CN108912310B - Polyfluorene derivative, luminescent layer of light-emitting diode and preparation method of luminescent layer - Google Patents
Polyfluorene derivative, luminescent layer of light-emitting diode and preparation method of luminescent layer Download PDFInfo
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Abstract
The invention discloses a polyfluorene derivative, a luminescent layer of a light-emitting diode and a preparation method thereof. The invention carries out Suzuki polymerization reaction on fluorene of S, S-dioxo-dibenzothiophene unit to obtain the polyfluorene derivative of which the side chain contains S, S-dioxo-dibenzothiophene unit or S-oxo-dibenzothiophene unit or dibenzothiophene and derivatives thereof. According to the invention, the side chain of the polyfluorene derivative is modified with the electron transport unit, the electron transport unit is complementary with the main chain which is dominant in hole transport, and the main chain is not directly conjugated with the electron-absorbing S, S-dioxo-dibenzothiophene, so that the polymer contains the electron transport unit and the hole transport unit, the spectral purity and the stability of the polymer are maintained, the improvement of the device efficiency is facilitated, and the polymer has good solubility and can be used for preparing the light emitting layer of the polymer light emitting diode.
Description
Technical Field
The invention belongs to the technical field of organic photoelectricity, and particularly relates to a polyfluorene derivative, a light-emitting layer of a light-emitting diode and a preparation method of the light-emitting layer.
Background
In 1990, the first polymer thin film electroluminescent device prepared using conjugated polymer PPV was published in the cavendish laboratory of cambridge university, england, and thus the introduction to the study of Polymer Light Emitting Diodes (PLEDs) was formally drawn. Compared with small molecule light emitting diodes, polymer light emitting diodes have the following advantages: (1) the large-area film can be prepared by methods such as solution spin coating, roll-to-roll and the like; (2) the electronic structure and the luminous color of the conjugated polymer can be easily adjusted by changing and modifying the chemical structure; (3) the conjugated polymer can avoid crystallization through modification, and further the stability of the device is improved.
The PLED device is composed of a cathode, an anode and an intermediate organic layer, wherein the organic layer generally comprises an electron transport layer, a light emitting layer and a hole transport layer, electrons and holes are respectively injected from the cathode and the anode and respectively migrate in a functional layer, then the electrons and the holes form excitons at proper positions, the excitons migrate within a certain range, and finally the excitons emit light.
The polymer luminescent material containing S, S-dioxo-dibenzothiophene in the main chain is a star material in the research field of PLED. The projects of Yang Wei and Martin R.Bryce combine a series of high-efficiency electroluminescent polymers based on S, S-dioxo-dibenzothiophene [ chem.Mater.2008,20, 4499-4506; advanced Functional Materials,2013,23, 4366-; macromolecules,2010,43,4481 and 4488; J.Mater.chem.C,2014,2, 5587-5592 ]. However, most S, S-dioxo-dibenzothiophene-based polymers achieve higher efficiency in a two-layer device structure, usually by introducing a hole transport layer in the PEDOT, PSS and the light-emitting layer. The reason is that the introduction of the S, S-dioxo-dibenzothiophene unit can obviously reduce the HOMO energy level of the polymer, improve the hole injection barrier and reduce the hole transmission performance while reducing the LUMO energy level of the polymer and improving the electron transmission performance of the polymer, so that the carrier transmission in the polymer is unbalanced, and the efficiency and the stability of the device are limited. Meanwhile, the introduction of the S, S-dioxo-dibenzothiophene unit with strong charge absorption property can form an ICT state in the main chain, which is not beneficial to the improvement of photoluminescence efficiency, so that the key point of improving the efficiency of the S, S-dioxo-dibenzothiophene polymer device is to improve the balance of carrier transport and improve the photoluminescence efficiency.
Disclosure of Invention
The invention provides a polyfluorene derivative and a preparation method thereof, and the invention provides a light-emitting layer of a light-emitting diode and a preparation method thereof.
In order to achieve the above object, the technical solution of the present invention is as follows,
a polyfluorene derivative is provided, the side chain of the polyfluorene derivative contains S, S-dioxo-dibenzothiophene unit or S-oxo-dibenzothiophene unit or dibenzothiophene and derivatives thereof, the side chain chemical structural formula of the polyfluorene derivative is shown as (I):
in the formula, x1、x2Is a mole fraction of the unit component, and 0<x1<0.5，0≤x2<0.5，x1+x2≤0.5；
n is a repeating unit, and n is an integer between 10 and 1000;
R1、R2is alkyl with 6-30 carbon atoms, cycloalkyl with 6-30 carbon atoms or alkoxy substituted phenyl with 6-30 carbon atoms;
Ar1、Ar2is the said R1Or an S, S-dioxo-dibenzothiophene unit or a substituted S, S-dioxo-dibenzothiophene unit; ar (Ar)3Is an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
Preferably, Ar is1And Ar2Are all selected from the R1Or any one of the following chemical structural formulas or derivatives thereof:
(ii) is attached to the 9-carbon of fluorene;
R3～R5is any one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 30 carbon atoms, or an alkoxy-substituted phenyl group having 1 to 30 carbon atoms.
Preferably, Ar is3Any one selected from the following chemical structural formulas or derivatives comprising the following chemical structural formulas:
represents a ligation site;
wherein R is6Is an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.
A preparation method of polyfluorene derivatives comprises the following steps:
reacting dibenzothiophene derivative with fluorene or fluorenone or fluorenol to obtain substituted fluorene containing dibenzothiophene derivative unit, and oxidizing the substituted fluorene containing dibenzothiophene derivative unit to obtain Ar containing S, S-dioxo-dibenzothiophene derivative unit1And Ar2And then the substituted fluorene containing the S, S-dioxo-dibenzothiophene derivative unit Ar1And Ar2Substituted fluorenes of, containing R1、R2Substituted fluorenes and Ar3After the unit is subjected to Suzuki polymerization reaction, sequentially adding phenylboronic acid and bromobenzene for end-capping reaction to obtain the polyfluorene derivative with the side chain containing S, S-dioxo-dibenzothiophene unit or S-oxo-dibenzothiophene unit or dibenzothiophene and derivatives thereof.
Preferably, the temperature of the Suzuki polymerization reaction is 80-85 ℃, and the time is 24-48 hours.
Preferably, the temperature of the end-capping reaction is 80-85 ℃ and the time is 4-8 hours.
A light-emitting layer of a light-emitting diode comprising the polyfluorene derivative having a side chain containing S, S-dioxo-dibenzothiophene units or S-oxo-dibenzothiophene units or dibenzothiophene and derivatives thereof according to any one of claims 1 to 3.
A preparation method of a light-emitting layer of a light-emitting diode is characterized in that a polyfluorene derivative containing S, S-dioxo-dibenzothiophene units or S-oxo-dibenzothiophene units or dibenzothiophene and derivatives thereof in a side chain is dissolved by an organic solvent, and a film is formed by spin coating, ink-jet printing or printing.
Preferably, the organic solvent is selected from any one of xylene, chlorobenzene and dichlorobenzene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the side chain of the polyfluorene derivative is modified with the electron transmission unit, and the side chain is complementary with the main chain which is dominant in hole transmission, so that the polymer contains the electron transmission unit and the hole transmission unit, and the reduction of the energy level of the main chain and the inhibition of the generation of an ICT state are avoided, thus the carrier transmission is more balanced, more holes and electrons are effectively compounded to generate excitons, and the luminous efficiency of the material is further improved. The electron transmission unit is connected to the side chain of the polymer, has small influence on the conjugated length of the main chain of the polymer, can not form strong intramolecular charge transfer, has small influence on the luminescence spectrum of the polymer, and can better maintain the color purity, the spectral purity and the stability of the polymer.
(2) The polyfluorene derivative with the side chain containing the S, S-dioxo-dibenzothiophene unit has the advantages of double-carrier transmission characteristic and good solubility, can simplify the preparation process of the device, can be used as a luminescent layer to obtain a single-layer polymer luminescent device with higher fluorescence quantum yield, and is beneficial to improving the electroluminescent performance and the device efficiency of a polymer light-emitting diode.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of a polymer P1 film.
FIG. 2 is a photoluminescence spectrum of a polymer P1 film.
FIG. 3 is a plot of Cyclic Voltammetry (CV) for polymer P1.
FIG. 4 is a graph of the electroluminescence spectrum of polymer P1.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of Compound M1
(1) Preparation of compound 1: dibenzothiophene (11g, 60mmol), iron powder (0.17g, 3mmol) and elemental bromine (3.1mL, 60mmol) were added to a 100mL three-necked flask, and the mixture was stirred under nitrogen at room temperature for 16 hours, then quenched with aqueous sodium bisulfite, extracted three times with dichloromethane, and the solvent was removed under reduced pressure to give a crude product, which was then purified by column chromatography with a yield of about 80%.
(2) Preparation of compound 2: compound 1(3.3g, 12.5mmol) was dissolved in dry tetrahydrofuran under nitrogen and then butyllithium (3.3g, 12.5mmol) was added to a 100ml three-necked flask, stirred at-78 deg.C for 2 hours under nitrogen, then 1-bromohexane (7.4g, 45mmol) was added and the reaction was continued for 1 hour, then quenched with water and extracted three times with dichloromethane, and the solvent was removed under reduced pressure to give the crude product, which was then purified by column chromatography in about 70% yield.
(3) Preparation of compound M1: adding 2, 7-dibromofluorenone (3.38g, 10mmol), compound 2(5.53g, 30mmol), methanesulfonic acid (0.96g, 10mmol) and 50ml carbon tetrachloride into a 100ml three-neck flask, and heating to 90 ℃ under nitrogen for reaction for 12 hours; after the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the crude product was purified with petroleum ether: dichloromethane ═ 6: column chromatography with eluent of mixed solvent 1(v/v) to obtain white solid 7.62g, yield 89%, (Mass spectrum: 856.8).
The chemical reaction equation is as follows:
preparation of Compound M2
(1) Preparation of compound 3: firstly, preparing 2, 4-dimethyl benzene magnesium bromide, adding 1-bromo-2, 4-dimethylbenzene (0.56g, 3mmol), magnesium chips (2.92g, 120mmol) and 2ml of anhydrous tetrahydrofuran into a 300ml two-mouth bottle, heating to initiate Grignard reaction under the protection of nitrogen, slowly dropwise adding 100ml of anhydrous tetrahydrofuran solution dissolved with 1-bromo-2, 4-dimethylbenzene (17.95g, 97mmol), after dropwise adding, heating at 60 ℃ for 1 hour for reaction to obtain 2, 4-dimethyl benzene magnesium bromide for later use;
adding 2, 7-dibromofluorenone (10.14g, 30mmol) and 100ml anhydrous tetrahydrofuran into a 300ml two-neck flask, cooling to-78 ℃, stirring for 1 hour, adding the prepared 2, 4-dimethylbenzene magnesium bromide solution (60ml, 60mmol) into the reaction flask, continuing to react for 1 hour at-78 ℃, quenching the reaction with water, extracting the product with dichloromethane, washing the organic phase with saturated aqueous sodium chloride solution, drying over anhydrous magnesium sulfate, evaporating off the solvent, and using petroleum ether: ethyl acetate ═ 6: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and light yellow solid 7.98g is obtained, the yield is 60 percent (mass spectrum: 444.2).
(2) Preparation of compound M2: compound 3(4.44g, 10mmol), compound 2(4.03g, 15mmol) and 80ml of anhydrous dichloromethane were charged in a 150ml two-necked flask, stirred for 1 hour, added with boron trifluoride diethyl etherate (2.13g, 15mmol), and further stirred at room temperature for 12 hours; the reaction was quenched with water, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, the solvent was evaporated, and the crude product was purified by petroleum ether: dichloromethane ═ 6: column chromatography with mixed solvent of 1(v/v) as eluent to obtain white solid 4.59g, yield 66% (mass spectrum: 694.6).
The chemical reaction equation is as follows:
preparation of Compound M3
Compound M2(2.08g, 3mmol) was dissolved in 15ml of acetic acid, and 20ml of hydrogen peroxide was added thereto, followed by heating and refluxing for 6 hours; stopping reaction, cooling, extracting with deionized water and ethyl acetate, suspending the organic phase, dissolving in 10ml of toluene, precipitating in methanol (300ml), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, and precipitated again into a methanol solution, filtered and dried to obtain 1.64g of a pale yellow solid in 75% yield (mass spectrum: 726.6).
The chemical reaction equation is as follows:
example 1
Preparation of Polymer P1
Synthesis of Polymer P1: 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-bis (4- (2-ethylhexyloxy) phenyl) fluorene (248.0mg,0.3mmol), 2, 7-dibromo-9, 9-bis (4- (2-ethylhexyloxy) phenyl) fluorene (175.8mg,0.24mmol), and compound M3(48.6mg,0.06mmol) were dissolved in 10mL of toluene under nitrogen protection, followed by addition of an aqueous tetraethylhydroxylamine solution (1mL, wt% ═ 25%), palladium acetate (1mg), and tricyclohexylphosphine (2 mg); heating to 80 ℃ for reaction for 24 hours, adding phenylboronic acid (20mg) for end capping for 6 hours, and then adding bromobenzene (0.2ml) for end capping for 6 hours at 80 ℃; stopping reaction, cooling, precipitating the organic phase in methanol (200ml), filtering, drying, extracting the crude product with methanol, acetone and n-hexane successively, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, and precipitated again in a methanol solution, filtered, and dried to obtain a white fibrous polymer. GPC: mn is 109KDa, PDI is 2.32, and the polymer has high molecular weight and is beneficial to improving the luminescence property.
The ultraviolet-visible absorption spectrum of the polymer P1 film is shown in FIG. 1, and it can be seen from FIG. 1 that the maximum absorption wavelength of the polymer P1 is 393 nm;
the photoluminescence spectrum of the polymer P1 film is shown in FIG. 2, and it can be seen from FIG. 2 that the maximum emission wavelength of the polymer is 438 nm;
the Cyclic Voltammetry (CV) spectrum of the polymer P1 is shown in FIG. 3, and it can be seen from FIG. 3 that the HOMO level of the polymer P1 is-5.73 eV, and the LUMO level is-2.14 eV;
the electroluminescence spectrum of the polymer P1 is shown in FIG. 4, and it can be seen from FIG. 4 that the maximum emission wavelength is 433 nm.
Example 2
Preparation of Polymer P2
The synthesis conditions of polymer P2 were the same as for polymer P1, except that:
polymer P2: 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-bis (4- (2-ethylhexyloxy) phenyl) fluorene (248.0mg,0.3mmol), 2, 7-dibromo-9, 9-bis (4- (2-ethylhexyloxy) phenyl) fluorene (175.8mg,0.24mmol), and compound M1(41.7mg,0.06 mmol). GPC: mn is 97KDa, PDI is 3.21.
Example 3
Light emitting diode and preparation of light emitting layer thereof
Taking Indium Tin Oxide (ITO) glass with the square resistance of 10 omega, sequentially using acetone, a detergent, deionized water and isopropanol for ultrasonic cleaning, and carrying out plasma treatment for 10 minutes; spin-coating a film of polyethoxythiophene (PEDOT: PSS ═ 1:1, w/w) doped with polystyrenesulfonic acid on ITO to a thickness of 40 nm; drying the PEDOT, namely the PSS film in a vacuum oven at the temperature of 80 ℃ for 8 hours; a solution of the commercially available PFO and polymer P1 in xylene (1.5 wt.%) was then spin coated onto the surface of the PEDOT: PSS film to a thickness of 80nm as the light emitting layer.
And finally, sequentially evaporating a 1.5 nm-thick CsF layer and a 120 nm-thick metal Al layer on the luminescent layer, wherein the device structure comprises: ITO/PEDOT PSS/Polymer/CsF/Al.
TABLE 1 Polymer electroluminescent device Properties
Compared with the PFO polymer without an electron transmission unit, the P1 polymer P1 with the S, S-dioxo-dibenzothiophene unit side chain introduced has obviously improved device performance compared with the PFO polymer without the electron transmission unit, which is found by comparing the data in the single-layer polymer light-emitting device of the polymer P1 and the classical PFO polymer with the same main chain structure, and shows that the introduction of the electron transmission unit into the side chain can improve the performance of the polyfluorene derivative in the single-layer light-emitting device, and the introduction of the electron transmission unit into the side chain basically does not influence the electroluminescence spectrum of the polymer.
The present invention is not limited to the above embodiments, and various other modifications, substitutions and alterations can be made without departing from the basic technical concept of the present invention by the common technical knowledge and conventional means in the field according to the above content of the present invention.
Claims (4)
1. A polyfluorene derivative characterized by the following structure:
wherein x =0.1, and Mn =109KDa, PDI =2.32 thereof.
2. A light-emitting layer of a light-emitting diode, characterized in that the light-emitting layer comprises the polyfluorene derivative according to claim 1.
3. A method for producing a light-emitting layer of a light-emitting diode, characterized in that the polyfluorene derivative according to claim 1 is dissolved in an organic solvent and formed into a film by spin coating, ink-jet printing or printing.
4. The method according to claim 3, wherein the organic solvent is selected from any one of xylene, chlorobenzene, and dichlorobenzene.
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| CN102186800A (en) * | 2008-10-14 | 2011-09-14 | 通用电气公司 | 2,5-linked polyfluorenes for optoelectronic devices |
| CN106565960A (en) * | 2016-11-11 | 2017-04-19 | 华南理工大学 | Block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, preparation method and application thereof |
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