CN107652272A - It is a kind of using ketone structure as the organic compound of parent nucleus and its application in OLED - Google Patents

It is a kind of using ketone structure as the organic compound of parent nucleus and its application in OLED Download PDF

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CN107652272A
CN107652272A CN201710908862.8A CN201710908862A CN107652272A CN 107652272 A CN107652272 A CN 107652272A CN 201710908862 A CN201710908862 A CN 201710908862A CN 107652272 A CN107652272 A CN 107652272A
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organic compound
formula
ketone
compound
key
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蔡啸
张兆超
李崇
唐丹丹
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Valiant Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

There is △ E by the organic compound of parent nucleus and its application in organic electroluminescence device, the compound of structure containing ketone the invention discloses a kind ofst<0.2eV, and 2.7eV<T1<3.0eV characteristic, aromatic heterocycle group is connected, destroys molecular symmetry, so as to the crystallinity of saboteur, avoid intermolecular aggtegation, the film forming having had.It is applied to the compounds of this invention as emitting layer material on Organic Light Emitting Diode, there are good photoelectric properties using the OLED of the compounds of this invention, disclosure satisfy that the requirement of panel manufacturing enterprise.

Description

It is a kind of using ketone structure as the organic compound of parent nucleus and its in OLED Using
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of based on the compound that ketone structure is core, with And its application as emitting layer material on Organic Light Emitting Diode.
Background technology
Organic Light Emitting Diode (OLED:Organic Light Emission Diodes) turn into very popular both at home and abroad Emerging flat-panel monitor product because when OLED display has self-luminous, wide viewing angle (up to more than 175 °), short reaction Between, high-luminous-efficiency, wide colour gamut, low-work voltage (3~10V), panel thin (being smaller than 1mm) and the characteristic such as rollable.OLED It is called star's flat display products of 21 century.As technology is more and more ripe, it is possible to be developed rapidly from now on, preceding It is limitless on the way.
Principle luminous OLED is by applying an applied voltage, after hole and electronics overcome interface energy barrier, by anode Injected with negative electrode, respectively enter the HOMO energy ranks of hole-transporting layer and the LUMO energy ranks of electron transfer layer；Then electric charge is additional The interface of hole-transporting layer and electron transfer layer is transferred under the driving of electric field, the energy jump at interface causes interface to have electric charge Accumulation；Electronics, hole are in the organic substance for have the characteristics of luminescence in conjunction with one exciton of formation, this exciton is in general ring Border is unstable, will be released energy afterwards in the form of light or heat and returns to stable ground state.Via electronics, hole in conjunction with It 25% is singlet excited that caused excitation state only has in theory, and remaining 75% be triplet excited state, by with phosphorescence or hot shape Formula revert to ground state.
Organic Light Emitting Diode (OLEDs) large-area flat-plate show and illumination in terms of application cause industrial quarters and The extensive concern of art circle.However, traditional organic fluorescence materials can only be lighted using 25% singlet exciton to be formed is electrically excited, device The internal quantum efficiency of part is relatively low (up to 25%).External quantum efficiency is generally less than 5%, also has with the efficiency of phosphorescent devices very big Gap.Although phosphor material because the strong SO coupling in heavy atom center enhances intersystem crossing, can effectively utilize electricity The singlet exciton to be formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material is present Expensive, stability of material is poor, and device efficiency tumbles the problems such as serious and limits its application in OLEDs.Hot activation is prolonged Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Should Class material typically has small poor (the △ E of singlet-tripletST), triplet excitons can be changed by anti-intersystem crossing Lighted into singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior Quantum efficiency can reach 100%.Meanwhile material structure is controllable, property is stable, cheap without precious metal, in OLEDs Field has a extensive future.
Although TADF materials can realize 100% exciton utilization rate in theory, following problem there are in fact：(1) T1 the and S1 states of design molecule have strong CT features, very small S1-T1 state energy gaps, although can be realized by TADF processes High T1→S1State exciton conversion ratio, but low S1 state radiation transistion speed is also resulted in, consequently it is difficult to have (or realizing) concurrently simultaneously High exciton utilization rate and high fluorescent radiation efficiency；(2) even if mitigating T exciton concentration quenching effects using doping device, greatly Efficiency roll-off is serious at higher current densities for the device of most TADF materials.
For the actual demand that current OLED shows Lighting Industry, the development of OLED material is also far from enough at present, falls After the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of organising using ketone structure as parent nucleus Compound and its application in OLED.Ketone compounds of the invention based on TADF mechanism are core as emitting layer material Applied on Organic Light Emitting Diode, there are good photoelectric properties using the OLED of the compounds of this invention, disclosure satisfy that The requirement of panel manufacturing enterprise.
Technical scheme is as follows：
A kind of organic compound using ketone structure as parent nucleus, shown in the structure such as formula (1) of the organic compound：
In formula (1), X be expressed as oxygen atom or；I is equal to 0 or 1；
Wherein, Ar1Represent singly-bound or C6-30Arlydene in one kind；
Wherein, R1、R2Selection formula (2) independently, formula (3) or structure shown in formula (4)；R1、R2Can be with identical It is or different；
Formula (2), formula (3) or formula (4) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL’2- CL’3Key or CL’3-CL’4Key connection is shown in formula (1) in structure.
The general structure of the organic compound is expressed as：
In It is any.
Ar in the formula (1)1The substituent on right side is：
In any Kind.
The concrete structure using ketone structure as the compound of parent nucleus is：
Any of.
A kind of organic electroluminescence device containing the organic compound, the organic electroluminescence device are included at least One one functional layer contains the organic compound using ketone structure as parent nucleus.
A kind of luminescent device for including the organic compound, using ketone structure as the organic of parent nucleus in the luminescent device Compound is as emitting layer material, for making organic electroluminescence device.
A kind of method for preparing the organic compound, the reaction equation occurred in the preparation process are：
Course of reaction is as follows：Weigh ketone halogenated compound andDissolved with toluene；Add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95 ~110 DEG C, react 10~24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
The ketone halide withMol ratio be 1:1.0~4.0；Pd2(dba)3With ketone halogen The mol ratio of compound is 0.006~0.02:1, the mol ratio of tri-butyl phosphine and ketone halide is 0.006~0.02:1, uncle The mol ratio of sodium butoxide and ketone halide is 1.0~4.0:1.
The present invention is beneficial to be had technical effect that：
The compounds of this invention is using ketone compounds as parent nucleus, the crystallinity of saboteur, avoids intermolecular aggregation and makees With having good heat endurance；The compound structure intramolecular includes electron donor (donor, D) and electron acceptor The combination of (acceptor, A) can increase Orbital Overlap, improve luminous efficiency, while connect aromatic heterocycle group to obtain The charge transfer state material that HOMO, LUMO are spatially separating, realizes small S1State and T1Energy level difference (the △ E of statest<0.2eV), so as to Reverse intersystem crossing is realized under the conditions of thermostimulation, while the compounds of this invention has high triplet (T1), is suitable as For emitting layer material materials'use, beneficial to energy transmission between Subjective and Objective material, capacity usage ratio is improved.
Compound of the present invention can be used as emitting layer material to be made applied to OLED luminescent devices, obtain good device Part shows, and the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile carried for device lifetime Rise clearly.Compound-material of the present invention has good application effect in OLED luminescent devices, has well Industrialization prospect.
Brief description of the drawings
Fig. 1 is the device architecture schematic diagram of the compounds of this invention application；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminous Layer, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be negative electrode layer.
Fig. 2 is the efficiency curve diagram that device measures at different temperatures.
Embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
The synthesis of the intermediate A of embodiment 1
Under nitrogen atmosphere, weigh raw material I and be dissolved in tetrahydrofuran, then raw material II and tetrakis triphenylphosphine palladium are added, Stir mixture, add wet chemical, by the mixed solution of above-mentioned reactant in reaction temperature at 70-90 DEG C, add Heat backflow 5-20 hours.After reaction terminates, cooling plus water, mixture are extracted with dichloromethane, and extract is done with anhydrous sodium sulfate It is dry, filter and concentrate under reduced pressure, gained residue crosses silicagel column purifying, obtains intermediate B；
The mol ratio of raw material I and raw material II is 1:1.0~1.5, the mol ratio of tetrakis triphenylphosphine palladium and raw material I is 0.001~0.02:1, the mol ratio of potassium carbonate and raw material I is 1.0~2.0:1, the ratio of tetrahydrofuran and raw material I is 1g:10 ~30mL.
By taking the synthesis of intermediate A 1 as an example：
In 250mL there-necked flasks, nitrogen is passed through, adds 0.04mol raw materials I -1,150mL tetrahydrofuran, 0.05mol originals Expect II -1,0.0004mol tetrakis triphenylphosphine palladiums, the K of stirring, then addition 0.06mol2CO3The aqueous solution (2M), is heated to 80 DEG C, back flow reaction 10 hours, sample point plate, reaction is completely.Natural cooling, extracted with 200mL dichloromethane, layering, extract With anhydrous sodium sulfate drying, filtering, filtrate revolving, silicagel column purifying is crossed, obtains intermediate A 1, HPLC purity 99.1%, yield 58.7%.Elementary analysis structure (molecular formula C19H11ClO2)：Theoretical value C, 74.40；H,3.61；Cl,11.56；O,10.43；Survey Examination value：C,74.37；H,3.63；Cl,11.55；O,10.45.ESI-MS(m/z)(M+)：Theoretical value 306.04, measured value are 306.13。
Intermediate A is prepared with the synthetic method of intermediate A 1, concrete structure is as shown in table 1.
Table 1
The synthesis of the compound 01 of embodiment 2
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 1,0.015mol raw material B1 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 99.12%, yield 48.90%.
Elementary analysis structure (molecular formula C39H23NO2)：Theoretical value C, 87.13；H,4.31；N,2.61；O,5.95；Test Value：C,87.15；H,4.29；N,2.58；O,5.98.ESI-MS(m/z)(M+)：Theoretical value 537.17, survey molecular weight 537.23。
The synthesis of the compound 10 of embodiment 3
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 2,0.015mol raw material B2 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 97.62%, yield 50.82%.
Elementary analysis structure (molecular formula C39H23NO2)：Theoretical value C, 87.13；H,4.31；N,2.61；O,5.95；Test Value：C,87.11；H,4.33；N,2.63；O,5.93.ESI-MS(m/z)(M+)：Theoretical value 537.17, survey molecular weight 537.21。
The synthesis of the compound 13 of embodiment 4
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.015mol raw material B3 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 97.6%, yield 52.8%.
Elementary analysis structure (molecular formula C37H19NO4)：Theoretical value C, 82.06；H,3.54；N,2.59；O,11.82；Test Value：C,82.09；H,3.51；N,2.56；O,11.84.ESI-MS(m/z)(M+)：Theoretical value 541.13, survey molecular weight 541.22。
The synthesis of the compound 26 of embodiment 5
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 4,0.015mol raw material B4 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 96.64%, yield 52.81%.
Elementary analysis structure (molecular formula C37H19NO4)：Theoretical value C, 82.06；H,3.54；N,2.59；O,11.82；Test Value：C,82.04；H,3.53；N,2.61；O,11.82.ESI-MS(m/z)(M+)：Theoretical value 541.13, survey molecular weight 541.24。
The synthesis of the compound 28 of embodiment 6
With embodiment 3, difference is to replace raw material B2 with raw material B4 the preparation method of compound 28.
Elementary analysis structure (molecular formula C43H23NO4)：Theoretical value C, 83.62；H,3.75；N,2.27；O,10.36；Test Value：C,83.66；H,3.71；N,2.29；O,10.34.ESI-MS(m/z)(M+)：Theoretical value 617.16, survey molecular weight 617.25。
The synthesis of the compound 35 of embodiment 7
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 5,0.015mol raw material B5 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 97.20%, yield 44.65%.
Elementary analysis structure (molecular formula C43H23NO4)：Theoretical value C, 83.62；H,3.75；N,2.27；O,10.36；Test Value：C,83.63；H,3.73；N,2.29；O,10.35.ESI-MS(m/z)(M+)：Theoretical value 617.16, survey molecular weight 617.19。
The synthesis of the compound 37 of embodiment 8
With embodiment 4, difference is to replace raw material B3 with raw material B6 the preparation method of compound 37.
Elementary analysis structure (molecular formula C37H19NO4)：Theoretical value C, 82.06；H,3.54；N,2.59；O,11.82；Test Value：C,82.09；H,3.51；N,2.55；O,11.85.ESI-MS(m/z)(M+)：Theoretical value 541.13, survey molecular weight 541.27。
The synthesis of the compound 43 of embodiment 9
With embodiment 4, difference is to replace raw material B3 with raw material B7 the preparation method of compound 43.
Elementary analysis structure (molecular formula C37H19NO4)：Theoretical value C, 82.06；H,3.54；N,2.59；O,11.82；Test Value：C,82.09；H,3.51；N,2.56；O,11.84.ESI-MS(m/z)(M+)：Theoretical value 541.13, survey molecular weight 541.26。
The synthesis of the compound 46 of embodiment 10
With embodiment 3, difference is to replace raw material B2 with raw material B7 the preparation method of compound 46.
Elementary analysis structure (molecular formula C43H23NO4)：Theoretical value C, 83.62；H,3.75；N,2.27；O,10.36；Test Value：C,83.65；H,3.76；N,2.25；O,10.34.ESI-MS(m/z)(M+)：Theoretical value 617.16, survey molecular weight 617.28。
The synthesis of the compound 48 of embodiment 11
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 6,0.015mol raw material B7 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 97.12%, yield 47.63%.
Elementary analysis structure (molecular formula C43H23NO4)：Theoretical value C, 83.62；H,3.75；N,2.27；O,10.36；Test Value：C,83.64；H,3.74；N,2.25；O,10.37.ESI-MS(m/z)(M+)：Theoretical value 617.16, survey molecular weight 617.33。
The synthesis of the compound 50 of embodiment 12
With embodiment 5, difference is to replace raw material B4 with raw material B8 the preparation method of compound 50.
Elementary analysis structure (molecular formula C43H31NO2)：Theoretical value C, 86.99；H,5.26；N,2.36；O,5.39；Test Value：C,86.97；H,5.28；N,2.37；O,5.38.ESI-MS(m/z)(M+)：Theoretical value 593.24, survey molecular weight 593.37。
The synthesis of the compound 80 of embodiment 13
With embodiment 5, difference is to replace raw material B4 with raw material B4 the preparation method of compound 80.
Elementary analysis structure (molecular formula C43H31NO2)：Theoretical value C, 86.99；H,5.26；N,2.36；O,5.39；Test Value：C,86.96；H,5.29；N,2.38；O,5.37.ESI-MS(m/z)(M+)：Theoretical value 593.24, survey molecular weight 593.36。
The synthesis of the compound 90 of embodiment 14
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mo intermediate A 7,0.015mol raw material B1 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 95.22%, yield 51.25%.
Elementary analysis structure (molecular formula C45H27NO2)：Theoretical value C, 88.07；H,4.43；N,2.28；O,5.21；Test Value：C,88.10；H,4.41；N,2.26；O,5.23.ESI-MS(m/z)(M+)：Theoretical value 613.20, survey molecular weight 613.27。
The synthesis of the compound 96 of embodiment 15
With embodiment 14, difference is to replace raw material B1 with raw material B7 the preparation method of compound 96.
Elementary analysis structure (molecular formula C49H27NO4)：Theoretical value C, 84.83；H,3.92；N,2.02；O,9.22；Test Value：C,84.81；H,3.91；N,2.05；O,9.23.ESI-MS(m/z)(M+)：Theoretical value 693.19, survey molecular weight 693.31。
The synthesis of the compound 112 of embodiment 16
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 8,0.015mol raw material B2 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 94.82%, yield 51.74%.
Elementary analysis structure (molecular formula C42H29NO)：Theoretical value C, 89.49；H,5.19；N,2.48；O,2.84；Test Value：C,89.47；H,5.21；N,2.47；O,2.85.ESI-MS(m/z)(M+)：Theoretical value 563.22, survey molecular weight 563.34。
The synthesis of the compound 146 of embodiment 17
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 9,0.015mol raw material B2 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 94.82%, yield 51.74%.
Elementary analysis structure (molecular formula C39H25NO)：Theoretical value C, 89.46；H,4.81；N,2.67；O,3.06；Test Value：C,89.47；H,4.79；N,2.66；O,3.08.ESI-MS(m/z)(M+)：Theoretical value 523.19, survey molecular weight 523.24。
The synthesis of the compound 162 of embodiment 18
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol intermediate A 10,0.03mol raw material B7 are added, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 Hour, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 95.61%, yield 49.50%.
Elementary analysis structure (molecular formula C49H29NO3)：Theoretical value C, 86.58；H,4.30；N,2.06；O,7.06；Test Value：C,86.59；H,4.32；N,2.04；O,7.05.ESI-MS(m/z)(M+)：Theoretical value 679.21, survey molecular weight 679.32。
The compounds of this invention can use as emitting layer material, to the compounds of this invention 01,10,13,26,28,35, 37th, 43,46,48,50,80,90,96,112 and 162 T is carried out respectively1Energy level, hot property, the measure of HOMO energy levels, testing result As shown in table 2.
Table 2
Note：Triplet T1It is the F4600 XRFs test by Hitachi, the test condition of material is 2 × 10-5's Toluene solution；Glass transition temperature TgBy differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimeters) Measure, 10 DEG C/min of heating rate；Thermal weight loss temperature TdIt is the temperature of the weightlessness 1% in nitrogen atmosphere, in Japanese Shimadzu Corporation TGA-50H thermogravimetric analyzers on be measured, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy levels be by Ionizing energy test system (IPS3) is tested, and is tested as atmospheric environment.
As shown in Table 3, the compounds of this invention has higher triplet and higher heat endurance, appropriate HOMO Energy level, it is suitable as emitting layer material；Meanwhile the compounds of this invention contains electron donor (donor, D) and electron acceptor (acceptor, A) so that reach poised state using the OLED electronics of the compounds of this invention and hole so that device is imitated Rate and life-span get a promotion.
19-36 and comparative example 1 describe the compound that the present invention synthesizes in detail and are used as hair in the devices by the following examples The application effect of photosphere material of main part.For embodiment 20-36 compared with embodiment 19, the manufacture craft of the device is identical, And employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, except that device The material of main part of middle luminescent layer is changed.Embodiment 19-36 is compared with comparative example 1, the luminescent layer of device described in comparative example 1 Material is using existing conventional raw material, and embodiment 19-36 device luminescent layer material of main part is using chemical combination of the present invention Thing.The structure composition of each embodiment obtained device is as shown in table 3.The performance test results of each device are shown in Table 4.
Embodiment 19
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 01 and GD-19 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5：5 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).The molecule of each compound Structural formula is as follows：
Specific preparation process is as follows：
As shown in figure 1, being washed to the ito anode layer 2 on transparent substrate layer 1, i.e., carry out neutralizing treatment successively, pure water is washed Wash, carry out ultraviolet-ozone washing after drying again to remove the organic residue on transparent ITO surfaces.Carrying out above-mentioned washing On ito anode layer 2 afterwards, using vacuum deposition apparatus, the molybdenum trioxide MoO that thickness is 10nm is deposited3Injected as hole Layer 3 uses, and the TAPC of 80nm thickness is and then deposited as hole transmission layer 4.After above-mentioned hole mobile material evaporation terminates, system Make the luminescent layer 5 of OLED luminescent devices, its structure uses material compound 01 to be used as material of main part including OLED luminescent layers 5, GD-19 is 5% weight ratio as dopant material, dopant material doping ratio, and luminescent layer thickness is 30nm.In above-mentioned luminescent layer 5 Afterwards, it is TPBI to continue vacuum evaporation electron transport layer materials, and the vacuum evaporation thickness of the material is 40nm, and this layer passes for electronics Defeated layer 6.On electron transfer layer 6, by vacuum deposition apparatus, lithium fluoride (LiF) layer that thickness is 1nm is made, this layer is electricity Sub- implanted layer 7.On electron injecting layer 7, by vacuum deposition apparatus, aluminium (Al) layer that thickness is 80nm is made, this layer is the moon Pole reflection electrode layer 8 uses.Common used material structure is as follows：
After completing OLED luminescent devices as described above, anode and negative electrode are connected with known drive circuit, surveyed The life-span of the current efficiency of metering device, luminescent spectrum and device.The test result of obtained device is shown in Table 4 and shown.
Table 3
Table 4
Explanation:Device detection performance is used as reference using comparative example 1；Current efficiency is in 10mA/cm2Under the conditions of measure；Longevity It is owner of the present invention and the OLED life-span tester of Shanghai University's joint research to order test system.
By the following examples 36~43 and comparative example 2 illustrate that the compound that synthesizes of the present invention is used as luminescent layer in the devices The application effect of dopant material.Of the present invention 36~43, the complete phase of device making technics compared with embodiment 19 of comparative example 2 Together, identical baseplate material and electrode material are employed, the thickness of electrode material is also consistent, the difference is that in device The dopant material of luminescent layer 5 converts, and doping concentration is changed into 7%.The structure of each embodiment device is as shown in table 5, device Test result is shown in Table 6.
Table 5
Table 6
Explanation:Device detection performance is using comparative example 2 as reference, and current efficiency is in 10mA/cm2Under the conditions of measure；Longevity It is owner of the present invention and the OLED life-span tester of Shanghai University's joint research to order test system.
The result of table 4 shows that the compounds of this invention can make as luminescent layer material of main part using with OLED luminescent devices, And compared with comparative example 1, either efficiency or life-span obtain larger change, particularly device than known OLED material The life-span is driven to obtain larger lifting.The result of table 6 show the compounds of this invention as luminescent layer dopant material can apply with OLED luminescent devices make, and compared with comparative example 2, either efficiency or life-span obtain larger than known OLED material Take on a new look, the driving life-span of particularly device obtains larger lifting.
Work limitation rate is also more stable at low temperature for OLED prepared by further material of the present invention, and device is real Apply example 29,37,41 and device comparative example 1 and carry out efficiency test in -10~80 DEG C of sections, acquired results are as shown in Table 7 and Figure 2.
Table 7
It was found from the data of table 7, embodiment 29,37,41 is the device architecture that material of the present invention and known materials are arranged in pairs or groups, and Device comparative example 1 is compared, and not only Efficiency at Low Temperature is high, and in temperature elevation process, efficiency steadily raises.
From the point of view of data above application, the compounds of this invention has well as emitting layer material in OLED luminescent devices Application effect, there is good industrialization prospect.
Although the present invention is disclosed by embodiment and preferred embodiment, it should be appreciated that public the invention is not restricted to institute The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute The scope of attached claim should be consistent with most wide explanation to cover all such modifications and similar arrangement.

Claims (7)

  1. A kind of 1. organic compound using ketone structure as parent nucleus, it is characterised in that the structure of the organic compound such as formula (1) shown in：
    In formula (1), X be expressed as oxygen atom orI is equal to 0 or 1；
    Wherein, Ar1Represent singly-bound or C6-30Arlydene in one kind；
    Wherein, R1、R2Selection formula (2) independently, formula (3) or structure shown in formula (4)；R1、R2Can be with identical or not Together；
    Formula (2), formula (3) or formula (4) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL’2-CL’3Key Or CL’3-CL’4Key connection is shown in formula (1) in structure.
  2. 2. organic compound according to claim 1, it is characterised in that the general structure of the organic compound represents For：
    Any of.
  3. 3. organic compound according to claim 1, it is characterised in that Ar in the formula (1)1The substituent on right side is：
    Any of.
  4. 4. organic compound according to claim 1, it is characterised in that described using ketone structure as the compound of parent nucleus Concrete structure is：
    Any of.
  5. A kind of 5. organic electroluminescence device containing any one of Claims 1 to 4 organic compound, it is characterised in that At least one layer of functional layer that the organic electroluminescence device includes contains the organic compound using ketone structure as parent nucleus.
  6. 6. a kind of luminescent device for including any one of the Claims 1 to 4 organic compound, it is characterised in that described luminous Using ketone structure it is the organic compound of parent nucleus as emitting layer material in device, for making organic electroluminescence device.
  7. A kind of 7. method for preparing any one of Claims 1 to 4 organic compound, it is characterised in that the preparation process The reaction equation of middle generation is：
    Course of reaction is as follows：Weigh ketone halogenated compound andDissolved with toluene；Add Pd2 (dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95~ 110 DEG C, react 10~24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
    The ketone halide withMol ratio be 1:1.0~4.0；Pd2(dba)3With ketone halide Mol ratio be 0.006~0.02:1, the mol ratio of tri-butyl phosphine and ketone halide is 0.006~0.02:1, the tert-butyl alcohol The mol ratio of sodium and ketone halide is 1.0~4.0:1.
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CN107964017A (en) * 2016-10-19 2018-04-27 江苏三月光电科技有限公司 Compound and organic electroluminescence device containing azepine triphenylene
WO2019196950A1 (en) * 2018-04-13 2019-10-17 江苏三月光电科技有限公司 Compound taking xanthone as core and preparation method thereof and application thereof in oled
WO2019196948A1 (en) * 2018-04-13 2019-10-17 江苏三月光电科技有限公司 Compound using aryl ketone as core, preparation method therefor and application thereof on oled
CN111848589A (en) * 2019-04-30 2020-10-30 江苏三月科技股份有限公司 Xanthone derivative, preparation method and application thereof, and light-emitting device comprising xanthone derivative

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CN106467497A (en) * 2016-08-18 2017-03-01 江苏三月光电科技有限公司 A kind of compound with anthrone as core and its application in OLED
CN106467483A (en) * 2016-08-18 2017-03-01 江苏三月光电科技有限公司 A kind of five-membered ring substituted compound with xanthone as core and its application
CN106496198A (en) * 2016-08-31 2017-03-15 江苏三月光电科技有限公司 A kind of organic compound and its application with pyridine as core

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CN106467497A (en) * 2016-08-18 2017-03-01 江苏三月光电科技有限公司 A kind of compound with anthrone as core and its application in OLED
CN106467483A (en) * 2016-08-18 2017-03-01 江苏三月光电科技有限公司 A kind of five-membered ring substituted compound with xanthone as core and its application
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CN107880058A (en) * 2016-09-30 2018-04-06 江苏三月光电科技有限公司 A kind of compound containing benzheterocycle and its application in OLED
CN107964017A (en) * 2016-10-19 2018-04-27 江苏三月光电科技有限公司 Compound and organic electroluminescence device containing azepine triphenylene
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WO2019196948A1 (en) * 2018-04-13 2019-10-17 江苏三月光电科技有限公司 Compound using aryl ketone as core, preparation method therefor and application thereof on oled
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CN110372691A (en) * 2018-04-13 2019-10-25 江苏三月光电科技有限公司 It is a kind of using xanthone as the compound of core, preparation method and its application on OLED
CN110372691B (en) * 2018-04-13 2021-10-22 江苏三月科技股份有限公司 Compound with xanthone as core, preparation method thereof and application thereof in OLED
CN111848589A (en) * 2019-04-30 2020-10-30 江苏三月科技股份有限公司 Xanthone derivative, preparation method and application thereof, and light-emitting device comprising xanthone derivative
CN111848589B (en) * 2019-04-30 2022-04-05 江苏三月科技股份有限公司 Xanthone derivative, preparation method and application thereof, and light-emitting device comprising xanthone derivative

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