CN105384764B - A kind of Organic charge transport material shown available for OLED and preparation method thereof - Google Patents
A kind of Organic charge transport material shown available for OLED and preparation method thereof Download PDFInfo
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- CN105384764B CN105384764B CN201510746355.XA CN201510746355A CN105384764B CN 105384764 B CN105384764 B CN 105384764B CN 201510746355 A CN201510746355 A CN 201510746355A CN 105384764 B CN105384764 B CN 105384764B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
Abstract
The invention discloses a kind of Organic charge transport material shown available for OLED, there is structure as shown below：
Description
Technical field
The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field, more particularly relate to a kind of available for what OLED was shown have
Machine charge transport materials and preparation method thereof.
Background technology
Phosphorescence Organic Light Emitting Diode（OLED）Because it can utilize triplet and singlet excitons, internal quantum efficiency exists
In theory up to 100%, the close attention of scholar in the industry and expert are caused.
Electroluminescent organic material is divided into organic electroluminescent fluorescent materials and the major class of organic electromechanical phosphorescent material two, fluorescence and phosphorus
Light is all the process of radiation transistion, and the final state of transition is all ground state, and both differences are that the former transition primary state is sharp
Send out singlet state, and the latter is excited triplet state, different from luminescence generated by light, in Organic Light Emitting Diodes, triplet excitons with
Singlet exciton generates simultaneously.The generation ratio of usual singlet exciton and triplet excitons is 1:3, singlet excitons spoke
Penetrate decay and keep spin conservation, what is sent is fluorescence；The attenuation of triplet exciton is spin forbidden, can only be sent faint
Phosphorescence.So in most of organic molecules, almost there is no phosphorescence to electroluminescent caused by the radiation transistion of triplet exciton
Contribution.Theoretically, luminous efficiency is minimum to luminous contribution not over 25%, only singlet exciton radioluminescence, because
This, for organic polymer fluorescent device, the basic reason that luminous efficiency is difficult to improve is that luminescence process is singlet
Exciton lights.
Initial stage is studied in organic luminescent device, in order to overcome the defects of only singlet exciton is luminous, has scholar to propose
The imagination of triplet emission, the research of subsequent organic electrophosphorescenpolymer are developed rapidly.Exploitation is most, application prospect is best
A kind of phosphor material is complex of iridium, because its triplet lifetime is shorter, has preferable luminescent properties, because phosphor material is solid
There is stronger triplet state quenching in body, typically by the use of complex of iridium as doping guest materials, made with the material of wider band gap
Doped body material, the acquisition high-luminous-efficiency that lights is trapped on object by energy transfer or directly by exciton.Therefore develop
Development of the phosphor material of function admirable to OLED is significant.
The content of the invention
It is an object of the invention to provide a kind of hole mobile material that can be effectively improved OLED efficiency.
The object of the present invention is achieved like this, the derivative of the amoxy dibenzothiophenes based on silicon tetraphenyl substitution,
It is characterized in that the compound has structure as shown below：
The preparation method of the above-mentioned Organic charge transport material shown available for OLED, is characterized in：, will under argon gas protection
Dibenzothiophenes -4- boric acid and two（4- bromophenyls）- phenyl silane, with 1mol：2.1 ~ 4.3mol ratio is added to reactant
In system；Add the palladium catalyst and PSQ silicon substrate co-catalysts of organic microporous polymer load；Add potassium carbonate or sodium carbonate and mix
Bonding solvent, 5 ~ 10h is reacted under the conditions of 50 ~ 100 DEG C, obtain the derivative of the amoxy dibenzothiophenes based on silicon tetraphenyl substitution
Thing, mixed solvent are that toluene+ethanol system or THF+ aqueous systems, syntheti c route are as follows：
。
A kind of application of the above-mentioned Organic charge transport material shown available for OLED in new energy field.
A kind of application of the above-mentioned Organic charge transport material shown available for OLED in OLED fields.
The maximum feature of the hole mobile material of the present invention is silicon tetraphenyl group and dibenzo thiophene of the both sides with amoxy
Fen is docked, and forms high performance hole mobile material, has larger difference with previously reported silicon tetraphenyl derivative, the serial material
Material has wider energy gap and higher triplet, excellent heat endurance.NPB is that the hole being widely used always passes
One of defeated material, its glass transition temperature Tg=98 DEG C, Tm=290 DEG C, mobility are 5.1 × 10-4cm2/ Vs, in order to improve molecule
Heat endurance, this patent have devised with silicon tetraphenyl and dibenzothiophene derivatives.
Beneficial effects of the present invention are as follows：
1. the present invention has the dibenzothiophenes of cavity transmission ability based on the connection of silicon tetraphenyl group, and in dibenzo thiophene
Fen both sides symmetrically carry amoxy functional group, it is possible to reduce intermolecular reunion and interaction.
2. the present invention has preferable heat endurance, wherein decomposition temperature is 460 DEG C, and glass transition temperature is 156 DEG C.
3. hole-transporting type material of main part of the present invention as OLED, with Ir（ppy）3As guest materials, device
Maximum current efficiency, power efficiency and external quantum efficiency be respectively for 76.9cd/A, 69.2Im/W, 27.6%；In high electric field（1
×106V/cm）When mobility be 2.0 × 10-5cm-2/Vs, show that the derivative has electron mobility.
4. branched amoxy functional group of dibenzothiophenes institute in the present invention, carbon number is odd number, is contained than adjacent
The stability of even-numbered carbon atom is high, stronger than the structure electron donation with even-numbered carbon atom, but if carbon number is grown again
If, intermolecular interaction can be hindered, closely can not effectively be piled up.
5. the present invention is connecting electric charge transmission functional group, effect of the transmission functional group by chemical bond on parent compound
Realize local transmission group high concentration heap, it is possible to form it is a kind of locally even in certain limit aligned orderly " aggregation
State " structure, improve charge transport properties.
This patent compound and the specific data comparisons of NPB such as following table：
| Compound name | Molecular weight | Fusing point/DEG C | Glass transition temperature/DEG C | Hole mobility/cm-2/Vs |
| NPB | 589 | 290 | 98 | 5.1×10-4 |
| I | 1046 | 331 | 156 | 5.7×10-3 |
As shown by data, hole-transporting type material of main part of the invention has excellent hole transport performance, while has electronics
Transmission characteristic, shown available for OLED.
Embodiment
The present invention is further described with reference to embodiments, it is necessary to which explanation is following embodiment only for clear
Understand the present invention, the invention is not restricted to the embodiment.
Properties of product test event and tester：
Thermogravimetric analysis is tested by Oniversal V2.4F TA Instruments types thermogravimetric analyzer, and DSC is by TA DSC
Q20 type differential scannings instrument determines.
Absorption spectrum is determined by UV-4802 type dual-beams ultraviolet-uisible spectrophotometer, fluorescence spectrum and fluorescent quantum effect
Rate is by 970CRT fluorescence spectrophotometer measurements.
The measurement of fluorescence quantum efficiency is using PBD as standard substance, and its Ф=1.0, fluorescence quantum efficiency is according to following public affairs
Formula is calculated：The integral area of Ф v=(As/Au) Ф s, wherein As, Au difference determinand and reference material emission spectrum, Ф s are
The luminous efficiency of reference material.
Japanese Shimadzu LC-10ATvp types high pressure liquid chromatograph (methanol：Acetonitrile=2：1, flow velocity 1ml/min)；Day island proper
Tianjin GC-14C, GC-17A gas chromatograph（DB-1 type pillars）；Japanese Shimadzu GCMS-2014C type mass spectrographs.
Embodiment 1, a kind of Organic charge transport material shown available for OLED, the material are based on silicon tetraphenyl and penta
The derivative of epoxide dibenzothiophenes, structure is as shown in formula I：
The preparation method of said derivative is as follows：
。
The wherein preparation of intermediate II：Under argon gas protection, two are sequentially added into there-necked flask（4- bromophenyls）- phenyl silane
74.2g, tetrahydrofuran 50ml, -78 DEG C are cooled to, 225mL n-BuLis are added dropwise, are added dropwise, stirred 1 hour at -78 DEG C,
Butyl borate 124.28g is slowly added dropwise again, insulation reaction automatic heating after 1 hour is added dropwise, reaction is overnight.Reacting
Water 400ml, concentrated hydrochloric acid 400ml, petroleum ether 550ml, stirring 2h are added in bottle.Organic layer washing to neutrality, boils off solvent twice,
By product under stirring, it is poured slowly into water, separates out solid, filtering, filter cake is dried after being eluted with petroleum ether and obtains II
52.8g.Yield is 83%.
The preparation of intermediate III：Into three-necked flask, the amoxy dibenzothiophenes 35.65g of 2,8- bis-, dichloro are sequentially added
Methane 700ml, stirring is opened, liquid nitrogen cooling is to -75 DEG C.In batches plus NBS18.7g, after adding, in -75 DEG C to -85 DEG C insulations
3h, after heating up naturally, sodium acid carbonate 30.0g+ water 1500ml mixed solution is added into reaction system, stirring separates organic
Phase, organic phase is washed with water to neutrality, products obtained therefrom with ethanol and petroleum ether is 1ml to dry by concentration organic phase：2ml mixing
Solvent is recrystallized, and obtains III 30.5 g, yield 70%.
I preparation：Under argon gas protection, III 47.9 g, II 21.2 g, polymer support load Pd are added into there-necked flask
Catalyst 0.1mol%, PSQ type silicon substrate co-catalyst 0.05mol%, the g of Anhydrous potassium carbonate 6.9, the mL of tetrahydrofuran 100, water
100 mL, 70 DEG C are reacted 6 hours, boil off solvent, with dichloromethane and water dissolution residual substance, washing, separate organic layer, organic
Layer is with 100mL washings twice to neutral, and after boiling off solvent, residue is through column chromatography for separation, and silica gel is 350 mesh, leacheate
For petroleum ether：Dichloromethane=3:1 (V/V), solvent is boiled off, toluene elutes after drying, and obtaining I46.5g yields after drying is
89%。
Embodiment 2, a kind of Organic charge transport material show available for OLED, the material for based on silicon tetraphenyl and
The derivative of amoxy dibenzothiophenes, structure is as shown in formula I：
The preparation method of said derivative is as follows：
。
The wherein preparation of intermediate II：Under argon gas protection, two are sequentially added into there-necked flask（4- bromophenyls）- phenyl silane
37.1g, tetrahydrofuran 30ml, -78 DEG C are cooled to, 113mL is added dropwise）N-BuLi, it is added dropwise, it is small in -78 DEG C of stirrings 1
When, then butyl borate 62.14g is slowly added dropwise, insulation reaction automatic heating after 1 hour is added dropwise, reaction is overnight.Anti-
Answer and water 200ml, concentrated hydrochloric acid 200ml, petroleum ether 300ml, stirring 2h are added in bottle.Organic layer washing boils off molten twice to neutrality
Agent, by product under stirring, it is poured slowly into water, separates out solid, filtering, filter cake is dried after being eluted with petroleum ether and obtains II
51.5g.Yield is 81%.
The preparation of intermediate III：Into three-necked flask, the amoxy dibenzothiophenes 73.3g of 2,8- bis-, dichloro are sequentially added
Methane 1500ml, stirring is opened, liquid nitrogen cooling is to -75 DEG C.In batches plus NBS37.4g, after adding, in -75 DEG C to -85 DEG C insulations
3h, after heating up naturally, sodium acid carbonate 60.0g+ water 2500ml mixed solution is added into reaction system, stirring separates organic
Phase, organic phase is washed with water to neutrality, products obtained therefrom with ethanol and petroleum ether is 1ml to dry by concentration organic phase：2ml mixing
Solvent is recrystallized, and obtains III 63.6 g, yield 73%.
I preparation：Under argon gas protection, III 95.8 g, II 42.4 g sodium carbonate 10.6g, toluene are added into there-necked flask
250 mL, the mL of ethanol 250,70 DEG C are reacted 6 hours, boil off solvent, with dichloromethane and water dissolution residual substance, washing, have been separated
Machine layer, organic layer are washed twice to neutrality with 300mL, and after boiling off solvent, residue is through column chromatography for separation, silica gel 350
Mesh, leacheate are petroleum ether：Dichloromethane=3:1 (V/V), solvent is boiled off, toluene is eluted after drying, and I90.9g is obtained after drying
Yield is 87%.Compound I：1H NMR (400 MHz, CDCl3)：8.23-8.14 (m, 4H, Ar-H), 7.88-
7.76 (m, 10H, Ar-H), 7.70 (dd, J=8.9,8.0 Hz, 4H, Ar-H), 7.61-7.51 (m, 2H,
Ar-H), 7.51-7.41 (m, 8H, Ar-H), 3.94（M, 8H, OCH2-H）, 1.29-1.71（m, 24H, CH2-H）,
0.96 (m, 12H, Me-H）；LC-MS （ESI）：1045[M-H]-, elementary analysis measured value（Calculated value）/%：C78.10
（78.12）, H6.96（6.94）, O6.14（6.12）, S6.12（6.13）, Si2.68（2.69）.
Fusing point：331 DEG C, glass transition temperature：156 DEG C, decomposition temperature：460℃
Absorption spectrum：λmax=310nm
Fluorescence spectrum：λmax=406nm
Hole mobility：5.7×10-3cm2/Vs
Identification confirms that the compound of synthesis is two { 4- [4-（Bis- amoxys of amoxy -2', 8'- of 2,8- bis-）（Dibenzo [b,
D] thienyl）Phenyl] } quadrosilan.
Claims (3)
- A kind of 1. Organic charge transport material shown available for OLED, it is characterized in that the material is based on silicon tetraphenyl and penta oxygen The derivative of base dibenzothiophenes, structure is as shown in formula I：The derivative has hole transporting properties, is shown available for OLED；The preparation method of the Organic charge transport material shown available for OLED, it is characterized in that：Under argon gas protection, by hexichol Bithiophene -4- boric acid and two (4- bromophenyls)-phenyl silanes, with 1mol：2.1~4.3mol ratio is added to reaction system In；Add the palladium catalyst and PSQ silicon substrate co-catalysts of organic microporous polymer load；Add potassium carbonate or sodium carbonate and mixing Solvent, 5~10h is reacted under the conditions of 50~100 DEG C, obtain the derivative of the amoxy dibenzothiophenes based on silicon tetraphenyl substitution Thing, mixed solvent are toluene+ethanol system or THF+ aqueous systems.
- A kind of 2. Organic charge transport material shown available for OLED answering in new energy field described in claim 1 With.
- A kind of 3. application of Organic charge transport material shown available for OLED in OLED fields described in claim 1.
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| US8563145B2 (en) * | 2006-06-02 | 2013-10-22 | Idemitsu Kosan Co., Ltd. | Material containing two or three dibenzofuran groups, dibenzothiophene groups, or a combination thereof, which is operable for organic electroluminescence elements, and organic electroluminescence elements using the material |
| CN102181282A (en) * | 2011-03-22 | 2011-09-14 | 天津大学 | Cavity transfer material with triphenylamine-bipyridyl structure and preparation method thereof |
| US8748012B2 (en) * | 2011-05-25 | 2014-06-10 | Universal Display Corporation | Host materials for OLED |
| JP6348380B2 (en) * | 2013-08-30 | 2018-06-27 | 日本放送協会 | Hole transport material |
| JP2015117210A (en) * | 2013-12-19 | 2015-06-25 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Silane compound and organic el element |
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Denomination of invention: An organic charge transfer material for OLED display and its preparation method Effective date of registration: 20220714 Granted publication date: 20171215 Pledgee: Rizhao bank Limited by Share Ltd. Yantai branch Pledgor: SHANDONG SHENGHUA NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980010517 |