CN104910372B - Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application - Google Patents
Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application Download PDFInfo
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- CN104910372B CN104910372B CN201510229873.4A CN201510229873A CN104910372B CN 104910372 B CN104910372 B CN 104910372B CN 201510229873 A CN201510229873 A CN 201510229873A CN 104910372 B CN104910372 B CN 104910372B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
Abstract
The invention discloses aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and the preparation method and application of transmission material.During preparation, under the conditions of 0 DEG C~40 DEG C, in the aqueous solution that aryl polyphenol compound is added to alkali catalyst, 1,3,5 equal three polychlorostyrene piperazine quasi-molecule is dissolved in organic solvent, it is added drop-wise to dropwise in aryl polyphenol compound, 0.5h~48h is reacted under the conditions of 0 DEG C~100 DEG C；Reacting liquid pH value, filtration washing are directly adjusted after reaction with diluted acid.The phenolic hydroxyl structure of the present invention is oxidized easily, form free radical intermediate state, therefore possess hole injection and transmission performance, there is preferable dissolubility in the big polar solvent such as dimethyl sulfoxide (DMSO) and alcohols simultaneously, and such as toluene, chlorobenzene, dichloromethane, chloroform low polar solvent are insoluble in, its corrosion can be resisted, in organic electro-optic device, including organic electroluminescent LED, there is preferable application prospect in terms of organic solar batteries device.
Description
Technical field
The present invention relates to the soluble hole note of hole injection and transmission molecular material, more particularly to novel one step process synthesis
Enter and transmission material, preparation method and its application in organic optoelectronic device field.
Background technology
Since Tang and VanSlyke in 1987 is prepared for plural layers electroluminescent device, organic light-emitting diodes have been invented
Manage (OLED), when organic electronics material and device experienced the fast development of nearly 30 years including Organic Light Emitting Diode etc.
Phase.At present, vacuum thermal evaporation film-forming technology prepares the electroluminescent device (OLED) of small molecule material and has been successfully applied to portion
Divide the display screen of electronic product；And with the organic polymer electroluminescent device (PLED) of solution processing type, in inexpensive, big face
Tool has great prospects for development in terms of product, Flexible Displays, inkjet printing, is forward position and the heat of current basic research and application study
Point direction.
Organic polymer electroluminescent device (PLED) based on solution processing technology, similar multilayer evaporation thin-film electro causes hair
Optical device is, it is necessary to which the method processed by solution prepares multilayer device.Therefore, the charge transport materials of solution processable are opened
Hair, for realizing that the commercial Application of whole soln processing has extremely important meaning.The head that the device of multilayer solution processing faces
It is erosion problem of the solvent to subsurface material, current device architecture to want problem：Electro-conductive glass (such as ITO etc.)/hole is injected
And transport layer (HIL/HTL, hole injection/transport layer), then upper strata is toluene, dimethylbenzene or chlorobenzene etc.
Weak polar solvent dissolves the luminescent material of film forming.Therefore, hole injection/transmission material needs invading efficiently against these solvents
Erosion.Poly- 3,4- ethylenedioxy thiophenes/poly styrene sulfonate (PEDOT:PSS) the high efficiency hole injection/transmission dissolved for water
Material, but it has stronger acidity, can corrode anode material on long terms, reduces the life-span of device.Therefore, exploitation is free of
Sulfonate radical, is provided simultaneously with good hole injection/transmission performance, is dissolved in relatively large polar solvent, and indissoluble or does not dissolve in
Other low polar organic solvents, such as toluene, chlorobenzene, dichloromethane, hole injection/transmission material of chloroform equal solvent, with non-
Often important meaning.
The content of the invention
Present invention aims to overcome that the shortcoming and deficiency of prior art there is provided the new soluble aryl polyphenol of a class with
The hole injection of 1,3,5- s-triazine crosslinking and transmission material and preparation method thereof, the dissolubility of the material has good solvent
Selectivity.
Another object of the present invention is to provide aryl polyphenol to inject with passing with 1,3,5- s-triazine cross-linked polymers hole
Defeated material injects the application with transmission material in organic optoelectronic device as hole.
The present invention is by one-step method by aryl diphenol or aryl triphenol and 1, and 3,5- equal three polychlorostyrene piperazine polymerizations are direct after reaction
Product is adjusted into pH value, filtration washing is that can obtain.Material of the present invention is due to aryl phenolic hydroxyl group therein and the sour structure of trimerization piperazine
In hydroxyl can occur oxidation reaction, there is electronic transfer process in the process, therefore possess hole injection and transmission performance.This
Invention material has phenolic hydroxyl structure, therefore has in dimethyl sulfoxide (DMSO) and alcohol preferable dissolubility, and is insoluble in such as toluene, chlorine
The low polar solvents such as benzene, dichloromethane, chloroform, can resist its corrosion.Therefore, hole injection can be used for making with transmission material
The multilayer device that standby solution is processed, it is to avoid the mutual erosion of hole injection/transport layer and active layer, can pass through solution processing method
Prepare plural layers device.This new hole injection and transmission material, prepare simply, can process film forming with solution, have
Machine photoelectric device, including organic electroluminescent LED, organic solar batteries, organic field effect tube, the perovskite sun
There is application prospect in terms of the devices such as energy battery, dye-sensitized cell, organic laser illumination, this processes organic light for whole soln
The development and industrialization of electronic material and device are significant.
The purpose of the present invention is achieved through the following technical solutions：
Aryl polyphenol and 1, the injection of 3,5- s-triazine cross-linked polymer holes and transmission material, with such as formula (I) or formula
(II) one kind in molecular structure：
Wherein Ar1For aryl diphenol structure, Ar2For aryl triphenol structure, wave represent aryl diphenol or aryl triphenol with
The coupled structures of 1,3,5- s-triazine.
The aryl polyphenol and 1, the injection of 3,5- s-triazine cross-linked polymer holes and the preparation method of transmission material, including
Following steps：
1) under the conditions of 0 DEG C~40 DEG C, in the aqueous solution that aryl polyphenol compound is added to alkali catalyst, by 1,3,
The equal three polychlorostyrene piperazine quasi-molecules of 5- are dissolved in organic solvent, are added drop-wise to dropwise in aryl polyphenol compound, in 0 DEG C~100 DEG C bars
0.5h~48h is reacted under part；
Described aryl polyphenol compound is aryl diphenol or the phenolic compounds of aryl three；Described aryl diphenol is containing two
The aryl compound of individual phenolic hydroxyl group；Described aryl triphenol is the aryl compound containing three phenolic hydroxyl groups；
Described alkali catalyst is sodium hydroxide, triethylamine, diisopropyl ethyl amine, potassium hydroxide, sodium carbonate, carbonic acid
One or more in potassium and cesium carbonate；
According to the molfraction meter of material, composition of raw materials composition is：10 parts of the equal three polychlorostyrene piperazines of 1,3,5-；Aryl Polyphenols list
5~50 parts of body；5~150 parts of base catalyst；
2) by step 1) obtained reaction mixture poured into a large amount of deionized waters, and solution ph is adjusted in dilute acid soln
Property, filtering, with water and organic solvent washing, obtains hole injection and transmission that aryl polyphenol is crosslinked 1,3,5- s-triazine structures
Material.
The molecular formula of the equal three polychlorostyrene piperazines of described 1,3,5- is：
Further to realize the object of the invention, it is preferable that described dilute acid soln is hydrochloric acid, sulfuric acid, acetic acid and fluoroform
One or more in sulfonic acid.
Described aryl diphenol is the one or more in following structural formula (1)-(12)；
Described aryl triphenol is following structural formula (13) and/or (14)；
The volume ratio 0.1-10 of organic solvent and water in described organic solvent and the mixed liquor of water:1.
Described organic solvent is the one or more in tetrahydrofuran, acetone, ether, acetonitrile and dioxane.
Described aryl polyphenol is with the injection of 1,3,5- s-triazine cross-linked polymers hole with transmission material in organic optoelectronic
Learn in device as hole injection and the application of transmission material；The organic optoelectronic device includes light emitting diode, organic
Hetero-junction solar cell, perovskite solar cell, dye-sensitized cell, organic laser illuminating device.
Aryl polyphenol of the present invention is dissolved in dimethyl with the injection of 1,3,5- s-triazine cross-linked polymers hole with transmission material
The big polar solvent such as sulfoxide and alcohol, reapplies in preparing organic optoelectronic device, is used as hole injection and transmission material.
Compared with prior art, the present invention has advantages below and beneficial effect：
1) hole of aryl polyphenol crosslinking 1,3,5- s-triazine structures of the present invention is injected with containing in transmission material
Multiple phenolic hydroxyl structures so that prepared material has preferable dissolubility in dimethyl sulfoxide (DMSO) and alcohol, is but insoluble in other
Low polar organic solvent, such as toluene, chlorobenzene, dichloromethane, chloroform.Therefore, aryl polyphenol crosslinking 1,3 of the present invention,
Hole injection and the transmission material of 5- s-triazine structures can be used for the multilayer device for preparing solution processing, it is to avoid hole is injected with passing
The mutual erosion of defeated layer and active layer.
2) aryl polyphenol of the present invention is crosslinked hole injection and the transmission material of 1,3,5- s-triazine structures, with tradition
With larger conjugated system hole injection with the poly- 3,4- ethylenedioxy thiophenes/poly styrene sulfonate of transmission material
(PEDOT:PSS) compare, due to aromatic ring and 1, be connected between 3,5- s-triazine units by ehter bond, belong to non-conjugated structure, because
This has wider band gap, very weak in visible ray and infrared Absorption, and light extraction efficiency will not be reduced in electroluminescent device, side
Just it is used for the preparation of transparency electrode.
3) aryl polyphenol of the present invention is crosslinked hole injection and the transmission material of 1,3,5- s-triazine structures, for for
For traditional PEDOT:PSS, spin-coating film is injected with transmitting material as hole on tin indium oxide (ITO) electro-conductive glass substrate
Material, electroluminescent device performance is close to use PEDOT:PSS injects the device with transmission material as hole.Due to phenol and right
Oxidation reaction easily occurs for the aryl polyphenol such as benzenediol, and the oxidizing process there occurs in the middle of electro transfer, generation phenol free radical
Body, while the phenol free radical intermediate can form the mutual variants of multiple resonance, it is potential can be injected as hole/transmit material
Material.
4) the hole injection of aryl polyphenol crosslinking 1,3,5- s-triazine structures of the present invention and transmission material preparation side
Method is simple, purification is convenient.
Brief description of the drawings
Fig. 1,2,3,4,5,6 are respectively the nucleus magnetic hydrogen spectrum of the product of embodiment 1,2,3,4,5,6；
Fig. 7 is substance assistant laser desorpted-flight time mass spectrum of embodiment 1.
Fig. 8 is that (device architecture is for the device of embodiment 1：ITO/HIL/HTL/p-PPV/CsF/Al maximum extrinsic current effect)
Rate figure.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples, it is necessary to explanation, embodiment not structure
Into limiting the scope of the present invention.
Embodiment 1
Hydroquinones (0.825g, 7.5mmol) is dissolved in 20mL sodium hydroxide (0.3g, 7.5mmol) aqueous solution,
The tetrahydrofuran solutions of 1,3,5- equal three polychlorostyrene piperazines (0.25M, 10mL, 2.5mmol) is slowly added dropwise under the conditions of lucifuge to reaction bulb
In.At room temperature after stirring 24h, tetrahydrofuran rotary distillation is removed, reactant mixture is poured into 100mL water, is adjusted with watery hydrochloric acid
Filter cake is washed with water to neutrality, filtering in pH, is dried to obtain 0.80g tan products.
Fig. 1 and Fig. 7 are respectively nucleus magnetic hydrogen spectrum and substance assistant laser desorpted-flight time mass spectrum, nucleus magnetic hydrogen spectrum test knot
It is really：1HNMR(d6-DMSO,400MHz,δ/ppm):6.55(s,2H),6.67-6.81(d,7H),6.94-7.09(m,7H),
7.25-7.41(m,7H),11.11-11.24(m,4H).It is multiplet in the signal of aromatic rings, and compared with raw material, card
Bright is not the signal of raw material, meets the feature of polymer, and it is hydroquinones and 1 to show sample, after 3,5- equal three polychlorostyrene piperazine couplings
The polymer of generation.Fig. 7 is the result of substance assistant laser desorpted-flight time mass spectrum, and the mass spectrographic mass-to-charge ratio is represented at this
Under test condition, polymer samples molecule is excited the molecular fragment peak of generation, it was demonstrated that the molecular weight of the embodiment polymer exists
Between 500-1312, and the molecular weight of polymer in itself is more than the corresponding molecular weight of the fragment peak.Polymer divides for testing
Dissolubility in the common solvents of son amount is poor, is difficult to measure its accurate molecular masses at present.
Embodiment 2
By 2,5- di-tert-butyl hydroquinones (1.67g, 7.5mmol) be dissolved in 20mL sodium hydroxide (0.9g,
22.5mmol) in the aqueous solution, 1,3,5- equal three polychlorostyrene piperazines (0.25M, 10mL, 2.5mmol) are slowly added dropwise under the conditions of lucifuge
Dioxane solution is into reaction bulb.After 60 DEG C of stirring 24h, reactant mixture is poured into 500mL water, adjusts pH to arrive with dilute sulfuric acid
Neutrality, filtering, and filter cake is washed with water, acetone, it is dried to obtain 1.5g Off-white products.
Fig. 2 is the nucleus magnetic hydrogen spectrum of embodiment 2,1HNMR(d6-DMSO,400MHz,δ/ppm):0.75-1.57(m,23H),
6.20-7.38(m,10H),8.38-8.88(m,2H),9.23(s,1H).It is multiplet in the signal of aromatic rings, and with
Raw material is compared, it was demonstrated that be not the signal of raw material, meets the feature of polymer, as a result show sample for 2,5- di-t-butyls to benzene two
The polymer generated after phenol and the equal three polychlorostyrene piperazine couplings of 1,3,5-.
Embodiment 3
Isosorbide-5-Nitrae-dihydroxy naphthlene (1.2g, 7.5mmol) is dissolved in 20mL sodium carbonate (0.8g, 7.5mmol) aqueous solution,
The tetrahydrofuran solutions of 1,3,5- equal three polychlorostyrene piperazines (0.25M, 10mL, 2.5mmol) is slowly added dropwise under the conditions of lucifuge to reaction bulb
In.After 60 DEG C of stirring 24h, reactant mixture is poured into 100mL water, adjusts pH to neutrality with spirit of vinegar, filters, and with water, third
Ketone washs filter cake, is dried to obtain 1.1g brown products.
Fig. 3 is the nucleus magnetic hydrogen spectrum of embodiment 3,1HNMR(d6-DMSO,400MHz,δ/ppm):4.52(s,1H),6.90-
8.04(m,21H),9.83(s,1H).It is multiplet in the signal of aromatic rings, and compared with raw material, it was demonstrated that it is not raw material
Signal, meet the feature of polymer, as a result show that sample is Isosorbide-5-Nitrae-dihydroxy naphthlene and 1, it is raw after 3,5- equal three polychlorostyrene piperazines couplings
Into polymer.
Embodiment 4
Hydroquinones (0.85g, 7.5mmol) is dissolved in 20mL triethylamine (1.51g, 15mmol) aqueous solution, kept away
The dioxane solutions of 1,3,5- equal three polychlorostyrene piperazines (0.75M, 10mL, 7.5mmol) is slowly added dropwise under optical condition to reaction bulb
In.At room temperature after stirring 24h, acetone rotary distillation is removed, reactant mixture is poured into 100mL water, adjust pH to arrive with watery hydrochloric acid
Neutrality, filtering, and filter cake is washed with water, acetone, it is dried to obtain 2.3g gray solid products.
Fig. 4 is the nucleus magnetic hydrogen spectrum of embodiment 4,1HNMR(d6-DMSO,400MHz,δ/ppm):4.46(s,9H),6.62-
6.92 (m, 2H), 6.91-7.11 (m, 3H), 7.28-7.48 (m, 5H), 11.20 (s, 1H).In the signal of aromatic rings, it is
Multiplet, and compared with raw material, it was demonstrated that it is not the signal of raw material, meets the feature of polymer, it is Isosorbide-5-Nitrae-two as a result to show sample
The polymer generated after hydroxyl naphthalene and the equal three polychlorostyrene piperazine connection of 1,3,5-.
Embodiment 5
Isosorbide-5-Nitrae-dihydroxy naphthlene (1.2g, 7.5mmol) is dissolved in the aqueous solution of 20mL cesium carbonate (4.88g, 22.5mmol)
In, the acetonitrile solutions of 1,3,5- equal three polychlorostyrene piperazines (0.75M, 10mL, 7.5mmol) is slowly added dropwise under the conditions of lucifuge to reaction bulb
In.After 60 DEG C of stirring 24h, reactant mixture is poured into 100mL water, filtered, and wash with clear water, acetone filter cake, dry
To 1.1g brown solids.
Fig. 5 is the nucleus magnetic hydrogen spectrum of embodiment 5,1HNMR(d6-DMSO,400MHz,δ/ppm):4.56(s,1H),6.77-
7.95 (m, 14H), 9.20-9.67 (d, 1H), 10.06 (s, 1H).It is multiplet in the signal of aromatic rings, and and raw material
Compare, it was demonstrated that be not the signal of raw material, meet the feature of polymer, it is Isosorbide-5-Nitrae-dihydroxy naphthlene and 1 as a result to show sample, and 3,5- is equal
The polymer generated after the coupling of three polychlorostyrene piperazines.
Embodiment 6
Bisphenol-A (0.95g, 7.5mmol) is dissolved in 20mL diisopropyl ethyl amine (1.94g, 15mmol) aqueous solution,
The tetrahydrofuran solutions of 1,3,5- equal three polychlorostyrene piperazines (0.25M, 10mL, 2.5mmol) is slowly added dropwise under the conditions of lucifuge to reaction
In bottle.After return stirring 24h, tetrahydrofuran rotary distillation is removed, reactant mixture is poured into 100mL water, is adjusted with dilute sulfuric acid
PH washs filter cake to neutrality, filtering with clear water, tetrahydrofuran, is dried to obtain 1.3g white solid products.
Fig. 6 is the nucleus magnetic hydrogen spectrum of embodiment 6,1HNMR(d6-DMSO,400MHz,δ/ppm):1.04-1.33(s,1H),
1.43-1.75 (m, 18H), 6.62 (d, 7H), 7.04-7.38 (m, 17H), 11.22 (s, 1H), 10.06 (s, 1H).In aromatic rings
Signal in, be multiplet, and compared with raw material, it was demonstrated that be not the signal of raw material, meet the feature of polymer, as a result show
Sample is the polymer generated after bisphenol-A and the coupling of 1,3,5- equal three polychlorostyrene piperazines.
Embodiment 7：Aryl polyphenol injects organic in green with transmission material with 1,3,5- s-triazine cross-linked polymers hole
Application performance in electroluminescent diode apparatus：
Aryl polyphenol is with the injection of 1,3,5- s-triazine cross-linked polymers hole with transmission material in green organic electroluminescent
The preparation process of diode (p-PPV)：
Acetone is used successively in tin indium oxide (ITO) electro-conductive glass substrate, and detergent, deionized water and isopropanol ultrasound are clear
Wash, after oven for drying, handled 4 minutes with PLASMA (oxygen plasma), further clean electro-conductive glass.
Hole injection and transport layer HIL/HTL (the hole injection/ being related in following preparation process
Transport layer) represent, five specific preparation methods of device are as described below：
By three aryl polyphenol of the gained of embodiment 1,2,3 and the injection of 1,3,5- s-triazine cross-linked polymers hole and transmission
Material uses dmso solution respectively, in the way of spin-coating film, is individually applied on three treated ito glass pieces respectively
The three aryl polyphenol and the injection of 1,3,5- s-triazine cross-linked polymers hole and transmission material of the gained of one layer of embodiment of cloth 1,2,3
Film, hole injection therein and transport layer HIL/HTL (hole injection/transport layer) expressions, HTL
Thickness is about 30nm.By substrate, 80 DEG C of dryings remove solvent in 8 hours in vacuum drying oven, and green luminescent material p-PPV is dissolved
In dimethylbenzene (o-xylene).Then, p-PPV solution is spin-coated on and has been coated with embodiment 1, the ITO glass of 2, No. 3 sample thin films
On glass.In addition, No. 1 device is control device, hole injection/transport layer is not added with.Above-described four slice, thin pieces are 4 × 10-4Pa
Vacuum under, evaporation metal CsF (1nm)/Al (100nm) negative electrode.
Device efficient lighting area is 0.17cm2, film thickness Tencor Alfa Step-500 surface profilers survey
It is fixed.The sedimentation rate and its thickness of metal electrode evaporation are determined with Sycon Instrument thickness/speed instrument STM-100.
Except the spin coating process of layer film is injected/transmitted in aryl polyphenol and 1,3,5- s-triazine cross-linked polymers hole in atmospheric environment
Complete outer, other all links are completed in the glove box of nitrogen environment.The corresponding material source of numbering of obtained device
It is shown in Table 1.
The polymer that embodiment 7 is related to is commercially produced product, and polymer p-PPV molecular structures are：
Wherein m, n, p distinguish the amount relative amount (unit is %) of the material of three monomers in representation polymer p-PPV, take
Value is between 0 to 100.
Table 1 is that (device architecture is for hole injection/transmission performances of embodiment 1,2 and 3 resulting materials：ITO/HIL/HTL/
p-PPV/CsF/Al)
The result of table 1 shows that the material of Application Example 1,2,3, using solution spin coating method film forming, prepares organic electroluminescence hair
The hole injection of optical diode and transport layer, maximum current efficiency and maximum external quantum efficiency (2.6%) be relatively not added with hole injection/
The efficiency (0.98%) of the device of transport layer, improves effect obvious.Organic electroluminescent LED is prepared for spin coating method
Hole injection/transport layer, it is very low to open bright voltage, maximum current efficiency 6.50cd/A.This be at present on aryl polyphenol and 1,3,
The report first applied with transmission material in organic electroluminescent diode apparatus is injected in 5- s-triazine cross-linked polymers hole.
Embodiment 8：Aryl polyphenol injects organic in blueness with transmission material with 1,3,5- s-triazine cross-linked polymers hole
Application performance in electroluminescent diode apparatus
Aryl polyphenol is with the injection of 1,3,5- s-triazine cross-linked polymers hole with transmission material in green organic electroluminescent
The preparation process of diode (p-PPV)：
Acetone is used successively in tin indium oxide (ITO) electro-conductive glass substrate, and detergent, deionized water and isopropanol ultrasound are clear
Wash, after oven for drying, handled 4 minutes with PLASMA (oxygen plasma), further clean electro-conductive glass.
Hole injection and transport layer HIL/HTL (the hole injection/ being related in following preparation process
Transport layer) represent, five specific preparation methods of device are as described below：
1st, No. 2 devices：By poly- 3,4- ethylenedioxy thiophenes/poly styrene sulfonate (PEDOT:PSS aqueous solution difference)
The independent spin coating PEDOT on 2 treated ito glass pieces:PSS films (40nm), then by the material dimethyl of embodiment 1
Sulfoxide is dissolved, and in the way of spin-coating film, PEDOT is had been coated with 2:One layer of implementation is respectively coated on the ito glass of PSS layer
The material film of example 1, thickness is respectively 10nm and 30nm.By above-mentioned substrate, 80 DEG C of dryings removing in 8 hours is molten in vacuum drying oven
Agent, then PVK (PVK, 35nm) is spin-coated on the material film of embodiment 1.Then, by blue emitting material PSF
Dimethylbenzene (o-xylene) is dissolved in, PSF solution is spin-coated on PVK layers.Finally, under 4 × 10-4Pa vacuum, gold evaporation
Belong to CsF (1nm)/Al (100nm) negative electrode, element manufacturing is completed.
No. 3 devices：In preparation process, first spin coating mode prepares PEDOT:PSS (40nm)/PVK (35nm) layer, Ran Hou
PEDOT:PSF layers (10nm) is prepared on PSS/PVK layers.
No. 4 devices：In preparation process, PVK layers (35nm) are prepared in spin coating mode, then at PVK (PVK)
Upper spin coating luminescent material PSF, prepares PSF layers (10nm).
In No. 5 devices, preparation process, with the material of spin coating mode spin coating embodiment 1 on ito glass, thickness is 20nm,
Then spin coating polyvinylcarbazole layer (PVK, the 35nm) in the material layer of embodiment 1, then the spin coating luminescent material on PVK layers
PSF layers (10nm).
Device efficient lighting area is 0.17cm2, film thickness Tencor Alfa Step-500 surface profilers survey
It is fixed.The sedimentation rate and its thickness of metal electrode evaporation are determined with Sycon Instrument thickness/speed instrument STM-100.
Except the spin coating process of aryl polyphenol and 1,3,5- s-triazine cross-linked polymers hole injection/transmission material film is in atmospheric environment
Outside middle completion, other all links are completed in the glove box of nitrogen environment.
The polymer that the present embodiment 8 is related to is commercially produced product, and polymer P SF molecular structures are：
The repeat unit number of monomer in wherein n representation polymers PSF, value is between 5 to 500.
Table 2 is that (device architecture is for hole injection/transmission performances of the resulting materials of embodiment 1：ITO/HIL/HTL/PSF/
CsF/Al)
The result of table 2 shows that, with embodiment material of the present invention, solution spin coating method film forming prepares organic electroluminescent
The hole injection of diode and transport layer, maximum current efficiency and the more traditional PEDOT/ of maximum external quantum efficiency (4.26%)
PVK injects the efficiency (2.75%) with the device of transport layer as hole, improves effect obvious.
It should be noted that embodiment is not limited the scope of the present invention, within the spirit and principles of the invention
Any modifications, equivalent substitutions and improvements done etc., should be included in the scope of the protection.
Claims (8)
1. aryl polyphenol and 1, the injection of 3,5- s-triazine cross-linked polymer holes and transmission material, it is characterised in that with such as formula
Or one kind in the molecular structure of formula (II) (I)：
Wherein Ar1For aryl diphenol structure, Ar2For aryl triphenol structure, wave represents aryl diphenol or aryl triphenol and 1, and 3,
The coupled structures of 5- s-triazine.
2. aryl polyphenol described in claim 1 injects the preparation side with transmission material with 1,3,5- s-triazine cross-linked polymers hole
Method, it is characterised in that comprise the following steps：
1) it is equal by 1,3,5- in the aqueous solution that aryl polyphenol compound is added to alkali catalyst under the conditions of 0 DEG C~40 DEG C
Three polychlorostyrene piperazine quasi-molecules are dissolved in organic solvent, are added drop-wise to dropwise in aryl polyphenol compound, under the conditions of 0 DEG C~100 DEG C
React 0.5h~48h；
Described aryl polyphenol compound is aryl diphenol or the phenolic compounds of aryl three；Described aryl diphenol is containing two phenol
The aryl compound of hydroxyl；Described aryl triphenol is the aryl compound containing three phenolic hydroxyl groups；
Described alkali catalyst be sodium hydroxide, triethylamine, diisopropyl ethyl amine, potassium hydroxide, sodium carbonate, potassium carbonate and
One or more in cesium carbonate；
According to the molfraction meter of material, composition of raw materials composition is：10 parts of the equal three polychlorostyrene piperazines of 1,3,5-；Aryl Polyphenols monomer 5
~50 parts；5~150 parts of base catalyst；
2) by step 1) obtained reaction mixture poured into a large amount of deionized waters, and solution ph is adjusted to neutral with dilute acid soln,
Filtering, with water and organic solvent washing, obtains hole injection and transmission material that aryl polyphenol is crosslinked 1,3,5- s-triazine structures
Material.
3. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole
Preparation method, it is characterised in that the dilute acid soln is the one or more in hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid.
4. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole
Preparation method, it is characterised in that described aryl diphenol is the one or more in following structural formula (1)-(12)；
。
5. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole
Preparation method, it is characterised in that described aryl triphenol is following structural formula (13) and/or (14)；
。
6. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole
Preparation method, it is characterised in that the volume ratio 0.1-10 of organic solvent and water in described organic solvent and the mixed liquor of water:1.
7. the aryl polyphenol according to claim 2 or 6 is injected with transmitting material with 1,3,5- s-triazine cross-linked polymers hole
The preparation method of material, it is characterised in that described organic solvent is in tetrahydrofuran, acetone, ether, acetonitrile and dioxane
It is one or more.
8. the aryl polyphenol described in claim 1 is injected with transmission material organic with 1,3,5- s-triazine cross-linked polymers hole
In optoelectronics device the application with transmission material is injected as hole；The organic optoelectronic device includes light-emitting diodes
Pipe, organic heterojunction battery, perovskite solar cell, dye-sensitized cell or organic laser illuminating device.
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| CN201510229873.4A CN104910372B (en) | 2015-05-07 | 2015-05-07 | Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application |
| PCT/CN2015/090685 WO2016176955A1 (en) | 2015-05-07 | 2015-09-25 | Polyarylphenol and 1,3,5-triazine crosslinked polymer hole injection/transport material, preparation method for same, and applications thereof |
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| CN201510229873.4A CN104910372B (en) | 2015-05-07 | 2015-05-07 | Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application |
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| CN104910372B (en) * | 2015-05-07 | 2017-10-20 | 华南理工大学 | Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application |
| CN107930606A (en) * | 2017-11-17 | 2018-04-20 | 中南大学 | One kind is containing triazine ring and azo bond functional group porous polymer sorbing material, porous polymer catalysis material and preparation and application |
| CN109593192B (en) * | 2018-12-05 | 2020-04-03 | 中国科学院长春应用化学研究所 | Polyarylether/polyarylene sulfide with heat-activated delayed fluorescence effect and preparation method and application thereof |
| CN111384275B (en) * | 2018-12-29 | 2021-08-10 | Tcl科技集团股份有限公司 | Thin film, preparation method thereof and light-emitting diode |
| CN110283098B (en) * | 2019-07-10 | 2021-10-26 | 华南理工大学 | Star-shaped aromatized inorganic acid radical semiconductor material and preparation and application thereof |
| CN111540830B (en) * | 2020-04-30 | 2022-03-29 | 华南理工大学 | Dopamine-doped perovskite solar cell and preparation method thereof |
| CN112940241B (en) * | 2021-02-08 | 2023-09-19 | 华南师范大学 | Triazine polymer and preparation method thereof |
| CN113410480B (en) * | 2021-06-18 | 2022-07-05 | 福州大学 | Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof |
| CN114292396B (en) * | 2021-12-02 | 2023-05-09 | 南京信息工程大学 | Porous material and preparation method and application thereof |
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|---|---|---|---|---|
| US3297639A (en) * | 1963-02-05 | 1967-01-10 | Lewellyn G Picklesimer | Polyethers of triazine and polyhydric aromatic compounds |
| CN101643651A (en) * | 2009-08-25 | 2010-02-10 | 四川大学 | Macromolecular intumescent flame resistance carbonizing agent with branching and crosslinking structure and preparation method and application thereof |
| CN102181051A (en) * | 2011-04-14 | 2011-09-14 | 大连理工大学 | Hyperbranched polyarylether containing triazine structure and preparation method thereof |
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| US6225378B1 (en) * | 1999-07-01 | 2001-05-01 | Industrial Technology Research Institute | Triazine hardener and epoxy composition containing the same |
| ATE284910T1 (en) * | 2000-01-05 | 2005-01-15 | Cambridge Display Tech Ltd | POLYMERS, THEIR PRODUCTION AND USE |
| CN101586033B (en) * | 2009-06-10 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Triazine carbonific containing aromatic chain structure and preparation method |
| CN101717396A (en) * | 2009-11-27 | 2010-06-02 | 南京邮电大学 | Triazine type photonic functional material and preparation and application method thereof |
| CN104910372B (en) * | 2015-05-07 | 2017-10-20 | 华南理工大学 | Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3297639A (en) * | 1963-02-05 | 1967-01-10 | Lewellyn G Picklesimer | Polyethers of triazine and polyhydric aromatic compounds |
| CN101643651A (en) * | 2009-08-25 | 2010-02-10 | 四川大学 | Macromolecular intumescent flame resistance carbonizing agent with branching and crosslinking structure and preparation method and application thereof |
| CN102181051A (en) * | 2011-04-14 | 2011-09-14 | 大连理工大学 | Hyperbranched polyarylether containing triazine structure and preparation method thereof |
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