule 8.73g, molecular weight 614, productive rate 83.1%
(4) the 4th steps
1000 milliliters of a bite bottles, join magnetic agitation, add above-mentioned 3rd step final product 8.73g(molecular weight 614,0.0142mol), phenylo boric acid 4.0g(molecular weight 122,0.0328mol), Pd (PPh
3)
4usage quantity 3.0g(molecular weight 1154,0.0026mol), sodium carbonate 220ml(2M), toluene 220ml, ethanol 220ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 4 hours, cooling, purifies with common post separation method, obtains 6.85g product, productive rate 79.1%.
Be dissolved in the THF of 100ml drying by 2, the 6-dibromine naphthalenes (molecular weight 284,0.02mol) of 5.7g ,-80 DEG C drip normal-butyl reason 20ml(2.5M, 0.05mol), stir 15min, then drip triisopropyl boric acid ester 30ml.Hydrolysis, regulate pH to separate out white boric acid derivatives 4.35g to neutral, productive rate is close to 100%.
Product MS(m/e): 610, ultimate analysis (C46H30N2): theoretical value C:90.46%, H:4.95%, N:4.59%; Measured value C:90.44%, H:4.94%, N:4.62%.
Embodiment 3
The synthesis of compound 2
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; In the 4th step, phenylo boric acid is changed into naphthalene-1-boric acid, obtain compound 2.
Product MS(m/e): 710, ultimate analysis (C54H34N2): theoretical value C:91.24%, H:4.82%, N:3.94%; Measured value C:91.20%, H:4.84%, N:3.96%.
Embodiment 4
The synthesis of compound 3
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; In the 3rd step, iodobenzene is changed into 2-iodine naphthalene, obtain compound 3.
Product MS(m/e): 710, ultimate analysis (C54H34N2): theoretical value C:91.24%, H:4.82%, N:3.94%; Measured value C:91.25%, H:4.80%, N:3.95%.
Embodiment 5
The synthesis of compound 4
Synthesis step has four steps, and first three walks the front three-step reaction be same as in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; And the reaction of the 4th step is same as three-step reaction, just iodobenzene is changed into phenyl-(1-naphthyl) amine, obtain compound 4.
Product MS(m/e): 892, ultimate analysis (C66H44N4): theoretical value C:88.76%, H:4.97%, N:6.27%; Measured value C:88.73%, H:4.94%, N:6.33%.
Embodiment 6
The synthesis of compound 5
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; In the 4th step, phenylo boric acid is changed into N-ethyl carbazole-3-boric acid, obtain compound 5.
Product MS(m/e): 844, ultimate analysis (C62H44N4): theoretical value C:88.12%, H:5.25%, N:6.63%; Measured value C:88.14%, H:5.22%, N:6.64%.
Embodiment 7
The synthesis of compound 6
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; And in the reaction of the 4th step, phenylo boric acid is changed into dibenzothiophene-2-boric acid, obtain compound 6.
Product MS(m/e): 822, ultimate analysis (C58H34N2S2): theoretical value C:84.64%, H:4.16%: 3.40%, S:7.79%; Measured value C:84.62%, H:4.18%: 3.43%, S:7.77%.
Embodiment 8
The synthesis of compound 7
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; And in the reaction of the 4th step, phenylo boric acid is changed into dibenzothiophene-4-boric acid, obtain compound 7.
Product MS(m/e): 822, ultimate analysis (C58H34N2S2): theoretical value C:84.64%, H:4.16%: 3.40%, S:7.79%; Measured value C:84.63%, H:4.17%: 3.44%, S:7.76%.
Embodiment 9
The synthesis of compound 8
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; And in the reaction of the 4th step, phenylo boric acid is changed into diphenylene-oxide-2-boric acid, obtain compound 8.
Product MS(m/e): 790, ultimate analysis (C58H34N2O2): theoretical value C:88.08%, H:4.33%, N:3.54%, O:4.05%; Measured value C:88.05%, H:4.35%, N:3.52%, O:4.08%.
Embodiment 10
The synthesis of compound 9
Synthesis step is same as the four-step reaction in embodiment 2, just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid; And in the reaction of the 4th step, phenylo boric acid is changed into diphenylene-oxide-4-boric acid, obtain compound 9.
Product MS(m/e): 790, ultimate analysis (C58H34N2O2): theoretical value C:88.08%, H:4.33%, N:3.54%, O:4.05%; Measured value C:88.06%, H:4.36%, N:3.52%, O:4.086%.
Embodiment 11
The synthesis of compound 10
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; Obtain compound 10.
Product MS(m/e): 610, ultimate analysis (C46H30N2): theoretical value C:90.46%, H:4.95%, N:4.59%; Measured value C:90.43%, H:4.93%, N:4.64%.
Embodiment 12
The synthesis of compound 11
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; And in the reaction of the 4th step, phenylo boric acid is changed into naphthalene-2-boric acid, obtain compound 11.
Product MS(m/e): 710, ultimate analysis (C54H34N2): theoretical value C:91.24%, H:4.82%, N:3.94%; Measured value C:91.20%, H:4.84%, N:3.96%.
Embodiment 13
The synthesis of compound 12
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; In the 3rd step, iodobenzene is changed as 2-iodine naphthalene, obtain compound 12.
Product MS(m/e): 710, ultimate analysis (C54H34N2): theoretical value C:91.24%, H:4.82%, N:3.94%; Measured value C:91.22%, H:4.85%, N:3.93%.
Embodiment 14
The synthesis of compound 13
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; In the 4th step, phenylo boric acid is changed into N-ethyl carbazole-3-boric acid, obtain compound 13.
Product MS(m/e): 844, ultimate analysis (C62H44N4): theoretical value C:88.12%, H:5.25%, N:6.63%; Measured value C:88.15%, H:5.21%, N:6.64%.
Embodiment 15
The synthesis of compound 14
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; In the 4th step, phenylo boric acid is changed into 8-phenyl dibenzothiophene-2-boric acid, obtain compound 14.
Product MS(m/e): 822, ultimate analysis (C58H34N2S2): theoretical value C:84.64%, H:4.16%: 3.40%, S:7.79%; Measured value C:84.66%, H:4.15%: 3.43%, S:7.76%
Embodiment 16
The synthesis of compound 15
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; In the 4th step, phenylo boric acid is changed into 8-phenyl dibenzothiophene-4-boric acid, obtain compound 15.
Product MS(m/e): 822, ultimate analysis (C58H34N2S2): theoretical value C:84.64%, H:4.16%: 3.40%, S:7.79%; Measured value C:84.67%, H:4.17%: 3.42%, S:7.74%
Embodiment 17
The synthesis of compound 16
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; And in the reaction of the 4th step, phenylo boric acid is changed into diphenylene-oxide-2-boric acid, obtain compound 16.
Product MS(m/e): 790, ultimate analysis (C58H34N2O2): theoretical value C:88.08%, H:4.33%, N:3.54%, O:4.05%; Measured value C:88.06%, H:4.37%, N:3.50%, O:4.07%.
Embodiment 18
The synthesis of compound 17
Synthesis step is same as the four-step reaction in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; And in the reaction of the 4th step, phenylo boric acid is changed into diphenylene-oxide-4-boric acid, obtain compound 17.
Product MS(m/e): 790, ultimate analysis (C58H34N2O2): theoretical value C:88.08%, H:4.33%, N:3.54%, O:4.05%; Measured value C:88.04%, H:4.36%, N:3.52%, O:4.08.
Embodiment 19
The synthesis of compound 18
Synthesis step has four steps, and first three walks the front three-step reaction be same as in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; And the reaction of the 4th step is same as three-step reaction, just iodobenzene is changed into pentanoic, obtain compound 18.
Product MS(m/e): 792, ultimate analysis (C58H40N4): theoretical value C:87.85%, H:5.08%, N:7.07%; Measured value C:87.83%, H:5.09%, N:7.08%.
Embodiment 20
The synthesis of compound 19
Synthesis step has four steps, and first three walks the front three-step reaction be same as in embodiment 2, and just in the first step, naphthalene-2,6-hypoboric acid is changed into naphthalene-1,5-hypoboric acid, by 2,4-bis-bromo nitrobenzene changes into 2,5-bis-bromo nitrobenzene; And the reaction of the 4th step is same as three-step reaction, just iodobenzene is changed into carbazole, obtain compound 19.
Product MS(m/e): 788, ultimate analysis (C58H36N4): theoretical value C:88.30%, H:4.60%, N:7.10%; Measured value C:88.35, H:4.57%, N:7.08%.
Embodiment 21
The Application Example of each compound of the present invention
Conveniently compare the performance of these luminous organic materials as hole mobile material and fluorescent host material, the present invention devises a simple electroluminescence device, hole injection layer material we select HAT, hole mobile material NPB is as comparative material.Organic luminous layer is made up of light emitting host and dopant material, and we use traditional light emitting host material EM1 as comparative material, and EM2 is as luminescent dopant material, and wherein the structure of HAT, NPB, EM1, EM2 is respectively:
In the embodiment of the present invention, the structure of organic electroluminescence device is:
Substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can use the substrate in conventional organic luminescence device, such as: glass or plastics.In organic electroluminescence device of the present invention makes, select glass substrate, ITO makes anode material.
Hole-injecting material can use the various many arylamine very easily providing electronics, also can use many cyano group class material of extreme electron deficiency, and such molecule usually uses its lowest unoccupied molecular orbital (LUMO) to transmit electronics.The hole-injecting material used in the present invention is HAT.
Hole transmission layer can adopt various tri-arylamine group material.The material of stating in the present invention can be used as hole mobile material in electroluminescence device, compares with traditional hole mobile material NPB.
Emitting layer material has many kinds.The material of stating in the present invention can be used as light emitting host material in electroluminescence device, and luminescent dopant material is EM2.
Electron transport layer materials has many kinds.In order to characterize the material of stating in the present invention, we use common AlQ3 as electron transport material here, and object compares material property in the present invention, do not lie in the excellence pursuing device performance.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as common cathode structures such as LiF/Al, Li2O/Al.Cathode material selected in organic electroluminescence device of the present invention makes is LiF/Al.
Embodiment 22
Compound in the present embodiment is as the hole mobile material in organic electroluminescence device, and prepared multiple organic electroluminescence device altogether, its structure is: ITO/HAT(40nm)/hole mobile material (40nm)/EM1:EM2 (30nm)/Alq
3(20nm)/LiF(0.5nm)/Al(150nm);
A contrast organic electroluminescence device, hole mobile material selects NPB, and all the other organic electroluminescence devices select material of the present invention.
In the present embodiment, organic electroluminescence device preparation process is as follows:
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10
-5~ 9 × 10
-3pa, on above-mentioned anode tunic, vacuum evaporation HAT is as hole injection layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Particular compound 4,5,6,7,8,9,14,17,18,19 on hole injection layer again in the present invention of evaporation one deck or NPB are as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Vacuum evaporation luminescent layer EM1 and EM2(ratio 85%:15% on hole transmission layer), evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck AlQ3 is as electron transport material respectively, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The upper vacuum evaporation thickness of electron transfer layer (ETL) be the LiF of 0.5nm as electron injecting layer, thickness is the negative electrode of Al layer as device of 150nm.
Organic electroluminescence device performance sees the following form:
| Compound number | Require brightness cd/m 2 | Voltage V | Current efficiency cd/A |
| NPB | 5000.00 | 6.8 | 25.1 |
| 4 | 5000.00 | 6.4 | 27.3 |
| 5 | 5000.00 | 6.5 | 27.8 |
| 6 | 5000.00 | 6.0 | 26.9 |
| 7 | 5000.00 | 6.4 | 28.5 |
| 8 | 5000.00 | 6.6 | 27.9 |
| 9 | 5000.00 | 6.3 | 28.4 |
| 14 | 5000.00 | 6.4 | 29.3 |
| 17 | 5000.00 | 6.2 | 28.3 |
| 18 | 5000.00 | 6.1 | 28.0 |
| 19 | 5000.00 | 6.5 | 27.8 |
Embodiment 23
Compound in the present embodiment is as the hole mobile material in organic electroluminescence device, prepare multiple organic electroluminescence device altogether, its structure is: ITO/HAT(40nm)/NPB(40nm)/light emitting host material: EM2 (85%:15%, 30nm)/Alq3(20nm)/LiF(0.5nm)/Al(150nm);
A contrast organic electroluminescence device, light emitting host material selection EM1, all the other organic electroluminescence devices select material of the present invention.
In the present embodiment, organic electroluminescence device preparation process is as follows:
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10
-5~ 9 × 10
-3pa, on above-mentioned anode tunic, vacuum evaporation HAT is as hole injection layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
On hole injection layer, evaporation one deck NPB is as hole transmission layer again, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Compound 1,2,3,10,11,12 on hole transmission layer in the present invention of vacuum evaporation luminescent layer or EM1, doping evaporation EM2(ratio 85%:15%), evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck AlQ3 is as electron transport material respectively, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The upper vacuum evaporation thickness of electron transfer layer (ETL) be the LiF of 0.5nm as electron injecting layer, thickness is the negative electrode of Al layer as device of 150nm.
Luminescent device performance sees the following form:
| Compound number | Require brightness cd/m2 | Voltage V | Current efficiency cd/A |
| EM1 | 5000.00 | 6.8 | 25.1 |
| 1 | 5000.00 | 6.4 | 27.4 |
| 2 | 5000.00 | 6.5 | 27.0 |
| 3 | 5000.00 | 6.3 | 28.3 |
| 10 | 5000.00 | 6.6 | 28.2 |
| 11 | 5000.00 | 6.3 | 28.5 |
| 12 | 5000.00 | 6.2 | 27.7 |
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce landing voltage, and improving current efficiency, is hole mobile material of good performance and light emitting host material.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.
Claims (10)
1. a luminous organic material, is characterized in that, has structure as shown in the formula (I):
Wherein:
Ar
1-Ar
8independently be selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6 ~ C30, the condensed-nuclei aromatics group of the substituted or non-substituted of C6 ~ C30, the substituted or non-substituted of C6 ~ C30 fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle, triarylamine group, aryl oxide group base group, C1 ~ C12 substituted or non-substituted aliphatic alkyl group in one.
2. luminous organic material according to claim 1, is characterized in that, described Ar
4and Ar
8be H simultaneously.
3. luminous organic material according to claim 1, is characterized in that, described Ar
1and Ar
5be separately phenyl, xenyl, naphthyl, anthryl, phenanthryl, perylene base, pyrenyl.
4. luminous organic material according to claim 1, is characterized in that, described Ar
2, Ar
3, A
6, Ar
7separately be selected from phenyl, naphthyl, anthryl, phenanthryl, perylene base, pyrenyl, carbazyl, the carbazyl of replacement, hexichol amido, N-phenylnaphthalene amino, dibenzothiophene base, dibenzofuran group.
5. luminous organic material according to claim 1, is characterized in that, described compound is selected from following structural formula:
6. the luminous organic material described in any one of claim 1-5, is applied in organic electroluminescence device.
7. the luminous organic material of a kind of organic electroluminescence device according to claim 6, is characterized in that, described luminous organic material can be used as hole-injecting material, hole mobile material or material of main part.
8. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The substrate material of described hole transmission layer contains the luminous organic material according to any one of claim 1-5.
9. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The substrate material of described hole injection layer contains the luminous organic material according to any one of claim 1-5.
10. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The substrate material of described organic luminous layer contains the luminous organic material according to any one of claim 1-5.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659593A (en) * | 2008-07-14 | 2010-03-03 | 葛来西雅帝史派有限公司 | Organic electroluminescent compound and organic electroluminescent device using the same |
| WO2013094999A2 (en) * | 2011-12-23 | 2013-06-27 | 주식회사 두산 | Organic compound, and organic electroluminescent device using same |
-
2013
- 2013-09-30 CN CN201310460738.1A patent/CN104513662A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659593A (en) * | 2008-07-14 | 2010-03-03 | 葛来西雅帝史派有限公司 | Organic electroluminescent compound and organic electroluminescent device using the same |
| WO2013094999A2 (en) * | 2011-12-23 | 2013-06-27 | 주식회사 두산 | Organic compound, and organic electroluminescent device using same |
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