The aromatic amine compound and its have that one kind containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenesOrganic electroluminescence devicesTechnical field
The present invention relates to organic photoelectrical material technical fields, and in particular to one kind containing 9,9 '-spiral shell, two fluorenes and dibenzo thiopheneThe aromatic amine compound and its organic electroluminescence device of pheno.
Background technology
Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) is after CRT (Cathode RayTube, cathode-ray tube), the third generation display technology after LCD (Liquid Crystal Display, liquid crystal display),With high brightness, high contrast, fine definition, wide viewing angle, wide colour gamut, low-power consumption, wide temperature, luminous efficiency height, reaction timeThe advantages that short, transparent, flexible, basic structure are made of indium-tin oxide anode, metallic cathode and organic matter layer between the two,It is Dual Implantations type luminescent device, electric energy is converted into the luminous energy of organic semiconducting materials molecule, using electroluminescentPhysical mechanism, different from traditional LCD display modes, OLED is not necessarily to backlight, has self luminous characteristic, use very thinCoating of organic material and glass substrate, when have electric current by when, these organic materials will shine.
According to the difference of function, OLED material is divided into luminescent material, hole mobile material, electron transport material etc..HoleTransmission material usually has low highest occupied molecular orbital (HOMO) value, most of to have low T1 values, therefore, is sent out in phosphorescenceThe exciton diffusion generated in photosphere is eventually led to hole transport bed boundary or hole transmission layer side in luminescent layer inner boundaryCharge in luminous or luminescent layer is unbalanced, to shine on the interface of hole transmission layer.On hole transport bed boundaryIn the case of shining, the excitation purity for organic electric element occur and efficiency are lower the problem of shortening with the service life.Therefore, compel to be essentialDevelop a kind of luminous auxiliary layer, the luminous auxiliary layer needs to have the highest occupied molecular orbital energy in hole transmission layerThe substance of grade and the highest of luminescent layer the occupied molecular orbital energy level of the highest between occupied molecular orbital energy level, and with heightT1 values, and with the hole mobility in drive voltage range appropriate.
Invention content
In view of the above-mentioned problems existing in the prior art, the present invention provides one kind and containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenesAromatic amine compound and its organic electroluminescence device.
The present invention provides the aromatic amine compound that one kind containing 9,9 '-spiral shell two fluorenes and dibenzothiophenes, structural formula such as formulas(I) shown in：
Wherein, Ar1Substituted or unsubstituted 9 selected from C25-C60,9 '-spiral shell, two fluorenes, Ar2Substitution selected from C16-C30 orUnsubstituted dibenzothiophenes, Ar3Substituted or unsubstituted aryl, C3-C60 selected from C6-C60 it is substituted or unsubstituted miscellaneousAryl, L1、L2、L3Independently selected from singly-bound, the substituted or unsubstituted divalent aryl of C6-C30, C3-C30 substitution or do not takeThe divalent heteroaryl radical in generation.
Preferably, the Ar1Selected from following group：
Wherein, R1、R2、R3、R4、R5、R6、R7Independently selected from hydrogen, the substituted or unsubstituted fat of cyano, halogen, C1-C6The substituted or unsubstituted heteroaryl of fat base, the substituted or unsubstituted aryl of C6-C30, C3-C30, A, B, C, D are independently selectedFrom condensing the phenyl on phenyl ring.
Preferably, the Ar1Selected from following group：
Wherein, R8、R9、R10、R11、R12Independently selected from hydrogen, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, secondBase, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, C6-C30 substituted or unsubstituted aryl, C3-C30 substitutionOr unsubstituted heteroaryl.
Preferably, the Ar2Selected from following group：
Wherein, E, F are independently selected from condensing the phenyl on phenyl ring.
Most preferably, the aromatic amine compound for containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenes is selected from as followsAny one in HT2-1 to HT2-186：
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device include cathode, anode andThe one or more organic matter layers being placed between the cathode and the anode；Contain 9 containing described in the organic matter layer,The aromatic amine compound of 9 '-spiral shell two fluorenes and dibenzothiophenes.
Preferably, the auxiliary layer that shines is contained in the organic matter layer；Contain containing described in the luminous auxiliary layerThere is the aromatic amine compound of 9,9 '-spiral shell two fluorenes and dibenzothiophenes.
More there is choosing, contains hole transmission layer simultaneously in the organic matter layer；Containing in the hole transmission layerThat states contains the aromatic amine compound of 9,9 '-spiral shell two fluorenes and dibenzothiophenes.
Beneficial effects of the present invention：
Aromatic amine compound provided by the invention containing 9,9 '-spiral shell two fluorenes and dibenzothiophenes, contains 9,9 '-spiral shells simultaneouslyThe dibenzothiophenes of two fluorenes sums.The planar inline benzene unit of the rigidity of spiro fluorene keeps its thermal stability and chemical stability all higher,Dibenzothiophenes equally increases the stability of molecule.The material has good cavity transmission ability and stability, and canTo realize the equalizing charge in luminescent layer, there is suitable highest occupied molecular orbital energy level, high T1 values and high refractive index,The luminous efficiency, heat resistance and service life of OLED device can be improved, and driving voltage can be reduced, is a kind of function admirableOLED material.
Specific implementation mode
Present invention firstly provides the aromatic amine compound that one kind containing 9,9 '-spiral shell two fluorenes and dibenzothiophenes, structure formula (I)sIt is as follows：
Wherein, Ar1Substituted or unsubstituted 9 selected from C25-C60,9 '-spiral shell, two fluorenes, Ar2Substitution selected from C16-C30 orUnsubstituted dibenzothiophenes, Ar3Substituted or unsubstituted aryl, C3-C60 selected from C6-C60 it is substituted or unsubstituted miscellaneousAryl, L1、L2、L3Independently selected from singly-bound, the substituted or unsubstituted divalent aryl of C6-C30, C3-C30 substitution or do not takeThe divalent heteroaryl radical in generation.
Divalent aryl of the present invention refer to aromatic hydrocarbon molecule two aromatic core carbon on respectively remove a hydrogen atom after, be leftBivalent group general name, can be valentbivalent monocyclic aryl or divalent fused ring aryl, such as can be selected from phenylene, sub- biphenylBase, sub- terphenyl, naphthylene, anthrylene, phenanthrylene, sub- pyrenyl, fluorenylidene or sub- benzo phenanthryl etc., but not limited to this.
Divalent heteroaryl radical of the present invention refers to that one or more of divalent aryl aromatic core carbon is replaced to obtain by hetero atomGroup general name, the hetero atom includes but not limited to oxygen, sulphur or nitrogen-atoms, and the divalent heteroaryl radical can be valentbivalent monocyclicHeteroaryl or divalent fused ring heteroaryl, such as sub-pyridyl group, sub- quinolyl, sub- carbazyl, sub- thienyl, sub- benzo can be selected fromThienyl, furylidene, sub- benzofuranyl, sub- pyrimidine radicals, sub- benzo pyrimidine radicals, sub- imidazole radicals or sub- benzimidazolyl etc.,But not limited to this.
Preferably, the Ar1Selected from following group：
Wherein, R1、R2、R3、R4、R5、R6、R7Independently selected from hydrogen, the substituted or unsubstituted fat of cyano, halogen, C1-C6The substituted or unsubstituted heteroaryl of fat base, the substituted or unsubstituted aryl of C6-C30, C3-C30, A, B, C, D are independently selectedFrom condensing the phenyl on phenyl ring.
Preferably, the Ar1Selected from following group：
Wherein, R8、R9、R10、R11、R12Independently selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, isopropyl, justThe substituted or unsubstituted heteroaryl of butyl, isobutyl group, tertiary butyl, the substituted or unsubstituted aryl of C6-C30, C3-C30.
Preferably, the Ar2Selected from following group：
Wherein, E, F are independently selected from condensing the phenyl on phenyl ring.
Contain 9,9 '-spiral shell, two fluorenes and the aromatic amine compound of dibenzofurans is preferably selected from following institute specifically, describedShow any one in HT2-1 to HT2-186：
Some tools of the aromatic amine compound of the present invention containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenes are enumerated aboveBody structure type, but the invention is not limited in these listed chemical constitutions, every based on structure shown in formula (I), Ar1、Ar2、Ar3And L1、L2、L3It should be all included for group as defined above.
The preparation method of aromatic amine compound of the present invention containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenes, can pass throughFollowing synthetic route is prepared：
Wherein, Ar1Substituted or unsubstituted 9 selected from C25-C60,9 '-spiral shell, two fluorenes, Ar2Substitution selected from C16-C30 orUnsubstituted dibenzothiophenes, Ar3Substituted or unsubstituted aryl, C3-C60 selected from C6-C60 it is substituted or unsubstituted miscellaneousAryl, L1、L2、L3Independently selected from singly-bound, the substituted or unsubstituted divalent aryl of C6-C30, C3-C30 substitution or do not takeThe divalent heteroaryl radical in generation.
Contain Ar3Aromatic amine compound (A) first with contain Ar1Bromide (B) occur Buchwald reaction, obtainIntermediate M；Intermediate M again with contain Ar2Bromide (C) occur Buchwald reaction, finally obtain target compound (I).
The present invention does not have special limitation, use well-known to those skilled in the art the above-mentioned reaction condition respectively reactedReaction condition, the preparation method is simple, and raw material is easy to get.
The present invention further provides a kind of organic electroluminescence device, the organic electroluminescence device include cathode,Anode and the one or more organic matter layers being placed between the cathode and the anode；Contain the present invention in the organic matter layerThe aromatic amine compound for containing 9,9 '-spiral shell two fluorenes and dibenzothiophenes preferably comprises hole note in the organic matter layerEnter at least one in layer, hole transmission layer, shine auxiliary layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layerLayer；Preferably, in the organic matter layer containing shine auxiliary layer, the luminous auxiliary layer between luminescent layer and anode, andAnd contain the aromatic amine compound for containing 9,9 '-spiral shell two fluorenes and dibenzothiophenes；Preferably, same in the organic matter layerShi Hanyou hole transmission layers, the hole transmission layer contain between the luminous auxiliary layer and anode, and containing describedThere is the aromatic amine compound of 9,9 '-spiral shell two fluorenes and dibenzothiophenes.
According to the present invention, the device architecture of use is preferred, Ke Yiwei：Transparent glass is as anode；4,4', 4 "-three[2- naphthylphenyls amino] triphenylamine (2-TNATA) is used as hole injection layer；N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines (NPB) or the compounds of this invention (HT2-1 to HT2-186) are used as hole transmission layer；Chemical combination of the present inventionObject (HT2-1 to HT2-186) is as the auxiliary layer that shines；(9- carbazoles) biphenyl of 4,4'- bis- (CBP) and two (1- phenyl-isoquinolin)(acetylacetone,2,4-pentanedione) closes iridium ((piq)2Ir (acac)) with 95:The mixture of 5 weight ratio is as luminescent layer；Bis- (2- methyl -8- hydroxylsBase quinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyls) aluminium (BAlq) be used as hole blocking layer；8-hydroxyquinoline aluminium (Alq3) conductElectron transfer layer；LiF is as electron injecting layer；Al is as cathode.
The organic electroluminescence device can be used for the application neck such as flat-panel monitor, lighting source, direction board, signal lampDomain.
By following embodiment, the present invention, but so as not to the limitation present invention are more fully explained.In the base of the descriptionOn plinth, those of ordinary skill in the art will without creative efforts, in disclosed entire scopeImplement the present invention and prepares other compounds according to the present invention.
The present invention is not particularly limited the source of the raw material employed in following embodiment, can be commercial product orIt is prepared using preparation method well-known to those skilled in the art.
Embodiment 1：The preparation of bromide B
The preparation of bromide B-l:
A) under nitrogen atmosphere, by the iodo- 3- methyl-bromobenzoates (10.0g, 30mmol) of 2-, phenyl boric acid (3.66g, 30mmol) andTetrakis triphenylphosphine palladium (1.7g, 1.46mmol) is dissolved in 100ml tetrahydrofurans, is stirred 30 minutes, is then dripped in 20 minutesAdd 50ml wet chemicals (1.63g, 11.18mmol), be refluxed overnight, wash, dichloromethane extraction evaporates organic solvent；B) obtained solid (8.5g, 255.0mmol) and sodium hydroxide (1.2g, 30mmol) are dissolved in 100ml ethyl alcohol, are flowed back 6 hours,After being cooled to room temperature, neutralized with the hydrochloric acid of 2M, filtering, obtained solid recrystallizes in ethanol；Crystal obtained by c) (10g,300ml methanesulfonic acids 30mmol) are dissolved in, stirs 24 hours, is poured into ice water at 30 DEG C, are filtered, are washed, it is dry, use bicarbonateAfter sodium water solution stirs 3 hours, filtering is washed to neutrality, recrystallizes in ethanol, obtains intermediate D-1；D) by 2- bromo biphenyls(7.88g, 34.0mmol) is dissolved in 120ml tetrahydrofurans, be added dropwise at -78 DEG C n-BuLi hexane solution (2.5M,15.6ml), time control is added in 10 minutes, keeps this temperature to stir 1 hour, under an argon by gained intermediate D-1It in tetrahydrofuran solution (150ml) the addition system of (8.06g, 26.0mmol), is neutralized, is used with sodium bicarbonate aqueous solution at room temperatureDichloromethane extracts, and organic layer is dried with anhydrous magnesium sulfate, is evaporated under reduced pressure, and gained crude product is dissolved in acetic acid (250ml), is addedAqueous hydrochloric acid solution (25ml, 35wt%), flows back 12 hours, is cooled to room temperature, purified with column chromatography (dichloromethane/just oneselfAlkane), obtain bromide B-1.
Bromide B-2 to B-41 can be prepared by above-mentioned reaction.
The preparation of bromide B-42：
By gained bromide B-1 (7.89g, 20mmol), connection boric acid pinacol ester (6.22g, 24mmol), 1,1 '-bis- (twoPhenylphosphine)-ferrocene-palladium chloride (II) dichloromethane complex (0.49g, 0.6mmol), potassium acetate (5.90g, 60mmol)It is reacted under reflux 16 hours with 79ml toluene, it is cooling, 26ml water is added, stirs 30 minutes, isolates organic phase, pass through short siliconDiatomaceous earth bed filters, and then evaporates organic solvent, gained crude product recrystallizes in heptane/toluene；Under argon atmospher, by obtained solid(6.64g, 15mmol), to bromo-iodobenzene (4.05g, 14.3mmol), tetrakis triphenylphosphine palladium (0.35g, 0.3mmol), toluene(43ml), aqueous sodium carbonate (2M, 21ml) are added in flask, and back flow reaction 8 hours is cooled to room temperature, is extracted with toluene, hadMachine mutually uses saturated common salt water washing to be purified with column chromatography after organic phase drying, obtain bromide B-42.
Bromide B-43 to B-52 can be prepared by the above method.
Embodiment 2：The preparation of aromatic amine compound A
The preparation of compound A-1：
Bromobenzene (4.71g, 30mmol), cuprous iodide (0.06g, 0.3mmol), 45ml liquefied ammonia are added in flask,100 DEG C are reacted 18 hours, filtering, and liquid finally obtains compound A-1 by extraction, washing, drying, removal organic solvent.
Compound A-2 to A-36 can be prepared by the above method.
Embodiment 3：The preparation of intermediate M
The preparation of intermediate M-1：Under argon atmospher, by bromide B-1 (5.93g, 15mmol), aromatic amine compound A-1(1.40g, 15mmol), sodium tert-butoxide (2.88g, 30mmol) are added in 150ml dehydrated toluenes, stir lower addition palladium(0.07g, 0.3mmol), tri-tert-butylphosphine (0.06g, 0.3mmol) reacts 8 hours at 80 DEG C.After cooling, by diatomite/Silica gel funnel is filtered, and filtrate removes organic solvent by vacuum distillation, residue obtained to be recrystallized in toluene, obtained by leachingSolid, it is dry, obtain intermediate M-1.
Intermediate M-2 to M-124 can be prepared by the above method.
Embodiment 4：The preparation of compound HT2-1
Under argon atmospher, to intermediate M-1 (4.08g, 10mmol), bromide C-1 (3.13g, 10mmol), three (two benzalBenzylacetone) two palladiums (0.14g, 0.15mmol), tri-tert-butylphosphine tetrafluoroborate (0.087g, 0.3mmol), sodium tert-butoxide50ml anhydrous dimethyl benzene is added in (1.9g, 20mmol), is flowed back 8 hours.50 DEG C are cooled to, is filtered by diatomite/silica gel, filterLiquid concentrates, and residue obtained to be purified with silica gel column chromatography, gained crude product recrystallizes in toluene, obtains compound HT2-1(4.22g, 6.6mmol), yield 66%.Mass spectrum m/z：640.56 (calculated values：639.82).Theoretical elemental content (%)C47H29NS：C,88.23；H,4.57；N,2.19；S,5.01.Survey constituent content (%)：C,88.18；H,4.56；N,2.17；S,4.96.The above results confirm that it is target product to obtain product.
Embodiment 5：The preparation of compound HT2-23
Compound M-1 is replaced with to the compound M-2 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-7, other steps are same as Example 4, you can obtain compound HT2-23.Mass spectrum m/z：641.75 (calculated values：639.82).Theoretical elemental content (%) C47H29NS：C,88.23；H,4.57；N,2.19；S,5.01.Survey constituent content(%)：C,88.19；H,4.59；N,2.16；S,5.03.The above results confirm that it is target product to obtain product.
Embodiment 6：The preparation of compound HT2-51
Compound M-1 is replaced with to the compound M-7 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-6, other steps are same as Example 4, you can obtain compound HT2-51.Mass spectrum m/z：656.46 (calculated values：657.81).Theoretical elemental content (%) C47H28FNS：C,85.82；H,4.29；F,2.89；N,2.13；S,4.87.Survey elementContent (%)：C,85.77；H,4.31；F,2.83；N,2.17；S,4.85.The above results confirm that it is target product to obtain product.
Embodiment 7：The preparation of compound HT2-80
Compound M-1 is replaced with to the compound M-18 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-10, other steps are same as Example 4, you can obtain compound HT2-80.Mass spectrum m/z：715.31 (calculateValue：715.91).Theoretical elemental content (%) C53H33NS：C,88.92；H,4.65；N,1.96；S,4.48.Survey constituent content(%)：C,88.90；H,4.61；N,1.99；S,4.43.The above results confirm that it is target product to obtain product.
Embodiment 8：The preparation of compound HT2-93
Compound M-1 is replaced with to the compound M-34 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-93, other steps are same as Example 4, you can obtain compound HT2-93.Mass spectrum m/z：877.59 (calculateValue：878.11).Theoretical elemental content (%) C66H39NS：C,90.28；H,4.48；N,1.60；S,3.65.Survey constituent content(%)：C,90.24；H,4.46；N,1.58；S,3.69.The above results confirm that it is target product to obtain product.
Embodiment 9：The preparation of compound HT2-113
Compound M-1 is replaced with to the compound M-54 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-8, other steps are same as Example 4, you can obtain compound HT2-113.Mass spectrum m/z：882.36 (calculateValue：881.11).Theoretical elemental content (%) C65H40N2S：C,88.61；H,4.58；N,3.18；S,3.64.Survey constituent content(%)：C,88.57；H,4.55；N,3.16；S,3.60.The above results confirm that it is target product to obtain product.
Embodiment 10：The preparation of compound HT2-125
Compound M-1 is replaced with to the compound M-66 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-5, other steps are same as Example 4, you can obtain compound HT2-125.Mass spectrum m/z：801.61 (calculateValue：802.05).Theoretical elemental content (%) C58H43NOS：C,86.86；H,5.40；N,1.75；O,1.99；S,4.00.Actual measurementConstituent content (%)：C,86.84；H,5.39；N,1.72；O,1.96；S,3.98.The above results confirm that obtain product produces for targetProduct.
Embodiment 11：The preparation of compound HT2-152
Compound M-1 is replaced with to the compound M-93 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-6, other steps are same as Example 4, you can obtain compound HT2-152.Mass spectrum m/z：945.09 (calculateValue：946.10).Theoretical elemental content (%) C67H38F3NS：C,85.06；H,4.05；F,6.02；N,1.48；S,3.39.Actual measurementConstituent content (%)：C,85.03；H,4.02；F,6.11；N,1.46；S,3.36.The above results confirm that obtain product produces for targetProduct.
Embodiment 12：The preparation of compound HT2-163
Compound M-1 is replaced with to the compound M-104 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-5, other steps are same as Example 4, you can obtain compound HT2-163.Mass spectrum m/z：918.25 (calculateValue：917.23).Theoretical elemental content (%) C67H52N2S：C,87.74；H,5.71；N,3.05；S,3.50.Survey constituent content(%)：C,87.71；H,5.67；N,3.01；S,3.53.The above results confirm that it is target product to obtain product.
Embodiment 13：The preparation of compound HT2-186
Compound M-1 is replaced with to the compound M-124 of equimolar amounts, bromide C-1 is replaced with equimolar amountsBromide C-20, other steps are same as Example 4, you can obtain compound HT2-186.Mass spectrum m/z：833.87 (metersCalculation value：834.09).Theoretical elemental content (%) C62H43NS：C,89.28；H,5.20；N,1.68；S,3.84.Actual measurement element containsIt measures (%)：C,89.26；H,5.17；N,1.64；S,3.80.The above results confirm that it is target product to obtain product.
Embodiment 14：The preparation of luminescent device 1
First, it is formed with the thickness vacuum deposition 2-TNATA of 60nm in the ITO layer (anode) for being formed in organic substrateHole injection layer；Hole transmission layer is formed with the thickness vacuum evaporation NPB of 60nm on above-mentioned hole injection layer；Later, existUsing the thickness vacuum evaporation compound HT2-23 of 20nm as luminous auxiliary layer on hole transmission layer；Then, above-mentioned luminous auxiliaryIt helps on layer with weight ratio as 95:5 CBP and (piq)2Ir (acac) vacuum depositions are as luminescent layer, thickness 30nm；Then,Hole blocking layer is formed with the thickness vacuum deposition BAlq of 10nm on above-mentioned luminescent layer；On above-mentioned hole blocking layer withThe thickness vacuum deposition Alq of 40nm3To form electron transfer layer；Then, LiF is deposited as electron injection using the thickness of 0.2nmLayer；Finally, cathode is formed with the thickness depositing Al of 150nm.
Embodiment 15：The preparation of luminescent device 2
Compound HT2-23 is replaced with compound HT2-64, other steps are identical as embodiment 14.
Embodiment 16：The preparation of luminescent device 3
Compound HT2-23 is replaced with compound HT2-93, other steps are identical as embodiment 14.
Embodiment 17：The preparation of luminescent device 4
Compound HT2-23 is replaced with compound HT2-103, other steps are identical as embodiment 14.
Embodiment 18：The preparation of luminescent device 5
Compound HT2-23 is replaced with compound HT2-125, other steps are identical as embodiment 14.
Embodiment 19：The preparation of luminescent device 6
Compound HT2-23 is replaced with compound HT2-130, other steps are identical as embodiment 14.
Embodiment 20：The preparation of luminescent device 7
Compound HT2-23 is replaced with compound HT2-154, other steps are identical as embodiment 14.
Embodiment 21：The preparation of luminescent device 8
Compound HT2-23 is replaced with compound HT2-158, other steps are identical as embodiment 14.
Embodiment 22：The preparation of luminescent device 9
Compound HT2-23 is replaced with compound HT2-164, other steps are identical as embodiment 14.
Embodiment 23：The preparation of luminescent device 10
Compound HT2-23 is replaced with compound HT2-172, other steps are identical as embodiment 14.
Embodiment 24：The preparation of luminescent device 11
Compound HT2-23 is replaced with compound HT2-179, other steps are identical as embodiment 14.
Embodiment 25：The preparation of luminescent device 12
NPB is replaced with compound HT2-23, other steps are identical as embodiment 14.
Embodiment 26：The preparation of luminescent device 13
NPB is replaced with compound HT2-51, other steps are identical as embodiment 14.
Embodiment 27：The preparation of luminescent device 14
NPB is replaced with compound HT2-80, other steps are identical as embodiment 14.
Embodiment 28：The preparation of luminescent device 15
NPB is replaced with compound HT2-94, other steps are identical as embodiment 14.
Embodiment 29：The preparation of luminescent device 16
NPB is replaced with compound HT2-112, other steps are identical as embodiment 14.
Embodiment 30：The preparation of luminescent device 17
NPB is replaced with compound HT2-125, other steps are identical as embodiment 14.
Embodiment 31：The preparation of luminescent device 18
NPB is replaced with compound HT2-155, other steps are identical as embodiment 14.
Embodiment 32：The preparation of luminescent device 19
NPB is replaced with compound HT2-158, other steps are identical as embodiment 14.
Embodiment 33：The preparation of luminescent device 20
NPB is replaced with compound HT2-179, other steps are identical as embodiment 14.
Comparative example：The preparation of luminescent device 21
Other than not forming luminous auxiliary layer this point, luminescent device has been made in method identical with embodiment 14.
Compound involved in the embodiment of the present invention and comparative example is as follows：
The luminescent properties for the organic electroluminescence device that the embodiment of the present invention is prepared are as shown in the table：
The above result shows that the aromatic amine compound for containing 9,9 '-spiral shell, two fluorenes and dibenzothiophenes of the invention is as hairLight auxiliary layer and hole transmission layer are applied in organic electroluminescence device, can improve the luminous efficiency of device, reduce deviceDriving voltage, be the luminous organic material of a kind of function admirable.
Obviously, the explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should refer toGo out, it, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical fieldBright some improvement and modification can also be carried out, these improvement and modification are also fallen within the protection scope of the claims of the present invention.