CN105753813A - Synthesis and organic luminescent device of bisphenothiazine dioxide derivative - Google Patents
Synthesis and organic luminescent device of bisphenothiazine dioxide derivative Download PDFInfo
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Abstract
The invention relates to a bisphenothiazine dioxide derivative and an application thereof, and belongs to the field of organic photoelectric material. Different aryl dibromides are adopted as a parent body and are connected with phenothiazine dioxide to form the bisphenothiazine dioxide derivative; with introduction of -SO2-, the compound has good electron transmission performance, and the electronic affinity of the compound and the stability of the compound in air are improved. The bisphenothiazine dioxide derivative can be used as an OLED luminescent device, is suitable for use as an electron transmission material of a blue fluorescent material and as a green phosphorescence electron transmission material and also has the potential of red color application, so that the bisphenothiazine dioxide derivative can be applied to a red-green-blue tri-phosphor doped main body material and also can be independently used as a hole transmission material, an electron transmission material or a luminescent layer.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly relate to a kind of double; two phenothiazine dioxide derivative and application thereof.
Background technology
The research of organic electroluminescence device starts from the '30s of eighties of last century, within 1936, organic fluorescent compounds dispersion is made thin film by Destriau in the polymer, obtain electroluminescent device the earliest, but this device is thicker due to thin film, cut-in voltage is significantly high, does not cause everybody attention at that time；But adopt vacuum-deposited method to be prepared for the anthracene thin film of 0.6 μ m-thick to nineteen eighty-two P.S.Vincett et al., the driving voltage of device is fallen below below 30V, this attention just starting to have attracted people；1987, it is 1 year with milestone significance for organic electroluminescence device, C.W.Tang etc. adopt ultrathin membrane technology, with a kind of diamine derivative N, N,-diphenyl-N, N ,-bis (3-methylphenyl)-1,1, biphenyl-4,4, diamine (TPD) are as hole transmission layer, using tris (8-hydroxyquinoline) aluminum (Alq3) as luminescent layer, made double-deck organic electroluminescence device, this device under 10V brightness up to 1000cd/m2, luminous efficiency is 1.51lm/W, and the life-span, this breakthrough made the research of organic electroluminescence device worldwide carry out rapidly and in depth more than 100 hours.
In order to obtain the practical organic electroluminescence device of high brightness, high efficiency, long-life and low turn-on voltage, people constantly develop new material and propose new device architecture etc..
C.Adachi in 1988 et al. proposes hole transmission layer, electron transfer layer and luminescent layer three-decker separately first, it is thus achieved that high brightness and long-life blue-light device；Within 1994, C.W.Tang reported first reaches the double-decker organic electroluminescence device of 10000 hours service life in the organic and inorganic EL international conference that Japan shore pine is held；1998, the Forrest group of Princeton university proposes phosphorescent coloring is applied to organic electroluminescence device first, thus breach the restriction lower than 25% of the device internal quantum efficiency, internal quantum efficiency is made to have reached 100% in theory, thus having started the frontier of Based on Organic Electrophosphorescence.In the same year, T.R.Hebner etc. has invented the ink-jet printing process preparing organic electroluminescence device, and this is that organic electroluminescence device provides bigger possibility from study direction market.Entering new century, various novel organic luminescent devices emerge in an endless stream especially, relatively representational: 2004, and lamination (tandem) organic electroluminescence device that L.S.Liao et al. makes, current efficiency is up to 136cd/A.
For equilbrium carrier charge velocity and the luminous efficiency improving device, in luminescent device, generally introduce one layer of electron transfer layer being made up of electron transport material and the hole transmission layer being made up of hole mobile material, but the introducing of electronics and hole transmission layer often results in the increase of element manufacturing cost.In order to simplify device architecture, reduce the driving voltage of device, the injection in balance electronic and hole, current research trend, in being concentrated in a molecule by the group of several functions, makes them have two or more functions (conduction of hole transport, electronics and luminescence etc.) simultaneously.
In current present Research, carbazole and derivant thereof belong to electron rich system, it is recognized that there is good cavity transmission ability, strong electron-withdrawing group group-SO-or-SO2-high molecular electron affinity and electron mobility can be put forward, and sulphur atom has located the state of oxidation, has non-oxidizability.This patent introduces strong electron-withdrawing group-SO in phenothiazine2-, electron transport ability substantially increases.Carbazole and oxidation of thiophene are combined in same a part, the electrogen that composition is core with phenothiazine dioxide framework unit, form bigger conjugated system, show high heat stability and high vitrification point, therefore become a promising organic photoelectrical material of class.
Summary of the invention
The technical problem to be solved is to provide a kind of double; two phenothiazine dioxide derivative and application thereof.
The technical scheme is that
A kind of double; two phenothiazine dioxide derivative, the double; two phenothiazine dioxide being parent with different aryl, its general structure is as follows:
。
Wherein, R represents substituted or unsubstituted carbon number is the aryl of 10-20, heterocyclic radical.
Preferred R is benzo phenanthryl, phenanthryl, anthryl, N-phenyl-carbazyl, naphthyl, pyrenyl.
Shown in described formula (1) containing double; two phenothiazine dioxide derivatives electroluminescent organic materials, concrete example is as follows, but the invention is not restricted to these example formula compounds.Should illustrate, following specifically shown substituent group, it is possible to enumerate as preferred substituent group in the present invention:
Present invention also offers a kind of preparation method containing double; two phenothiazine dioxide, it is characterised in that comprise the steps:
Step S1: add phenothiazine, two bromo-derivatives of different substituents, sodium tert-butoxide, three (dibenzalacetone) two palladium toluene, tri-butyl phosphine in the reaction vessel after degassed, fully obtains double; two phenothiazine compounds of flaxen different substituents after reaction；
Step S2: double; two phenothiazines of different substituents are added metachloroperbenzoic acid, ice bath reacts, and obtains double; two phenothiazine dioxide derivatives of different substituents.
In technique scheme, described step S1 particularly as follows:
Phenothiazine, two bromo-derivatives of different substituents and sodium tert-butoxide is added in the reaction vessel after degassed, and dissolve with toluene 100ml, add three (dibenzalacetone) two palladium, tri-butyl phosphine afterwards, 110 DEG C of backflows are overnight, after reactant liquor cooling, using 100ml dichloromethane extraction, saturated NaCl washes, anhydrous magnesium sulfate dries, it is evaporated organic facies, washes 2 times with 100ml petroleum ether, obtain double; two phenothiazine of faint yellow different substituents.
In technique scheme, described step S2 particularly as follows:
Double; two phenothiazines of different substituents and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid under ice bath, after ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, and is evaporated organic facies, crosses silica gel funnel and obtains double; two phenothiazine dioxide derivatives of different substituents.
Present invention also offers a kind of double; two phenothiazine dioxide derivative at organic electroluminescence device.
Use the OLED emitting device structure of material of the present invention, containing at least one luminescent layer 5, hole injection layer 3, hole transmission layer 4, electron transfer layer 6 and/or electron injecting layer 7 are set in this layer according to optional principle.OLED luminescent device includes Rotating fields as described below:
(1) anode/organic luminous layer 5/ negative electrode；
(2) anode/hole injection layer 3/ organic luminous layer 5/ negative electrode；
(3) anode/organic luminous layer 5/ electron injecting layer 7/ negative electrode；
(4) anode/hole injection layer 3/ organic luminous layer 5/ electron injecting layer 7/ negative electrode；
(5) anode/hole transmission layer 4/ organic luminous layer 5/ electron injecting layer 7/ negative electrode；
(6) anode/hole injection layer 3/ hole transmission layer 4/ organic luminous layer 5/ electron injecting layer 7/ negative electrode；
(7) anode/hole injection layer 3/ hole transmission layer 4/ organic luminous layer 5/ electron transfer layer 6/ negative electrode.
Making in OLED display, material can be made thin film by methods such as vapour deposition method, spin-coating method or casting methods and be formed by each layer.The thickness of each layer formed in this way is not particularly limited, can the character of respective material and suitable set, be generally the scope of 2nm～5000nm.Furthermore, the method for luminescent material thin-film is readily available uniform rete and not easily generates the experience of pin hole, it is preferable that vapour deposition method.Evaporation condition is it is generally preferred that in boat, heating-up temperature 50 DEG C～400 DEG C, vacuum 10-6Pa～10-3Pa, evaporation rate 0.01nm/s～50nm/s, substrate temperature-150 DEG C～300 DEG C, thickness 5nm～5um scope in suitable set.
Anode has the function injecting holes into hole transmission layer 4, and anode is generally made up of later material: such as metals such as aluminum, gold, silver, nickel, palladium or platinum；Such as metal-oxides such as Indium sesquioxide., stannum oxide, zinc oxide, indium stannum composite oxides, indium zinc composite oxides；Such as metal halides such as Copper diiodides；White carbon black；Or partially electronically conductive macromolecule etc..
Hole transmission layer is to inject the high efficiency in hole from anode and can effectively transmit the material of injected holes.Accordingly, it would be desirable to the ionization potential of this material is low, high to the permeability of visible ray, hole mobility high, stable in properties, in addition it is also necessary to the light being not likely to produce in preparation or when using becomes the impurity of trap (trap).Contact additionally, due to luminescent layer 5, hole transmission layer 4 is needed not make the light delustring of light emitting layer 5, and form exciplex not and between luminescent layer 5 and the common hole mobile material that lowers efficiency can be enumerated with N, N'-diphenyl-N, N'-bis-(2-naphthyl)-1,1 '-biphenyl-4, what 4'-diamidogen (NPB) was representative has the aromatic amine compounds of star radial configuration, carbazoles derivant etc. containing the aromatic diamine of plural tertiary amine, triphen amine.Namely these compounds can be used alone, but also also mix together two or more.
As at hole-injecting material functional material, it is possible to select arbitrary material to use from material known to the hole transmission layer 4 of OLED luminescent device.
Luminescent layer 5 is formed by luminescent substance, wherein, between the electrode being applied with electric field, this luminescent substance because of hole and electronics in conjunction with and excite, thus showing strong luminescence.Usual luminescent layer 5 contains the doping type material as luminescent substance and host material.In order to obtain high efficiency OLED luminescent device, the adoptable a kind of dopant material of its luminescent layer 5, or adopt multiple dopant material.Dopant material can be simple fluorescence or phosphor material, or is formed by different fluorescence and phosphorescence matched combined, and luminescent layer can be single emitting layer material, it is also possible to for the recombination luminescence layer material being superimposed.
The material of main part of luminescent layer not only needs possess ambipolar charge-transporting matter, simultaneously need to appropriate energy rank, excitation energy is efficiently transferred to guest emitting material, and the material of this class can enumerate diphenylethyllene aryl derivatives, stibene derivant, carbazole derivates, triarylamine derivatives, anthracene derivant, pyrene derivatives, coronene derivant etc..
Relative to material of main part, the incorporation of guest materials is preferably more than 0.01 weight %, below 20 weight %.The material of this class can enumerate the metal complex of iridium, nail, platinum, rhenium, palladium etc..
Form the material of the electron transfer layer 6 of above-mentioned OLED luminescent device, electronic transport property OLED material can be selected arbitrarily use by possessing, such material can be enumerated such as 1, 3, the benzimidazoles derivatives such as 5-tri-(1-naphthyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), metal complexs such as three (oxine) aluminum (Alq3), 2-(4 '-2-methyl-2-phenylpropane base)-5-(4 '-xenyl)-1, 3, the oxadiazole derivatives such as 4-diazole (PBD), 4, 7-diphenyl-1, the phenanthroline derivants such as 10-phenanthrene quinoline (BPhen), triazole derivative, quinoline, quinoxaline derivant etc..
The above-mentioned spendable cathode material of OLED luminescent device can be selected for work function less than the metal of 4eV, alloy, conductive compound and their mixture.Its concrete example is aluminum, calcium, magnesium, lithium, magnesium alloy, aluminium alloy etc..In order to obtain the luminescence of OLED efficiently, preferably the transmitance of at least one of electrode is set to more than 10%.Negative electrode can pass through dry method such as vacuum evaporation, vapour deposition or sputtering is formed.
The invention has the beneficial effects as follows:
Double; two phenothiazine dioxide derivatives of present invention synthesis are applied in organic electroluminescence device to obtain efficient electroluminescent properties, and its major advantage is as follows:
1, adopt with different aryl for parent, connect phenothiazine dioxide, introducing-SO in molecular system2-make it have good electronic transmission performance, it is greatly improved luminous efficiency.
2, there is good heat stability, glass transition temperature and decomposition temperature all significantly high.
3, such material has applicable molecular entergy level, be suitable as blue emitting material material of main part, there are the potentiality of red and green application simultaneously, therefore namely can be applicable to red-green-blue doping property material of main part, it is possible to separately as hole mobile material, electron transport material or luminescent layer.
Hereinafter principles of the invention and feature being described, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Detailed description of the invention:
Embodiment 1:
Phenothiazine 48.30mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.41mmol; tri-butyl phosphine 2.45mmol, 2,7-dibromo benzophenanthrene 16.20mmol; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.09mmol after washing 2 times, productivity is 87.00%.
2,7-double; two (10H-phenothiazine-10-base) benzophenanthrene 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear silica gel funnel of crossing obtains 10,10'-(2,7-benzo phenanthryl) double; two (10H-phenothiazine-5,5-dioxide) 10.50mmol, productivity is 75.00%.Mass spectrum: value of calculation is 686.80；Test value is 686.82.Elementary analysis: value of calculation is C:73.45；H:3.82；N:4.08；O:9.32；S:9.34；Test value is C:73.47；H:3.84；N:4.06；O:9.31；S:9.33.
Embodiment 2:
Phenothiazine 48.60mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.203mmol; tri-butyl phosphine 1.295mmol, 2,7-dibromo phenanthrene 16.20mmol; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.01mmol after washing 2 times, productivity is 86.48%.
Luxuriant and rich with fragrance to 2,7-double; two (10H-phenothiazine-10-base) 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear silica gel funnel of crossing obtains 10,10'-(2,7-phenanthryl) double; two (10H-phenothiazine-5,5-dioxide) 10.47mmol, and productivity is 74.79%.Mass spectrum: value of calculation is 636.74；Test value is 636.72.Elementary analysis: value of calculation is C:71.68；H:3.80；N:4.40；O:10.05；S:10.07；Test value is C:71.66；H:3.82；N:4.42；O:10.04；S:10.06.
Embodiment 3:
Phenothiazine 48.62mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.203mmol; tri-butyl phosphine 1.295mmol, 2,7-dibromo pyrene 16.20mmol; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.03mmol after washing 2 times, productivity is 87.58%.
2,7-double; two (10H-phenothiazine-10-base) pyrene 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear silica gel funnel of crossing obtains 10,10'-(2,7-pyrenyls) double; two (10H-phenothiazine-5,5-dioxide) 10.57mmol, and productivity is 75.50%.Mass spectrum: value of calculation is 660.76；Test value is 660.74.Elementary analysis: value of calculation is C:72.71；H:3.66；N:4.24；O:9.69；S:9.71；Test value is C:72.70；H:3.68；N:4.25；O:9.65；S:9.76.
Embodiment 4:
Phenothiazine 48.59mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.203mmol; tri-butyl phosphine 1.295mmol, 2,6-dibromoanthracene 16.20mmol; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.26mmol after washing 2 times, productivity is 88.02%.
2,6-double; two (10H-phenothiazine-10-base) anthracene 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear silica gel funnel of crossing obtains 10,10'-(2,6-anthryls) double; two (10H-phenothiazine-5,5-dioxide) 10.75mmol, and productivity is 76.79%.Mass spectrum: value of calculation is 636.74；Test value is 636.76.Elementary analysis: value of calculation is C:71.68；H:3.80；N:4.40；O:10.05；S:10.07；Test value is C:71.66；H:3.82；N:4.42；O:10.04；S:10.06.
Embodiment 5:
Phenothiazine 48.46mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.203mmol; tri-butyl phosphine 1.295mmol, 2,6-dibromine naphthalene 16.20mmol; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.06mmol after washing 2 times, productivity is 86.80%.
2,6-double; two (10H-phenothiazine-10-base) naphthalene 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear silica gel funnel of crossing obtains 10,10'-(2,6-naphthyls) double; two (10H-phenothiazine-5,5-dioxide) 10.51mmol, and productivity is 75.07%.Mass spectrum: value of calculation is 586.68；Test value is 586.66.Elementary analysis: value of calculation is C:69.61；H:3.78；N:4.77；O:10.91；S:10.93；Test value is C:69.63；H:3.77；N:4.76；O:10.90；S:10.94.
Embodiment 6:
Phenothiazine 48.50mmol and sodium tert-butoxide 48.49mmol is added after in reaction bulb and add toluene 33ml; when nitrogen protection; after stirring 10min; add three (dibenzalacetone) two palladium 0.203mmol; the bromo-9-phenyl carbazole 16.20mmol of tri-butyl phosphine 1.295mmol, 3,6-bis-; taking a breath three times, 110 DEG C of backflows are overnight.Reaction terminates, post processing, and dichloromethane 100ml extracts, after being evaporated organic facies, a small amount of dichloromethane precipitates out product with petroleum ether after dissolving, and the product petroleum ether 100ml of precipitation washes 3 times, ethanol 100ml, obtaining light yellow product 14.08mmol after washing 2 times, productivity is 86.91%.
3,6-double; two (10H-phenothiazine-10-base) 9-phenyl carbazole 14.00mmol and dichloromethane being added in reaction bulb, be slowly dividedly in some parts metachloroperbenzoic acid 35.00mmol under ice bath, after rear ice bath reaction 30min, back flow reaction is overnight.Reaction washes organic facies with saturated sodium bicarbonate after terminating, after be evaporated organic facies, rear cross silica gel funnel [3,6-(9-phenyl carbazole bases)] double; two (10H-phenothiazine-5, the 5-dioxide) 10.47mmol that obtains 10,10'-, productivity is 74.79%.Mass spectrum: value of calculation is 701.81；Test value is 701.79.Elementary analysis: value of calculation is C:71.88；H:3.88；N:5.99；O:9.12；S:9.14；Test value is C:71.86；H:3.86；N:5.98；O:9.15；S:9.16.
Contrast test:
Hereinafter, the OLED material of present invention synthesis application effect on device is described in detail by Application Example and comparative example.
Application Example 1(blue-fluorescence device):
Thickness to the transparent electrode layer 2(transparent electrode layer 2 with transparent substrate layer 1 is 220nm) carry out photoetching and etching, form the figure of the transparent electrode layer 2 of the rule needed, immediately above-mentioned glass transparent substrate layer 1 is washed, be namely sequentially carried out neutralizing treatment, pure water, after drying carry out the ultraviolet-ozone washing organic residue to remove transparent electrode layer 2 surface again.
On the anode of the transparent substrate layer 1 carried out after above-mentioned washing, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum are about 5.0x10 to utilize vacuum deposition apparatus-5Pa), the compound shown in evaporation following formula (1) is the layer of 60nm as the NPB of hole mobile material, making thickness, and this layer is hole injection layer 3.
On hole injection layer 4, by vacuum deposition apparatus, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum is about 5.0x10-5Pa), being deposited with one layer of following formula (2), its thin film thickness is 10nm, and this layer of organic material uses as the hole transmission layer 4 of luminescent device.
Then on above-mentioned hole transmission layer 4, the MAND as Blue-light emitting host material shown in following formula, i.e. compound shown in formula (3), adulterate with the DSA-Ph ［ i.e. compound shown in structural formula (4) ］ as blue light dopant material and steam altogether, the weight ratio that doping content is 5% of DSA-Ph doping MAND, its thickness is 25nm.This layer of organic material uses as the luminescent layer 5 of device.
On above-mentioned luminescent layer, by vacuum deposition apparatus (Mo crucible, evaporation rate 0.1nm/s, vacuum 5.0 × 10-5Pa), double; two phenothiazine dioxide of preparation in the evaporation embodiment of the present invention 1, make the electron transfer layer 6 that thickness is 30nm.
On electron transfer layer 6, by vacuum deposition apparatus (Mo crucible, evaporation rate 0.1nm/s, vacuum about 5.0 × 10-5Pa), making lithium fluoride (LiF) layer that thickness is 1nm, this layer is electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus (BN crucible, evaporation rate 0.1nm/s, vacuum about 5.0 × 10-5Pa), making aluminum (Al) layer that thickness is 150nm, this layer is that reflection electrode layer 8 uses.
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, measure the luminous efficiency of device, the I-E characteristic of luminescent spectrum and device.The measurement of the above-mentioned device characteristics of luminescence is to utilize briliancy determinator (Co., Ltd.'s TOPCON system, trade name BM7) to carry out.
Application Example 2(green phosphorescent device)
The present embodiment difference from Example 1 is in that: the luminescent layer 5 of OLED luminescent device adopts phosphor material to arrange in pairs or groups, and the concrete Subjective and Objective material structure used is as follows.The used material structure doping ratio of OLED luminescent layer 5 is: CBP material 30% weight ratio shown in structural formula (5), TPBi material 63% weight ratio shown in doped structure formula (6), Ir(ppy shown in doped structure formula (7))3Material 7% weight ratio.
In order to verify and compare the characteristic of compound of the present invention, the OLED material that known OLED material substitutes the present invention is used to carry out device checking.The OLED structure that comparative example 1 adopts is identical with the device architecture of embodiment 4.
The making of comparative example 1(blue-fluorescence OLED luminescent device)
Comparative example 1 and Application Example 1 institute the difference is that, hole transmission layer 4 material of OLED luminescent device compound shown in embodiment 1 changes the hole mobile material TCTA of following structural formula (8) into.
The making of comparative example 2(green phosphorescent OLED luminescent device)
Comparative example 1 and Application Example 2 institute the difference is that, hole transmission layer 4 material of OLED luminescent device compound shown in embodiment 1 changes the hole mobile material TCTA of structure above (8) into.
The luminosity of gained compound and comparative sample in table 1 embodiment 1-6
Be can be seen that by the result of table 1, no matter OLED material of the present invention is at blue-fluorescence OLED luminescent device, or in green phosphorescent OLED luminescent device, all embody good performance, when in embodiment 1, material described in compound 001 uses as OLED luminescent device electron transfer layer 6, it is no matter efficiency or the life-span that drives that the life-span all obtains bigger change, particularly device than known OLED material obtains bigger lifting.Apply simultaneously to green OLED phosphorescent devices that the contrast traditional material of device in the embodiment 2 of phosphorescent OLED luminescent device makes and be no matter efficiency or the life-span all obtains lifting by a relatively large margin.
Should being used for from the data above seeing, of the present invention pair of phenothiazine dioxide class organic electroluminescent compounds has good application effect in OLED luminescent device, has good industrialization prospect.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (5)
1. a double; two phenothiazine dioxide derivative, it is characterised in that phenothiazine dioxide substituent group, general structure is as follows:
Formula I
In formula I, it is the aryl of 10-20, heterocyclic radical that R represents substituted or unsubstituted carbon number.
2. the electroluminescent material containing double; two phenothiazine dioxide derivatives according to claim 1, it is characterised in that described is the one in the compound 001 ~ 006 shown in following structural formula containing double; two phenothiazine dioxide derivatives:
。
3. the preparation method containing double; two phenothiazine dioxide, comprises the steps:
Step S1: add phenothiazine, two bromo-derivatives of different substituents, sodium tert-butoxide, three (dibenzalacetone) two palladium toluene, tri-butyl phosphine in the reaction vessel after degassed, fully obtains double; two phenothiazine compounds of flaxen different substituents after reaction；
Step S2: double; two phenothiazines of different substituents are added metachloroperbenzoic acid, ice bath reacts, and obtains double; two phenothiazine dioxide derivatives of different substituents.
4. the organic luminescent device that a described pair of phenothiazine dioxide derivative is made, it includes the first electrode, the second electrode and is placed in the one or more organic compound layers between described first electrode, described second electrode, it is characterized in that, at least one described organic compound layer comprises described pair of phenothiazine dioxide derivative.
5. the application of a described pair of phenothiazine dioxide derivative, it is characterised in that described pair of phenothiazine dioxide derivative is used as blue-fluorescence electron transport material or green phosphorescent electron transport material in described organic electroluminescence device.
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