CN102585171A - Ether chain substituted conjugate polycationic electrolyte material and application thereof - Google Patents
Ether chain substituted conjugate polycationic electrolyte material and application thereof Download PDFInfo
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- CN102585171A CN102585171A CN2011104581240A CN201110458124A CN102585171A CN 102585171 A CN102585171 A CN 102585171A CN 2011104581240 A CN2011104581240 A CN 2011104581240A CN 201110458124 A CN201110458124 A CN 201110458124A CN 102585171 A CN102585171 A CN 102585171A
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Abstract
The invention provides an ether chain substituted conjugate polycationic electrolyte material and application thereof. Each material molecule contains a plurality of conjugate aromatic rings which have semiconductor property and are used as a main body structure, and each aromatic ring side chain is bonded with alkyl or alkoxy (or acetate or phosphate) metal cations. The material has very good electron injection or transmission capability and special solubility, avoids interface miscibility on the premise that the electron transmission performance of the material is not affected, and can be applied to an electron transmission or injection layer of an organic electroluminescent device and used as a cathode interface material for an organic solar cell.
Description
Technical field
The invention belongs to photovaltaic material applicating technology field, being specifically related to one type is the conjugated polyelectrolytes material and the application in organic electroluminescence device (OLED) and organic solar batteries (OPV) thereof of side chain with sulphonate (or acetate, phosphoric acid salt) metallic cation and alkyl (or ether chain).
Background technology
Organic polymer is as a kind of good electroluminescent material; Because it has light weight, flexibility and good film-forming properties; Simultaneously can when being manufactured with organic electroluminescence devices and organic solar batteries, adopt technology such as spin coating, spray ink Printing; Large-area preparation can be realized, and, cost of manufacture can be greatly reduced with respect to micromolecular evaporation coating technique.Thereby organic polymer ripple be widely used in aspects such as flexible flat panel display device, illumination, polymer light-emitting device and polymer solar battery.
1963; People such as M.Pope add above 100V voltage on the anthracene crystal, first observed has arrived organic electroluminescent phenomenon (J.Chem.Phys., 1963; 38; 2024), still too high driving voltage and lower luminous efficiency and life-span did not cause people's attention at that time far away from inorganic electroluminescence device.1987, Deng Qingyun (C.W.Tang) doctor proposed to prepare with vacuum vapour deposition the OLED device (Appl.Phys.Lett., 1987,52,913) of bilayer film first, and its external quantum efficiency under less than the voltage of 10V has reached 1%; People's reported first such as nineteen ninety R.H.Friend polymer LED (Nature, 1990,347,539), organic electroluminescent research has got into a brand-new stage since then.
The Deng Qingyun of Kodak (EastmanKodak) company in 1986 has proposed to adopt the organic semiconductor material with conjugated system to make organic solar cell device and has used the bi-layer devices of giving body and acceptor first.At that time, (CuPc) was with perylene diimide (perylene tetracarboxylic) had formed the bilayer structure of p type and n type organic semiconductor material to Tang between ito transparent electrode and A1 negative electrode through the vacuum evaporation CuPc.The energy conversion efficiency that device obtains under the light source irradiation of AM2 is about 1% (Appl.Phys.Lett.1986,48,183).Nineteen ninety-five Yu Gang etc. has proposed the notion of body phase heterojunction type organic solar batteries.They are with MEH-PPV and PCBM blend by a certain percentage, and having prepared structure through spin-coating method is ITO/MEH-PPV:C
60The optics of/Ca is 20mW/cm in intensity
2, wavelength is that the open circuit voltage of device (V oc) is 1.6V under the monochromatic ray irradiation of 430nm, short-circuit current (Isc) is 2mA/cm
2, the charge-trapping rate is 29%, PCE reaches 2.9% (Science, 1995,270 (15): 1789).From then on the research and development of organic solar batteries have obtained quick swift and violent development.
In order to separate from this layer better in the hole that makes the hole be injected into the HOMO track of luminescent layer material better or in active layer material, to produce; The work content of anode material should be as far as possible be complementary with the HOMO of luminescent layer material or active layer material; General anode material is the tin indium oxide (ITO) of layer of transparent now, and its work function is about 4.8 electron-volts.Yet many luminescent layer materials or active layer material HOMO energy level the 5.2-5.8 electron-volt or more than, clearly the work function of ITO and they do not match.A kind of terms of settlement is between them, to add one deck hole transport layer material, and now in the polymkeric substance photoelectric device, make land used many also success be PEDOT [EP0686662] material.
The electronic mobility of organic materials is high far away from its hole mobility usually, and injection in electronics, hole (taking-up) and transmission balance are the primary factor that obtains high efficiency organic electroluminescence device (OLED) and organic electric solar energy battery (OPV).Usually the metal A l that uses higher work content (4.2ev) is as negative electrode, and the bigger potential barrier of LOMO energy level (2.7-3.4ev) existence with many luminescent layers or active layer material is unfavorable for the injection or the taking-up of electronics.For the electronics that makes electronics be injected into the LUMO track of luminescent layer material better or in active layer material, to produce is separated from this layer better, the work content of cathode material should be as far as possible be complementary with the LUMO of luminescent layer material or active layer material.In order to realize this purpose; Usually between luminescent layer or active coating and negative electrode, add one deck electron transfer layer, carry out embellishing cathode interface, improve the injection or the taking-up of electronics; Improve carrier balance, realize high-level efficiency organic electroluminescence device (OLED) and organic electric solar energy battery (OPV).
Usually the Ca (2.9ev) of the low work content of use or Ba (2.7ev) are as embellishing cathode interface.But owing to Ca, Ba are reactive metals, all very sensitive to oxygen and steam, one side can influence the life-span of device, needs extremely expensive encapsulation on the other hand, has increased device cost.Therefore, need to excavate other embellishing cathode interface material.
Summary of the invention:
The objective of the invention is deficiency to prior art; Provide a kind of and contain sulphonate (or acetate, phosphoric acid salt) metallic cation simultaneously and the ether chain is the conjugated polyelectrolytes material of side chain; It has special solvability, under the prerequisite that does not influence its electronic transmission performance, avoids the interface miscible.
The present invention also provides said conjugated polyelectrolytes material as electron transfer layer or the application of electron injecting layer in luminous, photovoltaic (opto-electronic conversion, photaesthesia) device.
The ether chain replaces conjugation polycation electrolyte material, and its structural formula is following:
Wherein, R is an alkyl, and X is a water soluble group, and M is a metallic cation, Ar
1A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes, R
1And R
2Be ether chain, Ar
2A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes.
Said metallic cation is an alkalimetal ion.
Said alkalimetal ion is Li
+, Na
+, K
+, Rb
+, Cs
+Any one.
Said water soluble group is any one in sulfonic group, carboxyl and the phosphate.
Said electrolyte is as the electric transmission of organic electroluminescence device or the application of input horizon, and the concrete implementation of its application is: take multilayered structure between luminescent layer material and cathodic metal, to insert the polyelectrolytes film that skim contains said electrolyte.
Said electrolyte is as the application of the cathode interface material of organic solar batteries.
Said electrolyte is as the application of the cathode interface material of organic solar batteries; It is characterized in that the concrete implementation of its application is: take multilayered structure between active layer material and cathodic metal, to insert the polyelectrolytes film that skim contains said electrolyte.
Technique effect of the present invention is embodied in:
(1) polymkeric substance of the present invention generally is dissolved in the environmentally friendly solvents such as alcohol or water; Differ bigger with the luminescent layer material in the existing photoelectric device or the solvability of active layer material; Luminescent layer material or active layer material one deck can be dissolved in some conventional solvents such as toluene, THF, chloroform, methylene dichloride; Therefore when making device, adds material of the present invention and can not corrode luminescent layer or active layer material, thus enhance device stability and prolongation device work-ing life.
(2) polymkeric substance of the present invention can add skim between luminescent layer (or active coating) and cathodic metal electrode through modes such as spin coating, spray ink Printings; Need not long-time heating or ultraviolet light to change its solvability; Device preparation technology is simple, suitable a large amount of industrialization.
(3) polymkeric substance of the present invention injects or transmission realizing excellent electronics in the red, green, blue three-colour light-emitting material of which kind of band gap and any high work function metal.
(4) polymer materials of the present invention has good thermostability, and the stability of device itself also has raising greatly, in organic and macromolecular LED image display and organic solar batteries technology, the potential using value is arranged.
(5) after polymer materials of the present invention adds in luminous and the photovoltaic device as boundary material, not only do not influence other performances of device, and can also improve the efficient of device greatly.
Description of drawings
Fig. 1 is a material structure formula of the present invention.
Fig. 2 is for having or not P1 compound among the present invention as the comparison diagram of current density-brightness-voltage (J-L-V) curve of the luminescent device of electron injecting layer material prepn based on the luminescent layer material of F8BT.
Fig. 3 is for being that active layer material has or not P1 compound among the present invention as the comparison diagram of current density-voltage (J-V) curve of the solar cell device of interfacial layer material prepn based on P3HT.
Fig. 4 is for having or not P3 compound among the present invention as the comparison diagram of luminous efficiency-voltage (LE-V) curve of the luminescent device of electron injecting layer material prepn based on the luminescent layer material of F8BT.
Embodiment
Referring to Fig. 1, a kind of ether chain of the present invention replaces conjugation polycation cathode interface material, and its structure is:
Wherein, R is an alkyl, and X is water soluble group (like sulphonate, carboxylate salt, a phosphoric acid salt), and M is that metallic cation is (like Li
+, Na
+, K
+, Rb
+, Cs
+), Ar
1A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes, R
1And R
2Be ether chain, Ar
2A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes.
Ar shown in the following formula
1, Ar
2, RXM, R
1, R
2Concrete structure is as shown in table 1:
Table 1: Ar among the formula I
1, Ar
2, RXM, R
1, R
2The structure of each
The ether chain that is provided in according to the present invention replaces the structural formula of conjugation polycation electrolyte material, can list following several for example following:
Ar
1Be benzene, R is a butoxy, and XM is a sulphonate, Ar
2Be fluorenes, its structural formula is:
Perhaps Ar
1Be benzene, R is an alkoxyl group, and XM is a carboxylate salt, Ar
2Be fluorenes, its structural formula is:
Perhaps Ar
1Be thiophene, R is an alkoxyl group, and XM is a sulphonate, Ar
2Be benzene, its structural formula is:
The general preparation method of the compound that proposes among the present invention may further comprise the steps:
Side chain is the synthetic of cationic monomer 1:
With Ar with one or more hydroxyls
1Monomer is dissolved in the methyl-sulphoxide (DMSO); Sodium hydroxide with Tetrabutyl amonium bromide 50wt% under nitrogen protection adds in this solution; With 1, the methyl-sulphoxide of 4-butyl sultone (DMSO) solution dropwise adds in the reaction solution, is reflected at stirred overnight at room temperature under the nitrogen protection at last.After reaction finishes reaction solution being poured into has deposition to separate out in the acetone, filter, and get thick product with washing with alcohol and carry out recrystallization with acetone and get white solid.
Side chain is boric acid ester monomer 2 synthetic of ether chain:
In reaction flask, add the Ar that side chain has one or more ether chains
2Dibrominated monomer and THF; After temperature is reduced to-78 ℃, under nitrogen protection, slowly drip n-Butyl Lithium to reaction flask, under this temperature; React after 1 hour Virahol tetramethyl ethylene ketone boric acid ester is added in the reaction flask with syringe fast, will react then and slowly rise to room temperature reaction and spend the night.Reaction finishes the back and use chloroform extraction, organic layer with saturated common salt water washing three times after, with anhydrous sodium sulfate drying, filtration, concentrated.Thick product gets white needle-like crystals with ethyl alcohol recrystallization.
Synthesizing of conjugated polyelectrolytes material:
Further specify technical scheme of the present invention through instance below, so that understand content of the present invention better:
Embodiment 1: preparation 1,3-two bromo-5-(4-butoxy sodium sulfonate) benzene
With 3; The 5-dibromophenol is dissolved in the methyl-sulphoxide (DMSO), and the sodium hydroxide with Tetrabutyl amonium bromide 50wt% under nitrogen protection adds in this solution, at last with 1; The methyl-sulphoxide of 4-butyl sultone (DMSO) solution dropwise adds in the reaction solution, is reflected at stirred overnight at room temperature under the nitrogen protection.After reaction finishes reaction solution being poured into has deposition to separate out in the 500mL acetone, filter, and get thick product with washing with alcohol and carry out recrystallization with acetone and get white solid (productive rate: 85.6%)
Embodiment 2: preparation 2,7-hypoboric acid pinacol ester-9,9-two (2-(2-ethoxy ethoxy) ethyl) fluorenes
In two mouthfuls of flasks of 100mL, with 2,7-two bromo-9; 9-two (2-(2-ethoxy ethoxy) ethyl) fluorenes is dissolved in the dry tetrahydrofuran; The low temperature that reaction system is placed-78 ° ℃ slowly dropped to n-Butyl Lithium (2.5M in hexane) in the reaction flask under nitrogen protection, under this temperature after bath for some time; React after 1 hour Virahol tetramethyl ethylene ketone boric acid ester is added in the reaction flask with syringe fast, will react then and slowly rise to room temperature reaction and spend the night.Reaction finishes the back ethyl alcohol recrystallization and gets white solid (productive rate: 68%).
Embodiment 3: work as Ar
1Be benzene, R is a butoxy, and XM is a sulphonate, Ar
2Be fluorenes, its structural formula is distinguished as follows:
Preparation conjugated polyelectrolytes material (P1):
With purifying good 2,7-two bromo-9,9-two (4-butyl sulfonic acid sodium) fluorenes, 2; 7-hypoboric acid pinacol ester-9,9-dioctyl fluorene, yellow soda ash and palladium join in the Shi Langke reaction flask, under nitrogen protection, zero(ppm) water and THF are added reaction flask respectively; Reaction is heated to 70 ℃ and refluxed 7 days; Dialyse with semi-permeable membranes after being cooled to room temperature, after having dialysed water is removed the gained solid, use normal hexane, ETHYLE ACETATE, methyl alcohol to carry out the Suo Shi extracting successively.Revolve the steaming methanol extract liquid at last and get straight product (productive rate: 90.2%).
Embodiment 4: preparation 1,4-two bromo-3,6-two (2-(2-ethoxy ethoxy) ethyl carboxylic acid sodium) benzene
With 1, the sodium hydroxide that 4-two bromo-3,6-two (2-(2-ethoxy ethoxy) ethyl carboxylic acid) benzene add 50wt% adds in this solution and stirred 4 hours, has deposition to separate out, and filters, and carries out recrystallization with ethanol and get white solid (productive rate: 81.0%)
Embodiment 5: work as Ar
1Be benzene, R is an alkoxyl group, and XM is a carboxylate salt, Ar
2Be fluorenes, its structural formula is:
Preparation conjugated polyelectrolytes material (P2):
With purifying good 1; 4-two bromo-3,6-two (2-(2-ethoxy ethoxy) ethyl carboxylic acid sodium) benzene, 2,7-hypoboric acid pinacol ester-9; 9-two (2-(2-ethoxy ethoxy) ethyl) fluorenes, yellow soda ash and palladium join in the Shi Langke reaction flask; Under nitrogen protection, zero(ppm) water and THF are added reaction flask respectively, reaction is heated to 70 ℃ and refluxed 7 days, dialyses with semi-permeable membranes after being cooled to room temperature; After having dialysed water is removed the gained solid, use normal hexane, ETHYLE ACETATE, methyl alcohol to carry out the Suo Shi extracting successively.Revolve the steaming methanol extract liquid at last and get straight product (productive rate: 87.4%).
Embodiment 6: preparation 4,7-two bromo-5,6-two (4-butoxy sodium sulfonate) diazosulfide
With 4,7-two bromo-5,6-dihydroxyl benzo thiadiazoles is dissolved in the absolute ethyl alcohol, adds sodium methylate, under nitrogen protection, is heated to 70 ℃, and then with 1, the 4-butyl sultone dropwise adds in the reaction solution, is reflected at the nitrogen protection refluxed and spends the night.After reaction finishes reaction solution being poured into has deposition to separate out in the 500mL acetone, filter, and get thick product with washing with alcohol and carry out recrystallization with acetone and get white solid (productive rate: 80.3%)
Embodiment 7:Ar
1Be diazosulfide, R is a butoxy, and XM is a sulphonate, Ar
2Be fluorenes, its structural formula is:
Preparation conjugated polyelectrolytes material (P3):
With purifying good 4,7-two bromo-5,6-two (4-butoxy sodium sulfonate) diazosulfide, 2; 7-hypoboric acid pinacol ester-9; 9-dioctyl fluorene, yellow soda ash and palladium join in the Shi Langke reaction flask, under nitrogen protection, zero(ppm) water and THF are added reaction flask respectively, and reaction is heated to 70 ℃ and refluxed 7 days; Place unsaturated carbonate lithium solution to dialyse 5 days reaction solution with semi-permeable membranes after being cooled to room temperature; Then with it placing deionized water dialysis 7 days, after having dialysed water is removed the gained solid, use normal hexane, ETHYLE ACETATE, methyl alcohol to carry out the Suo Shi extracting successively.Revolve the steaming methanol extract liquid at last and get straight product (productive rate: 93.3%).
Be application example below:
Embodiment 8: ito glass is used micron order ITO scavenger specially, deionized water, acetone and Virahol ultrasonic cleaning successively, and it is subsequent use that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO uses UV-O
3About 10 minutes of plasma treatment.Available from Bayer company, impact plies is with the spin coating of sol evenning machine (KW-4A) high speed with PEDOT:PSS aqueous dispersions (about 1%) in selection, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.In white vase, after the weighing, change luminescent material F8BT over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve, with 0.22 micron membrane filtration.The luminescent layer optimum film thickness is the 70-90 nanometer.Thickness is measured with the TENCORALFA-STEP-500 surface profiler.P1 is dissolved in methyl alcohol, be mixed with the solution of 0.5mg/ml concentration, with 0.22 micron membrane filtration.It is spin-coated on the luminescent layer F8BT about 10 nanometers of its thickness with sol evenning machine.After in the vacuum filtration storehouse, draining, aluminium electrode vapor deposition vacuum tightness in vacuum plating unit reaches 3 * 10
-4Accomplish when Pa is following.All preparation processes are all carried out in the glove box of nitrogen inert atmosphere is provided.The I-E characteristic of device, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated photodiode.Measuring result is as shown in table 1, and table 1 is based on F8BT green glow polymkeric substance, with the electroluminescent properties of P1 as the device of electron injecting layer.
Voltage, luminosity, the current efficiency value of each device during the maximum external quantum efficiency of table 1
Fig. 2 is for having or not P1 compound among the present invention as the comparison diagram of current density-brightness-voltage (J-L-V) curve of the luminescent device of electron injecting layer material prepn based on the luminescent layer material of F8BT; ■ and represent that respectively structure is device brightness-voltage and current density-voltage relationship of ITO/PEDOT:PSS/F8BT/Al among the figure; Among the figure ● with zero represent that respectively structure is device brightness-voltage and current density voltage relationship of ITO/PEDOT:PSS/F8BT/P1/Al; By curve among the figure can know add the P1 compound as electron injecting layer after, the brightness of device all has significantly and improves.
Embodiment 9: ito glass is used micron order ITO scavenger specially, deionized water, acetone and Virahol ultrasonic cleaning successively, and it is subsequent use that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO uses UV-O
3About 10 minutes of plasma treatment.Available from Bayer company, impact plies is with the spin coating of sol evenning machine (KW-4A) high speed with PEDOT:PSS aqueous dispersions (about 1%) in selection, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.In white vase, after the weighing, change donor material P3HT and acceptor material PCBM over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve blend, with 0.22 micron membrane filtration.Thickness is measured with TENCOR ALFA-STEP-500 surface profiler.P1 is dissolved in methyl alcohol, be mixed with the solution of 0.5mg/ml concentration, with 0.22 micron membrane filtration.It is spin-coated on the luminescent layer P3HT about 10 nanometers of its thickness with sol evenning machine.After in the vacuum filtration storehouse, draining, aluminium electrode vapor deposition vacuum tightness in vacuum plating unit reaches 3 * 10
-4Accomplish when Pa is following.All preparation processes are all carried out in the glove box of nitrogen inert atmosphere is provided.The structure of this organic solar batteries device is: ITO/PEDOT (40nm)/P3HT:PCBM (80nm)/P1 (10nm)/Al.
Embodiment 10: with ito glass use successively micron order ITO scavenger specially,, deionized water, acetone and Virahol ultrasonic cleaning, it is subsequent use that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO uses UV-O
3About 10 minutes of plasma treatment.Available from Bayer company, impact plies is with the spin coating of sol evenning machine (KW-4A) high speed with PEDOT:PSS aqueous dispersions (about 1%) in selection, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.In white vase, after the weighing, change luminescent material F8BT over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve, with 0.22 micron membrane filtration.The luminescent layer optimum film thickness is the 70-90 nanometer.Thickness is measured with TENCOR ALFA-STEP-500 surface profiler.P2 is dissolved in methyl alcohol, be mixed with the solution of 0.5mg/ml concentration, with 0.22 micron membrane filtration.It is spin-coated on the luminescent layer F8BT about 10 nanometers of its thickness with sol evenning machine.After in the vacuum filtration storehouse, draining, aluminium electrode vapor deposition vacuum tightness in vacuum plating unit reaches 3 * 10
-4Accomplish when Pa is following.All preparation processes are all carried out in the glove box of nitrogen inert atmosphere is provided.The I-E characteristic of device, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated photodiode.Measuring result is as shown in table 2, and table 2 is based on F8BT green glow polymkeric substance, with the electroluminescent properties of P2 as the device of electron injecting layer.
Voltage, luminosity, the current efficiency value of each device during the maximum external quantum efficiency of table 2
Fig. 3 is for being that active layer material has or not P1 compound among the present invention as the comparison diagram of current density-voltage (J-V) curve of the solar cell device of interfacial layer material prepn based on P3HT; ■ representes that structure is device current density-voltage relationship of ITO/PEDOT:PSS/P3HT/Al among the figure; representes that structure is device current density-voltage relationship of ITO/PEDOT:PSS/P3HT/P1/Al among the figure; By curve among the figure can know add the P1 compound as the cathode interface layer after, the current density of device all has significantly and improves.
Embodiment 11: with ito glass use successively micron order ITO scavenger specially,, deionized water, acetone and Virahol ultrasonic cleaning, it is subsequent use that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO uses UV-O
3About 10 minutes of plasma treatment.Available from Bayer company, impact plies is with the spin coating of sol evenning machine (KW-4A) high speed with PEDOT:PSS aqueous dispersions (about 1%) in selection, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.In white vase, after the weighing, change luminescent material F8BT over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve, with 0.22 micron membrane filtration.The luminescent layer optimum film thickness is the 70-90 nanometer.Thickness is measured with TENCOR ALFA-STEP-500 surface profiler.P3 is dissolved in methyl alcohol, be mixed with the solution of 0.5mg/ml concentration, with 0.22 micron membrane filtration.It is spin-coated on the luminescent layer F8BT about 10 nanometers of its thickness with sol evenning machine.After in the vacuum filtration storehouse, draining, aluminium electrode vapor deposition vacuum tightness in vacuum plating unit reaches 3 * 10
-4Accomplish when Pa is following.All preparation processes are all carried out in the glove box of nitrogen inert atmosphere is provided.The I-E characteristic of device, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated photodiode.Measuring result is as shown in table 3, and table 3 is based on F8BT green glow polymkeric substance, with the electroluminescent properties of P3 as the device of electron injecting layer.
Voltage, luminosity, the current efficiency value of each device during the maximum external quantum efficiency of table 3
Fig. 4 is for having or not P3 compound among the present invention as the comparison diagram of luminous efficiency-voltage (LE-V) curve of the luminescent device of electron injecting layer material prepn based on the luminescent layer material of F8BT; ■ representes that structure is device luminous efficiency-voltage relationship of ITO/PEDOT:PSS/F8BT/Al among the figure; Among the figure ◆, ▲ with ● represent that respectively P3 concentration in methyl alcohol is that 1.5mg/ml, 1.0mg/ml, 0.5mg/ml resulting structures are device luminous efficiency-voltage relationship of ITO/PEDOT:PSS/F8BT/P3/Al; By curve among the figure can know add the P3 compound as electron injecting layer after; The efficient of device all has significantly and to improve, and when the concentration of P3 is 0.5mg/ml obtained device most effective.
Claims (8)
1. the ether chain replaces conjugation polycation electrolyte material, it is characterized in that its structural formula is following:
Wherein, R is an alkyl, and X is a water soluble group, and M is a metallic cation, Ar
1A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes, R
1And R
2Be ether chain, Ar
2A kind of in benzene, fluorenes, diazosulfide, pyridine, pyrroles, thiophene, triphenylamine, dipyridyl, the spiral shell fluorenes.
2. ether chain according to claim 1 replaces conjugation polycation electrolyte material, it is characterized in that said metallic cation is an alkalimetal ion.
3. ether chain according to claim 2 replaces conjugation polycation electrolyte material, it is characterized in that said alkalimetal ion is Li
+, Na
+, K
+, Rb
+, Cs
+Any one.
4. replace conjugation polycation electrolyte material according to claim 1 and 2 described ionogen material ether chains, it is characterized in that said water soluble group is any one in sulfonic group, carboxyl and the phosphate.
5. any said electrolyte of claim 1～4 is as the electric transmission of organic electroluminescence device or the application of input horizon.
6. electrolyte according to claim 5 is as the electric transmission of organic electroluminescence device or the application of input horizon; It is characterized in that the concrete implementation of its application is: take multilayered structure between luminescent layer material and cathodic metal, to insert the polyelectrolytes film that skim contains said electrolyte.
7. any said electrolyte of claim 1～4 is as the application of the cathode interface material of organic solar batteries.
8. according to of the application of any said electrolyte of claim 7 as the cathode interface material of organic solar batteries; It is characterized in that the concrete implementation of its application is: take multilayered structure between active layer material and cathodic metal, to insert the polyelectrolytes film that skim contains said electrolyte.
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| CN107706318A (en) * | 2017-10-16 | 2018-02-16 | 深圳市华星光电半导体显示技术有限公司 | Electron transfer layer ink-jet printing ink and preparation method thereof |
| CN110698654A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院长春应用化学研究所 | Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107706318A (en) * | 2017-10-16 | 2018-02-16 | 深圳市华星光电半导体显示技术有限公司 | Electron transfer layer ink-jet printing ink and preparation method thereof |
| WO2019075866A1 (en) * | 2017-10-16 | 2019-04-25 | 深圳市华星光电半导体显示技术有限公司 | Electron transport layer inkjet printing ink and preparation method therefor |
| CN107706318B (en) * | 2017-10-16 | 2020-06-26 | 深圳市华星光电半导体显示技术有限公司 | Electronic transmission layer ink-jet printing ink and preparation method thereof |
| US10781326B2 (en) | 2017-10-16 | 2020-09-22 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Ink-jet printing ink of an electron transport layer and its manufacturing method |
| CN110698654A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院长春应用化学研究所 | Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof |
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