CN108250214A - Oxa- spiro fluorene triphenylamine derivative, preparation method and its usage - Google Patents

Oxa- spiro fluorene triphenylamine derivative, preparation method and its usage Download PDF

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CN108250214A
CN108250214A CN201810004552.8A CN201810004552A CN108250214A CN 108250214 A CN108250214 A CN 108250214A CN 201810004552 A CN201810004552 A CN 201810004552A CN 108250214 A CN108250214 A CN 108250214A
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oxa
hole
spiro fluorene
dried
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CN108250214B (en
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廖良生
蒋佐权
王亚坤
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Suzhou Jiuxian New Material Co ltd
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Suzhou University
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    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract

The invention discloses a kind of oxa- spiro fluorene triphenylamine derivative, preparation method and its usage, oxa- ring spiro fluorene triphenylamine derivative of the invention has the poor singlet triplet of very little and thermal stability and hole transporting property.By efficiently controlling the rigidity of material of main part structure, conjugated degree and electrophilic intensity, the singlet triplet difference of material is allow accurately to regulate and control to be allowed to reduce, and significantly reduce the cut-in voltage of device.Also, the material in the present invention has excellent resonant energy transfer performance.Compared with common phosphorescent light body material, device performance and efficiency roll-off have obtained the raising of matter.In addition to this, in very low object concentration（0.5 wt%）Under doping condition, power efficiency still can reach the peak efficiency based on such material（58 every watt of lumens）.This result is to play the role of directiveness using reduction concentration to reduce the cost of manufacture of Phosphorescent light emitting diode.

Description

Oxa- spiro fluorene triphenylamine derivative, preparation method and its usage
Technical field
The invention belongs to organic photoelectrical material technical fields, and in particular to prepared by a kind of oxa- spiro fluorene triphenylamine derivative Method and application thereof.
Background technology
Organic electroluminescent is a kind of selfluminous element, by clipping luminescent layer between a pair of electrodes and applying voltage, from Cathode (first electrode) injected electrons and anode (second electrode) injected holes are compounded to form molecular exciton in the centre of luminescence, And the molecular exciton releases energy to shine when returning to ground state.Organic electroluminescence device is with voltage is low, brightness is high, color The characteristics such as purity is good, visual angle is wide, response is fast, thermal adaptability is good are widely used in the production of the electronics such as computer, mobile phone, MP3, TV Product display.Electroluminescent organic material is generally divided into singlet fluorescent dye and triplet state phosphorescent coloring, wherein due to single line State fluorescence can only utilize 25% exciton due to transition speed, and remaining 75% exciton all passes through the form or other of heat Radiationless mode is lost, and triplet state phosphorescence shines since heavy atoms effect can utilize 100% exciton, makes luminous efficiency remote Stronger concentration quenching effect is had at high concentrations far more than singlet fluorescence radiation but triplet emitter, can be dropped The luminous efficiency of low luminescent layer causes organic luminescent device performance relatively low.Therefore, in present organic electroluminescence device mostly Using host-guest system structure, i.e., fluorescent dye or phosphorescent coloring are dispersed in certain concentration in main substance, to avoid Concentration quenching and triplet-triplet are buried in oblivion, and improve device performance.
In RGB (R-G-B) colour system, red OLEDs is by especially more concerns.This is mostly derived from optics, red Color has longest wavelength in the spectrum of visible ray, it means that the scattering of light is minimum, therefore can be from than its allochromatic colour The distance of bigger is adjusted to see.In addition, red can improve our feeling of risk, therefore be widely used as eye-catching warning mark. For example, the automaker as Audi and BMW, which has announced it, uses red OLED as the light-duty technology of taillight Plan.In addition to this, because organic material can be deposited or printed on the 3-D substrates with any shape, there is no need to carry on the back Optical drive, and radiate in the process almost without work.Although with good prospect, organic phosphorescent devices are usual High object doping concentration is needed to realize the requirement of high brightness.And high concentration then necessarily causes the cost of organic phosphorescent devices to increase Add.Therefore the cost that any realization high brightness efficiency reduces device simultaneously is still a stubborn problem.
Invention content
The object of the present invention is to provide a kind of new material, (singlet-triplet state difference is small, and resonant energy transfer is effective Deng), it makes it possible under low object doping concentration still normal use or realizes higher effect under low object doping concentration Rate.To solve the problems, such as to reduce organic phosphorescent devices cost.
To achieve the above object, the present invention provides following technical solution：
A kind of oxa- spiro fluorene triphenylamine derivative has the chemical constitution shown in formula (I)：
Wherein, main body is oxa- spiro fluorene triphenylamine, and substituent R 1-R8 is independently selected from hydrogen, cyano, two (trimethylbenzenes Base) boron fluoride, 2- azepines pyridine, 3- azepines pyridine, 2,4- diphenyl -1,3,5-triazines.
Preferably, the oxa- spiro fluorene triphenylamine derivative includes the derivative of following formula II-Ⅸ：
(1) substituent R 2 is cyano, and R1, R3-R8 substituent group are hydrogen, are named as OSTFP1, structural formula such as formula (II)
It is shown：
(2) substituent R 2 is two (trimethylphenyl) boron fluorides, and R1, R3-R8 substituent group are hydrogen, are named as OSTFP2, are tied Shown in structure such as formula (III)：
(3) substituent R 3 is 2- azepine pyridines, and R1-R2, R4-R8 substituent group are hydrogen, are named as OSTFP3, structural formula is such as Shown in formula (IV)
(4) substituent R 5 is 3- azepine pyridines, and R1-R4, R6-R8 substituent group are hydrogen, are named as OSTFP4, structural formula is such as Shown in formula (V)：
(5) substituent R 8 is 2,4- diphenyl -1,3,5-triazines, and R1-R7 substituent groups are hydrogen, are named as OSTFP5, are tied Shown in structure formula such as formula (VI)：
(6) substituent R 2 is cyano, and R6 is 2- azepine pyridines, and R1-R3, R5, R7-R8 substituent group are hydrogen, are named as OSTFP6, shown in structural formula such as formula (VII)：
(7) substituent R 2 is cyano, and R4 is 3- azepine pyridines, and R2-R3, R5-R8 substituent group are hydrogen, are named as OSTFP7, Shown in its structural formula such as formula (VIII)：
(8) substituent R 3 is 3- azepine pyridines, and R7 is cyano, and R1-R2, R4-R6, R8 substituent group are hydrogen, are named as OSTFP8, shown in structural formula such as formula (Ⅸ)：
Purposes of the oxa- spiro fluorene triphenylamine derivative of the present invention in organic electroluminescence red phosphorescent device.
The present invention also provides a kind of organic electroluminescence comprising the oxa- ring spiro fluorene triphenylamine derivative material of main part is red Color phosphorescent devices, including glass, the Conducting Glass layer being attached on glass, the hole note being bonded with Conducting Glass layer Enter layer, the hole transmission layer being bonded with hole injection layer, the luminescent layer being bonded with hole transmission layer, the hole being bonded with luminescent layer Barrier layer, the electron transfer layer being bonded with hole blocking layer, the cathode layer being bonded with electron transfer layer, the luminescent layer is by leading Body material and guest materials composition, the material of main part be formula (I) described structure derivative, the guest materials be with The complex of iridium of cyclic metal complexes.
Preferably, the complex of iridium is that the acetylacetone,2,4-pentanedione to glow bis- (2- methyldiphenyls simultaneously [F, H] quinoxaline) closes Iridium (Ir (MDQ)2(acac))。
Further, the doping concentration of the guest materials is not higher than 2.0wt%.
A kind of preparation method of organic electroluminescence red phosphorescent device of the present invention, includes the following steps：
(1) transparent electro-conductive glass substrate is pre-processed；
(2) the vacuum evaporation hole injection layer on ITO electro-conductive glass；
(3) vacuum evaporation hole transmission layer and electronic barrier layer on hole injection layer；
(4) process being deposited using double source is made with the oxa- spiro fluorene triphenylamine derivative described in claims 1 or 2 Based on material, there is organic luminous layer of the complexes of red light iridium as guest materials of cyclic metal complexes, in organic luminous layer On vacuum evaporation hole blocking layer and electron transfer layer；
(5) vacuum evaporation cathode layer on the electron transport layer.
Further, the hole injection layer be molybdenum trioxide or 2,3,6,7,10,11- six cyano-Isosorbide-5-Nitrae, 5,8,9,12- Six azepine triphenylenes, the hole transmission layer be N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines, 4, 4-N, the N carbazyl of '-two biphenyl or 1,1 '-two 4,4 '-dimethyltrianiline thiacyclohexane；The electron transfer layer is 1,3,5. 3 (N- phenyl -2- benzimidazolyl-2 radicals) benzene, 4,7- diphenyl -1,10- phenanthrolenes or bis- (3,5- bis- (4- pyridines) the base benzene of 4,6- Base) -2- methylpyrimidines；The cathode layer is Liq and Al.
Further, the evaporation rate of the hole injection layer isThe hole transmission layer and electronic blocking Layer evaporation rate beThe evaporation rate of the organic luminous layer isThe hole blocking layer and electronics pass The evaporation rate of defeated layer is
Further, the coating film thickness of the hole injection layer is 1-50nm；The hole transmission layer and electronic barrier layer Coating film thickness be 10-80nm；The coating film thickness of the organic luminous layer is 5-50nm；The hole blocking layer and electron-transport The coating film thickness of layer is 10-80nm；The Liq layer thickness is 1-5nm, and the Al layer thickness is 50-200nm.
Advantageous effect：The present invention provides a kind of oxa- spiro fluorene triphenylamine derivative, preparation method and its usage, the present invention Oxa- spiro fluorene triphenylamine derivative be applied to organic electroluminescence red phosphorescent device in, efficient electroluminescent properties can be obtained. The present invention is with Ir (MDQ)2(acac) the organic electroluminescence red phosphorescent device prepared for guest materials, maximum brightness efficiency are reachable 63.6 every watt of lumens.Meanwhile when object concentration is down to 0.5wt%, the material of main part based on the present invention can still realize 58 lumens Every watt of efficiency.This efficiency is not only the peak efficiency based on this object, and is real under such low object doping concentration It is existing.In addition to this, the cut-in voltage minimum of device can be down to 2.1V.Device performance based on material of main part of the present invention with it is similar its The property of its device is compared, and is obtained for qualitative leap, to reduce Phosphorescent cost in the future and realizing that its commercialization is established Important basis.The present invention improves rigidity by being inserted into an oxygen atom in spiro fluorene triphenylamine, reduces the single line of skeleton State energy, meanwhile, by the electron-withdrawing ability size of control introducing group, the conjugated degree of material increases compound and effectively divides Son amount, makes singlet-triplet difference of material greatly reduce.The material of the present invention also shows good resonance energy simultaneously Amount transfer and stability.
Description of the drawings
Fig. 1 is main body prepared by the embodiment of the present invention 1 and the UV-visible absorption spectrum of guest materials and main body material The fluorescence spectra of material.
Fig. 2 is the transient state spectrogram of material of main part prepared by the embodiment of the present invention 1；(a) film and solution for being OSTFP2 Under (embedded) transient state fluorescence spectrum；(b) the transient state fluorescence spectrum for (embedded) under the film and solution of OSTFP1.
Fig. 3 is the EL device structure schematic diagram of the present invention, wherein 1 is substrate；2 be hole injection layer (HIL)；3 For hole transmission layer (HTL)；4 be electronic barrier layer (EBL)；5 be organic luminous layer (EML)；6 be hole blocking layer (HBL)；7 For electron transfer layer (ETL)；8 be electron injecting layer (EIL)；9 be cathode.
Fig. 4 is the launching light spectrogram of the electroluminescent device of the present invention；(a) electricity during main body is done for OSTFP1 and OSTFP2 Photoluminescence spectrogram；(b) for CBP main body is done and electroluminescent light spectrogram when B4PyMPM does electron transfer layer；(c) it is done for CBP Main body and TPBI do electroluminescent light spectrogram during electron transfer layer.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, detailed retouch is carried out to the technical solution in the embodiment of the present invention It states, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention Embodiment, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made Example, shall fall within the protection scope of the present invention.
Embodiment 1
Step 1：4.23 grams of adjacent bromo-iodobenzenes are dissolved in 80mL o-dichlorohenzenes, and sequentially add phenoxazine under protection of argon gas 1.83 grams of piperazine, 0.7 gram of cuprous iodide, 5.0 grams of 18 0.1 gram of 6 ethers of hat and potassium carbonate are in 200 milliliters of reaction bulb.In argon gas After the lower reflux of protection 48 hours, reaction solution is cooled to room temperature.Solvent is by Rotary Evaporators except dry.Reaction solid is dissolved in 80mL bis- In chloromethanes, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.It adds in silica gel and is spin-dried for gained Solid dichloromethane/petroleum ether=3:7 (volume ratios) cross column, are spin-dried for obtaining 3.04 grams of 2- bromine oxa- triphenylamines, yield 90%.Step Rapid two：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, it will 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then 1.3 grams of 2- bromine Fluorenones are existed It is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under argon gas protection.After low-temp reaction 1 hour, room temperature is gradually increased to, instead After answering 12 hours, 5mL water is added in reaction, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL dichloromethane, With 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.It will be spin-dried for obtained solid and be dissolved in 45mL ice vinegar In acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.The solid of gained is used Dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 2.1 grams of 2- bromine oxa- ring spiro fluorene triphenylamines, yield 84%.
Step 3：By 2.0 grams of 2- bromine oxa- spiro fluorene triphenylamines, 0.4 gram of cuprous cyanide is placed on added with 50 milliliters of N-methyl pyrroles In the 100ml double-neck flasks of pyrrolidone.After 180 degree is reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 water, separation has Machine layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, are spin-dried for 1.34 grams of OSTFP1, yield 75%.
Embodiment 2
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：2.0 grams of 2- bromine oxa- spiro fluorene triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled down To -78 DEG C, 2.0mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.1 gram two (trimethylphenyl) boron fluoride is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.Low-temp reaction 2 hours Afterwards, room temperature is gradually increased to, after reacting 12 hours, 5mL water is added in reaction, is then spin-dried for solvent by decompression.Solid It is dissolved in 80mL dichloromethane, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.Use dichloromethane Alkane/petroleum ether=7:3 (volume ratios) cross column, are spin-dried for obtaining 1.95 grams of OSTFP2, yield 73%.
Embodiment 3
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.3 grams of 3- bromine fluorenes Ketone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, it is gradually increased to room After reacting 12 hours, 5mL water is added in reaction for temperature, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL dichloromethanes In alkane, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.It will be spin-dried for obtained solid and be dissolved in 45mL In glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained is consolidated Body dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 1.8 grams of 3- bromine oxa- ring spiro fluorene triphenylamines, yield 72%.
Step 3：By 2.0 grams of 3- bromine oxa- spiro fluorene triphenylamines, 0.6 gram of 2- azepine pyridine boronic acid is placed on 60/5ml dioxies six In the 100ml double-neck flasks of ring/water.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 dichloromethane, point From organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, are spin-dried for Obtain 1.7 grams of OSTFP3, yield 68%.
Embodiment 4
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.3 grams of 4- bromine fluorenes Ketone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, it is gradually increased to room After reacting 12 hours, 5mL water is added in reaction for temperature, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL dichloromethanes In alkane, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.It will be spin-dried for obtained solid and be dissolved in 45mL In glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained is consolidated Body dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 1.7 grams of 4- bromine oxa- ring spiro fluorene triphenylamines, yield 70%.
Step 4：By 2.0 grams of 4- bromine oxa- spiro fluorene triphenylamines, 0.6 gram of 2- azepine pyridine boronic acid is placed on 60/5ml dioxies six In the 100ml double-neck flasks of ring/water.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 dichloromethane, point From organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, are spin-dried for Obtain 1.6 grams of OSTFP4, yield 66%.
Embodiment 5
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.3 grams of 1- bromine fluorenes Ketone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, it is gradually increased to room After reacting 12 hours, 5mL water is added in reaction for temperature, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL dichloromethanes In alkane, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.It will be spin-dried for obtained solid and be dissolved in 45mL In glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained is consolidated Body dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 1.7 grams of 1- bromine oxa- ring spiro fluorene triphenylamines, yield 70%.
Step 4：By 2.0 grams of 1- bromine oxa- spiro fluorene triphenylamines, 1.3 grams of 2,4- diphenyl -1,3,5-triazines boric acid are placed on In the 100ml double-neck flasks of 60/5ml dioxane/water.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.With 4 × 50 2 Chloromethanes extracts, and detaches organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (bodies Product ratio) column is crossed, it is spin-dried for obtaining 2.34 grams of OSTFP5, yield 73%.
Embodiment 6
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.84 grams of 2,6- Dibromo fluorenone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, gradually rise To room temperature, after reacting 12 hours, 5mL water is added in reaction, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL bis- In chloromethanes, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.Obtained solid will be spin-dried for be dissolved in In 45mL glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained Solid dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 2.0 grams of 2,6- dibromo oxa- ring spiro fluorene triphenylamines, Yield 69%.
Step 4：By 1.5 grams of 2,6- dibromo oxa- spiro fluorene triphenylamines, 0.4 gram of cuprous cyanide is placed on added with 50 milliliters of n-formyl sarcolysine In the 100ml double-neck flasks of base pyrrolidones.After 180 degree is reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 water, point From organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, obtain 1.2 grams of intermediates, yield 89%.
Step 5：By 1.2 grams of above-mentioned intermediates, 0.3 gram of 2- azepine pyridine boronic acid is placed on 60/5ml dioxane/water In 100ml double-neck flasks.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 dichloromethane, separation is organic Layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, be spin-dried for 0.86 Gram OSTFP6, yield 72%.
Embodiment 7
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.84 grams of 2,4- Dibromo fluorenone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, gradually rise To room temperature, after reacting 12 hours, 5mL water is added in reaction, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL bis- In chloromethanes, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.Obtained solid will be spin-dried for be dissolved in In 45mL glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained Solid dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 2.2 grams of 2,4- dibromo oxa- ring spiro fluorene triphenylamines, Yield 73%.
Step 4：By 1.5 grams of 2,6- dibromo oxa- spiro fluorene triphenylamines, 0.4 gram of cuprous cyanide is placed on added with 50 milliliters of n-formyl sarcolysine In the 100ml double-neck flasks of base pyrrolidones.After 180 degree is reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 water, point From organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, obtain 1.3 grams of intermediates, yield 90%.
Step 5：By 1.2 grams of above-mentioned intermediates, 0.3 gram of 2- azepine pyridine boronic acid is placed on 60/5ml dioxane/water In 100ml double-neck flasks.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 dichloromethane, separation is organic Layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, be spin-dried for 0.90 Gram OSTFP7, yield 75%.
Embodiment 8
Step 1：It is same as 1 step 1 of embodiment.
Step 2：It is same as 1 step 2 of embodiment.
Step 3：1.52 grams of 2- bromine oxa- triphenylamines are dissolved under protection of argon gas in 80mL tetrahydrofurans, are cooled to -78 DEG C, 2.38mL n-BuLis are slowly added to by constant pressure funnel in solution, are reacted 1 hour.Then by 1.84 gram 3,7- Dibromo fluorenone is dissolved in 40mL tetrahydrofurans and is added drop-wise in reaction solution under protection of argon gas.After low-temp reaction 1 hour, gradually rise To room temperature, after reacting 12 hours, 5mL water is added in reaction, is then spin-dried for solvent by decompression.Solid is dissolved in 80mL bis- In chloromethanes, with 50mL washings organic layer three times.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate.Obtained solid will be spin-dried for be dissolved in In 45mL glacial acetic acid and 10mL niacin, then 4 hours postcoolings of reflux to room temperature are filtered and are flushed three times with petroleum ether.Gained Solid dichloromethane/petroleum ether=4:6 (volume ratios) cross column, are spin-dried for obtaining 2.2 grams of 3,7- dibromo oxa- ring spiro fluorene triphenylamines, Yield 73%.
Step 4：By 1.5 grams of 3,7- dibromo oxa- spiro fluorene triphenylamines, 0.4 gram of cuprous cyanide is placed on added with 50 milliliters of n-formyl sarcolysine In the 100ml double-neck flasks of base pyrrolidones.After 180 degree is reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 water, point From organic layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, obtain 1.2 grams of intermediates, yield 88%.
Step 5：By 1.2 grams of above-mentioned intermediates, 0.3 gram of 3- azepine pyridine boronic acid is placed on 60/5ml dioxane/water In 100ml double-neck flasks.After 90 degree are reacted 24 hours, it is gradually cooling to room temperature.It is extracted with 4 × 50 dichloromethane, separation is organic Layer.Organic layer is spin-dried for after being dried with anhydrous sodium sulfate, with dichloromethane/petroleum ether=7:3 (volume ratios) cross column, be spin-dried for 0.85 Gram OSTFP8, yield 70%.
Here is the Application Example of the compounds of this invention：
Prepare the preferred embodiment of device：
As shown in figure 3, the typical structure of OLED device is：1/ anode of substrate/hole injection layer (HIL), 2/ hole transmission layer (HTL) 3/ electronic barrier layer (EBL), 4/ organic luminous layer (EML), 5/ hole blocking layer (HBL), 6/ electron transfer layer (ETL), 7/ electricity Sub- 8/ cathode 9 of implanted layer (EIL).
Substrate uses transparent conducting glass substrate, and molybdenum trioxide (MoO may be used in hole injection layer3) or 2,3,6, N, N'- hexichol may be used in 7,10,11- six cyano-Isosorbide-5-Nitrae, 5,8,9,12- six azepine triphenylenes (HAT-CN), hole transmission layer Base-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines (NPB),-two carbazyl biphenyl (CBP) of 4,4-N, N ' or 1,1 '-two 4,1,3,5. three (N- phenyl -2- benzimidazolyl-2 radicals) may be used in 4 '-dimethyltrianiline thiacyclohexane (TAPC), electron transfer layer Benzene (TPBi), 4,7- diphenyl -1,10- phenanthrolenes (Bphen) or bis- (3,5- bis- (4- pyridines) base the phenyl) -2- first of 4,6- Yl pyrimidines (B4PyMPM).Device architecture can be that single-shot photosphere can also be multi-luminescent layer, and it can be that single doping is tied that every layer, which shines, Structure may be more doped structures.Feux rouges object closes iridium (Ir for (acetylacetone,2,4-pentanedione) bis- (2- methyldiphenyls simultaneously [f, h] quinoxaline) (MDQ)2(acac)).In order to verify that guest materials of the present invention can work normally at low concentrations, object concentration highest is set as 2.0wt% is reduced to 1.0wt% and 0.5wt% in gradient.
Embodiment 9
Compound OSTFP1 using the present invention is as OLED device material of main part, 2.0wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac) (20nm, 2.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm).
Device fabrication process is as follows：Transparent electro-conductive glass substrate is ultrasonically treated in commercial detergent, in deionization It rinses in water, is cleaned repeatedly three times with deionized water, acetone, ethyl alcohol, be baked to moisture of going out completely under a clean environment, use Ultraviolet lamp and ozone treatment ITO electro-conductive glass.Processed ITO electro-conductive glass is placed in vacuum chamber, it is evacuated to 3.0 × 10-4-4.0×10-4Pa, vacuum evaporation HAT-CN is as hole injection layer (HIL), evaporation rate on ITO electro-conductive glassCoating film thickness is 10nm；Vacuum evaporation TAPC is hindered as hole transmission layer (HTL) and electronics on hole injection layer Barrier (EBL), evaporation rate areCoating film thickness is 45nm；Then using the process of double source vapor deposition, with the present inventionization Material based on conjunction object OSTFP1, using Ir (MDQ)2(acac) as the first organic luminous layer (EML) of dyestuff, control vapor deposition Rate isCoating film thickness is 20nm, Ir (MDQ)2(acac) doping concentration is 2.0wt%.It is true on organic luminous layer One layer of B4PyMPM is deposited in skyPlating Film thickness is 45nm；It is used as device cathodes for vacuum evaporation Liq and Al layers on the electron transport layer, the Liq layer thickness is 2nm, The Al layer thickness is 120nm.
Embodiment 10
Compound OSTFP1 using the present invention is as OLED device material of main part, 1.0wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac)(20nm, 1.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 11
Compound OSTFP1 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 12
Compound OSTFP2 using the present invention is as OLED device material of main part, 2.0wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac)(20nm, 2.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 13
Compound OSTFP2 using the present invention is as OLED device material of main part, 1.0wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac)(20nm, 1.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 14
Compound OSTFP2 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 15
Compound OSTFP3 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP3:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 16
Compound OSTFP4 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP4:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 17
Compound OSTFP5 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP5:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 18
Compound OSTFP6 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP6:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 19
Compound OSTFP7 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP7:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Embodiment 20
Compound OSTFP8 using the present invention is as OLED device material of main part, 0.5wt%Ir (MDQ)2(acac) it is Red phosphorescent dye, device architecture are：
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP8:Ir(MDQ)2(acac)(20nm, 0.5wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm), device fabrication process is the same as embodiment 9.
Comparative example 1
Using (9- carbazoles) biphenyl of 4,4'- bis- (CBP) as OLED device material of main part, Ir (MDQ)2(acac) it is red Phosphorescent coloring, device architecture are：ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/CBP:Ir(MDQ)2(acac) (20nm,
2.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm).
Device fabrication process is as follows：Transparent electro-conductive glass substrate is ultrasonically treated in commercial detergent, in deionization It rinses in water, is cleaned repeatedly three times with deionized water, acetone, ethyl alcohol, be baked to moisture of going out completely under a clean environment, use Ultraviolet lamp and ozone treatment ITO electro-conductive glass.Processed ITO electro-conductive glass is placed in vacuum chamber, it is evacuated to 3.0 × 10-4~4.0 × 10-4Pa, vacuum evaporation HAT-CN is as hole injection layer (HIL), evaporation rate on ITO electro-conductive glassCoating film thickness is 10nm；Vacuum evaporation TAPC is hindered as hole transmission layer (HTL) and electronics on hole injection layer Barrier (EBL), evaporation rate areCoating film thickness is 45nm；Then using the process of double source vapor deposition, based on CBP Material, using Ir (MDQ)2(acac) as the organic luminous layer of dyestuff (EML), control evaporation rate isCoating film thickness is 20nm, Ir (MDQ)2(acac) doping concentration is 2.0wt%；One layer of B4PyMPM of vacuum evaporation makees on organic luminous layer Hole blocking layer (HBL) and electron transfer layer (ETL), evaporation rate for device areCoating film thickness is 45nm；In electronics As device cathodes, the Liq layer thickness is 2nm for Liq and Al layers of vacuum evaporation in transport layer, and the Al layer thickness is 120nm.
Comparative example 2
Using (9- carbazoles) biphenyl of 4,4'- bis- (CBP) as OLED device material of main part, Ir (MDQ)2(acac) it is red Phosphorescent coloring, device architecture are：ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/CBP:Ir(MDQ)2(acac) (20nm,
2.0wt% doping concentrations)/TPBI (45nm)/Liq (2nm)/Al (120nm).
Device fabrication process is as follows：Transparent electro-conductive glass substrate is ultrasonically treated in commercial detergent, in deionization It rinses in water, is cleaned repeatedly three times with deionized water, acetone, ethyl alcohol, be baked to moisture of going out completely under a clean environment, use Ultraviolet lamp and ozone treatment ITO electro-conductive glass.Processed ITO electro-conductive glass is placed in vacuum chamber, it is evacuated to 3.0 × 10-4~4.0 × 10-4Pa, vacuum evaporation HAT-CN is as hole injection layer (HIL), evaporation rate on ITO electro-conductive glassCoating film thickness is 10nm；Vacuum evaporation TAPC is hindered as hole transmission layer (HTL) and electronics on hole injection layer Barrier (EBL), evaporation rate areCoating film thickness is 45nm；Then using the process of double source vapor deposition, based on CBP Material, using Ir (MDQ)2(acac) as the organic luminous layer of dyestuff (EML), control evaporation rate isCoating film thickness is 20nm, Ir (MDQ)2(acac) doping concentration is 2.0wt%；One layer of TPBI of vacuum evaporation is as device on organic luminous layer The hole blocking layer (HBL) and electron transfer layer (ETL), evaporation rate of part beCoating film thickness is 45nm；In electron-transport As device cathodes, the Liq layer thickness is 2nm for Liq and Al layers of vacuum evaporation on layer, and the Al layer thickness is 120nm.
Comparative example 3
Using oxa- spiro fluorene triphenylamine (OSTFP) as OLED device material of main part, Ir (MDQ)2(acac) it is red phosphorus Photoinitiator dye, device architecture are：ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP:Ir(MDQ)2(acac) (20nm,
2.0wt% doping concentrations)/B4PyMPM (45nm)/Liq (2nm)/Al (120nm).
Device fabrication process is the same as embodiment 9.
The device architecture of embodiment 9-20 and comparative example 1-3 are shown in Table 1：
Table 1
Current versus brightness-voltage characteristic of device is measured by carrying the Keithley sources of corrected silicon photoelectric diode What system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) was completed, electroluminescent spectrum It is by Photo research companies PR655 spectrometer measurements, all measurements are completed in atmosphere at room temperature.
The device data of embodiment 9-20 and comparative example 1-3 are shown in Table 2：
Table 2
By above-mentioned 9-20 devices effect it is found that the material of main part of the present invention is applied in organic electroluminescence red phosphorescent device, Efficient electroluminescent properties can be obtained.Based on material of the present invention during material (embodiment 11), based on Ir (MDQ)2(acac Organic electroluminescence red phosphorescent device, maximum brightness efficiency is up to 63.6 every watt of lumens.Meanwhile object concentration down to During 0.5wt% (embodiment 12), the material of main part based on the present invention can still realize the efficiency of 58 every watt of lumens.This efficiency is not only It is the peak efficiency based on this object, and is realized under such low object doping concentration.And for 1 device of comparative example, Under this concentration, the peak (Fig. 4 b) of exciplex is produced.Even if when concentration increases to 2.0wt%, it still can be observed and swashs The peak of base complex.Therefore, B4PyMPM transport layers are replaced TPBI to avoid such influence by us.From device effect it is found that i.e. When making a concentration of 2.0wt% of object, the Resonance energy transfer of convention body material is still apparent insufficient (Fig. 4 c), and efficiency is remote Far below the material of main part of the present invention.In addition to this, the cut-in voltage minimum of device can be down to 2.1V.With unsubstituted oxaspiro Fluorenes triphenylamine (OSTFP) is as OLED device material of main part (comparative example 3), and the performance of prepared device is still well below implementation Device prepared by example 9-20.Device performance based on material of main part of the present invention all obtains compared with the property of similar other devices Qualitative leap, to reduce Phosphorescent cost in the future and realizing that important basis has been established in its commercialization.
Meanwhile compared with Chinese patent CN104892578A fluorenes spiral shell triphenylamine derivatives with having disclosed and application thereof, this The material of main part of invention has smaller singlet-triplet.It, on the one hand can be with by going out to be inserted into oxygen atom in triphenylamine Improve the rigidity of material, on the other hand can enhance the electron donation of triphen amine moiety, so as to reduce its singlet energy level and Singlet-triplet is poor.For technical result, the latter shows the advantage become apparent.With documents fluorenes spiral shell three Bis- (4,6- difluorophenyl pyridinatos-N, the C2') pyridinecarboxylics of blue light in anil and application thereof (CN104892578A) close Iridium (FIrpic) is compared, and the present invention is using the Ir (MDQ) 2 (acac) with red emission.Meanwhile even if documents exist The peak power efficiency that (15wt%) is obtained under the conditions of high doping concentration also only has 36 every watt of lumens, is well below the present invention Make 58 every watt of the lumens obtained under very low concentrations (0.5wt%).Meanwhile file of the present invention is aimed to solve the problem that and is remained at low concentrations High efficiency is obtained, and documents are referred to without any.Technical result based on solution problem content difference and present invention protrusion, Thus file of the present invention has better advantage compared with documents.
In conclusion the present invention improves rigidity by being inserted into an oxygen atom in spiro fluorene triphenylamine, skeleton is reduced Singlet energy, meanwhile, the electron-withdrawing ability size of group is introduced by control, the conjugated degree of material, increasing compound has Molecular weight is imitated, makes singlet-triplet difference of material greatly reduce.The material of the present invention is also shown well altogether simultaneously Energy transfer of shaking and stability.
Therefore, in all respects, the present embodiments are to be considered as illustrative and not restrictive, this The range of invention is indicated by the appended claims rather than the foregoing description, it is intended that by falling in the equivalent requirements of the claims All changes in meaning and scope are included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should It considers the specification as a whole, the technical solutions in each embodiment can also be properly combined, forms those skilled in the art The other embodiment being appreciated that.

Claims (10)

1. oxa- spiro fluorene triphenylamine derivative, which is characterized in that there is the chemical constitution shown in formula (I)：
Wherein, main body is oxa- spiro fluorene triphenylamine, and substituent R 1-R8 is independently selected from hydrogen, cyano, two (trimethylphenyl) fluorine Change boron, 2- azepines pyridine, 3- azepines pyridine or 2,4- diphenyl -1,3,5-triazines.
2. oxa- spiro fluorene triphenylamine derivative according to claim 1, which is characterized in that the oxa- spiro fluorene triphenylamine spreads out Biology includes the derivative of following formula II-Ⅸ：
3. any one oxa- spiro fluorene triphenylamine derivative described in claims 1 or 2 is preparing organic electroluminescence red phosphorescent device In purposes.
4. organic electroluminescence red phosphorescent device including glass, the Conducting Glass layer being attached on glass, is served as a contrast with electro-conductive glass The hole injection layer of bottom fitting, the hole transmission layer being bonded with hole injection layer, the luminescent layer being bonded with hole transmission layer, with The hole blocking layer of luminescent layer fitting, the electron transfer layer being bonded with hole blocking layer, the cathode layer being bonded with electron transfer layer, It is characterized in that：The luminescent layer is made of material of main part and guest materials, and the material of main part is claims 1 or 2 The oxa- spiro fluorene triphenylamine derivative, the guest materials are the complexes of red light iridium with cyclic metal complexes.
5. organic electroluminescence red phosphorescent device according to claim 4, it is characterised in that：The complexes of red light iridium is The acetylacetone,2,4-pentanedione that glows bis- (2- methyldiphenyls simultaneously [F, H] quinoxaline) closes iridium.
6. organic electroluminescence red phosphorescent device according to claim 4, it is characterised in that：The doping of the guest materials It is a concentration of to be not higher than 2.0wt%.
It is 7. a kind of as claim 4,5 or the preparation method of 6 any one of them organic electroluminescence red phosphorescent devices, feature exist In including the following steps：
(1) transparent electro-conductive glass substrate is pre-processed；
(2) the vacuum evaporation hole injection layer on ITO electro-conductive glass；
(3) vacuum evaporation hole transmission layer and electronic barrier layer on hole injection layer；
(4) process being deposited using double source, using the oxa- spiro fluorene triphenylamine derivative described in claims 1 or 2 as master Body material has organic luminous layer of the complexes of red light iridium of cyclic metal complexes as guest materials, on organic luminous layer Vacuum evaporation hole blocking layer and electron transfer layer；
(5) vacuum evaporation cathode layer on the electron transport layer.
8. the preparation method of organic electroluminescence red phosphorescent device according to claim 7, which is characterized in that the hole note Enter layer for molybdenum trioxide or 2,3,6,7,10,11- six cyano-Isosorbide-5-Nitrae, 5,8,9,12- six azepine triphenylenes, the hole transmission layer For N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines,-two carbazyl biphenyl of 4,4-N, N ' or 1,1 ' - 2 4,4 '-dimethyltrianiline thiacyclohexane；The electron transfer layer for 1,3,5. 3 (N- phenyl -2- benzimidazolyl-2 radicals) benzene, 4, 7- diphenyl -1,10- phenanthrolenes or bis- (3,5- bis- (4- pyridines) base the phenyl) -2- methylpyrimidines of 4,6-；The cathode layer For Liq and Al.
9. the preparation method of organic electroluminescence red phosphorescent device according to claim 7, which is characterized in that the hole note The evaporation rate for entering layer isThe evaporation rate of the hole transmission layer and electronic barrier layer isIt is described to have The evaporation rate of machine luminescent layer isThe evaporation rate of the hole blocking layer and electron transfer layer is
10. the preparation method of organic electroluminescence red phosphorescent device according to claim 7, which is characterized in that the hole The coating film thickness of implanted layer is 1-50nm；The coating film thickness of the hole transmission layer and electronic barrier layer is 10-80nm；It is described to have The coating film thickness of machine luminescent layer is 5-50nm；The coating film thickness of the hole blocking layer and electron transfer layer is 10-80nm；It is described Liq layer thickness is 1-5nm, and the Al layer thickness is 50-200nm.
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CN110079304A (en) * 2019-05-24 2019-08-02 武汉华星光电半导体显示技术有限公司 A kind of thermal activation delayed fluorescence compound, preparation method and its application
CN111548485A (en) * 2020-06-17 2020-08-18 山西能源学院 Conjugated microporous organic polymer and preparation method and application thereof
CN111620890A (en) * 2020-06-12 2020-09-04 苏州大学 Compound, organic electronic device comprising same, and display device or lighting device
CN113717171A (en) * 2021-09-09 2021-11-30 武汉华星光电半导体显示技术有限公司 Organic compound, preparation method thereof and light-emitting device

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109761822A (en) * 2019-01-23 2019-05-17 苏州久显新材料有限公司 Fluorene kind derivative and electronic device
CN109761822B (en) * 2019-01-23 2021-06-18 苏州久显新材料有限公司 Fluorene derivative and electronic device
CN110079304A (en) * 2019-05-24 2019-08-02 武汉华星光电半导体显示技术有限公司 A kind of thermal activation delayed fluorescence compound, preparation method and its application
CN111620890A (en) * 2020-06-12 2020-09-04 苏州大学 Compound, organic electronic device comprising same, and display device or lighting device
CN111620890B (en) * 2020-06-12 2022-12-06 苏州大学 Compound, organic electronic device including the same, and display device or lighting device
CN111548485A (en) * 2020-06-17 2020-08-18 山西能源学院 Conjugated microporous organic polymer and preparation method and application thereof
CN113717171A (en) * 2021-09-09 2021-11-30 武汉华星光电半导体显示技术有限公司 Organic compound, preparation method thereof and light-emitting device

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