CN105860032A - Organic semiconductor materials containing 2,9-dialkyl-6-alkoxy phenanthridine unit and preparation method and application thereof - Google Patents

Organic semiconductor materials containing 2,9-dialkyl-6-alkoxy phenanthridine unit and preparation method and application thereof Download PDF

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CN105860032A
CN105860032A CN201610116838.6A CN201610116838A CN105860032A CN 105860032 A CN105860032 A CN 105860032A CN 201610116838 A CN201610116838 A CN 201610116838A CN 105860032 A CN105860032 A CN 105860032A
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phenanthridines
dialkyl
alkoxyl
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CN105860032B (en
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黄飞
黄允平
应磊
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses organic semiconductor materials containing 2,9-dialkyl-6-alkoxy phenanthridine and a preparation method and an application thereof. The organic semiconductor materials are prepared by carrying out a reaction of 2,9-dialkyl-6-alkoxy phenanthridine halogenated derivatives and a monomer containing an aromatic group structure under a metal catalyst, wherein the aromatic group and a 2,9-dialkyl-6-alkoxy phenanthridine unit are connected in a conjugate manner. The invention discloses a method for synthesis of 2,9-dialkyl-6-alkoxy phenanthridine by a phenanthridone isomerization reaction; a series of organic semiconductor materials containing the 2,9-dialkyl-6-alkoxy phenanthridine unit are synthesized and are applied in the field of organic optoelectronic devices, and solar cell devices with high open circuit voltage and deep blue polymer blue light devices are obtained.

Description

A kind of organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit and Its preparation method and application
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to a class and contain 2,9-dialkyl group-6-alkoxyl phenanthridines Organic semiconducting materials of unit and preparation method thereof with it in the application of organic photoelectric technical field.
Background technology
Organic photoelectrical material, by feat of the Photophysics of its uniqueness, has light weight, and processing is simple, low cost and energy Make the plurality of advantages such as large-area flexible device, obtain vast concern during the decade at this.
In terms of organic photovoltaic cell, seminar's report monolayer has been had this year to gather in Nature Communication Compound cell power conversion efficiency has been over 10% (DOI:10.1038/ncomms6293), this imply that organic sun electricity Will there be wide commercial promise in pond.But relative to inorganic solar cell, the energy conversion efficiency of organic photovoltaic cell is the most inclined Low, this forces each Research Team still to put into a lot of energy for this.Except device architecture, processing technology are continued to optimize, Scientific research personnel the most constantly researches and develops new photoactive layer material, fundamentally to improve the efficiency of organic photovoltaic cell.Affect organic The parameter of efficiency of solar cell has short circuit current, fill factor, curve factor, also open-circuit voltage.Wherein the above two can pass through optimised devices Structure optimize with processing technology, open-circuit voltage is the most substantially fixed against the structure optimization of light active material and improves, such as, press The HOMO energy level of low material.To this end, the method that researcher always searches for reducing polymer HOMO energy level.
Organic Light Emitting Diode, by feat of advantages such as low cost, low-power consumption, high color rendering index (CRI)s, shows to dive in huge market Power, is in depth studied over 20 years at this for this electroluminescent material.Polyfluorene is readily synthesized by feat of it, preparation cost is low With advantages such as higher fluorescence quantum efficiencies, it is referred to as star's material of blue light frequency-doubling material.Due to the 9-in polyfluorene structure Position carbon atom easily produces Fluorenone during device works so that it is luminescent spectrum is unstable, and the emission peak of green glow occurs. People, by S, the S-dioxo-dibenzothiophene unit that adulterates in polyfluorene, make exciton on S, S-dioxo-dibenzothiophene unit Compound, to prevent fluorenes unit to be converted into Fluorenone when excited state.But the electron-withdrawing power of S, S-dioxo-dibenzothiophene unit Relatively strong, directly contribute the polymer energy band after doping narrower, spectrum is the most blue.It is necessary to find a kind of ratio S for this, S-dioxy- Weak and the stable structure of dibenzothiophenes electron-withdrawing power is as the doping unit of polyfluorene, to improve the stability of blue-light device Excitation with blue light.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of 2,9-dialkyl group-6-alkoxyl phenanthridines unit organic Semi-conducting material and preparation method and application.
The purpose of the present invention is achieved through the following technical solutions.
A kind of containing 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, described organic semiconducting materials Structural formula is as shown in Equation 1:
Wherein, x, y are respectively in described organic semiconducting materials 2,9-dialkyl group-6-alkoxyl phenanthridines unit and aromatic radical The relative amount of group Ar；M is the number of π unit；R1It it is the alkyl of 1 to 30 carbon numbers；R2For hydrogen atom or 1 to 30 The alkyl of carbon number；N is the degree of polymerization of described organic semiconducting materials；
Ar is for replacing or unsubstituted group, and wherein, substituted radical is ethenylidene, ethynylene, monocycle arlydene, The miscellaneous Asia of dicyclo arlydene, three rings and the arlydene of above ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and above ring Aryl, and the group formed by singly linked 2-6 arlydene.Ar is being total to of electron deficiency conjugate unit or electron rich Yoke unit, wherein, electron deficiency conjugate unit is diazosulfide, benzotriazole, naphtho-thiadiazoles, aphthotriazoles, pyrrolo- Pyrroledione, indigo, bioxindol, quinoxaline, benzene-naphthalene diimide, imidodicarbonic diamide, thieno acid imide, quinoxaline etc., rich electricity Son conjugate unit be benzene, naphthalene, anthracene, phenanthrene, pyrene, aphthacene, Benzo[b, fluorenes, spiral shell fluorenes, indane fluorenes, pyrroles, benzopyrrole, two Aniline, the double thiophene of triphenylamine, carbazole, indole carbazole, thiophene, bithiophene, three bithiophenes, benzothiophene, thieno hexichol, benzo Fen, furan, benzofuran, benzo Coumarin etc..
π is connection 2, the conjugate unit of 9-dialkyl group-6-alkoxyl phenanthridines unit unit and aromatic group Ar, for benzene, naphthalene, Thiophene, bithiophene, selenophen, tellurium fen, furan, pyrroles, thiophene are coughed up, thiazole, oxazole, triazole or other contain carbon-carbon double bond, carbon nitrogen Any one in the conjugate unit of key.
Described 0 < x < 1,0 < y < 1, x+y=1；M is the natural number of 0 to 10000；N is the natural number of 1 to 10000.
Further, described R1For straight chain, side chain or the cyclic alkyl chain of 1-30 carbon atom, one of them or many Individual carbon atom is replaced by oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group, nitro, one or Multiple hydrogen atoms are by halogen atom, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro Replace；R2For hydrogen atom or the straight chain of 1-30 carbon atom, side chain or cyclic alkyl chain, wherein one or more carbon atom quilts Oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, and one or more hydrogen are former Son is replaced by halogen atom, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
Further, the example of suitable aromatic group Ar includes but not limited to such as lower unit or substituted such as lower unit:
R in structure above is the alkyl of hydrogen or 1-30 carbon atom, and wherein one or more carbon atoms are former by oxygen Son, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, one or more hydrogen atom quilts Halogen atom, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace.
Further, the example of suitable π unit includes but not limited to such as lower unit or substituted such as lower unit:
R in structure above is the alkyl of hydrogen or 1-30 carbon atom, wherein one or more carbon atoms by oxygen atom, Thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, and one or more hydrogen atoms are former by halogen Son, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace.
The effect of Ar group and π unit is: use different Ar groups and π unit, can be to obtained organic half The optical property of conductor material effectively regulates and controls；Can be by the further modification to Ar group in derivant and π unit, system The standby high performance organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit.
The invention provides the simple conjunction of a kind of organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit One-tenth method.
The invention provides a kind of organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit organic too Application in positive electricity pond and Organic Light Emitting Diode.
The organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit that the present invention provides is by the following method Prepare:
1, by the halogen of biphenyl lactams isomerization in the basic conditions synthesis 2,9-dialkyl group-6-alkoxyl phenanthridines unit Change derivant.
2, metal catalyzed coupling reaction: containing above-mentioned Ar or π-Ar-π, will there is metal coupling reactive functional Monomer and 2, the halide derivative of 9-dialkyl group-6-alkoxyl phenanthridines unit reacts under metallic catalyst, obtains functionalization Containing the 2 of Ar or π-Ar-π structure, 9-dialkyl group-6-alkoxyl phenanthridine derivatives, in this step can be different by changing Aromatic group Ar structure and π unit, that designs different Ar or π-Ar-π structures has metal catalyzed coupling reaction activity official's energy The monomer of group, such that it is able to regulation gained contains 2, the photoelectricity of 9-dialkyl group-6-alkoxyl phenanthridines unit organic semiconducting materials Performance, prepares a series of containing 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines, and is applied to organic sun electricity In pond device and Organic Light Emitting Diode.
Little molecule and polymer is characterized by nuclear magnetic resonance, NMR (NMR), mass spectrum (MS) or gel permeation chromatography (GPC) etc. Material structure, characterizes their electrochemical properties by cyclic voltammetry, by ultraviolet-visible spectrometer test polymer material The spectral quality of material, characterizes the luminescent properties of polymer by photoluminescence spectra, is prepared as photoelectric device simultaneously and characterizes it Photoelectric properties.
The synthesis organic photovoltaic cell active layer when 2,9-dialkyl group-6-alkoxyl phenanthridines unit and electron deficiency unit copolymerization During material, cyclic voltammetry test shows that this kind of material has deeper HOMO value, is conducive to obtaining high open-circuit voltage, is suitable to It is applied in fields such as organic photovoltaic cells；Ultraviolet-visible absorption spectroscopy shows that this kind of material has wider absorption, absorbs While reach about 600 nanometers, this shows that this kind of material likely can have preferable application prospect at organic sun laminated cell.
The synthesis Organic Light Emitting Diode activity when 2,9-dialkyl group-6-alkoxyl phenanthridines unit and electron rich unit copolymerization During layer material, cyclic voltammetry test show containing organic semiconducting materials there is deeper HOMO value, energy gap reaches 3.11eV； The absworption peak using fluorescence spectrum to record its solution is 414nm, and the emission peak of thin film is 429nm；The emission peak of thin film is 429 to receive Rice, the edge of the fluorescence emission spectrum of thin film is in 500 nanometers, it can be seen that PFPO Yu PFPO88 is all the indigo plant that excitation is the highest Light-emitting material.
With prior art ratio, main advantages of the present invention are:
1, the present invention make use of lactams group isomerization to synthesize 3,8-bis-bromo-2,9-dialkyl group-6-alcoxyl cleverly Base phenanthridines unit, synthetic route is simple, is easily purified.
2, the present invention containing 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, introduce functionalization Aromatic group Ar and π unit, successfully by this kind of materials application in organic photovoltaic cell and Organic Light Emitting Diode.
3,2 are utilized, the weak electron withdrawing properties of 9-dialkyl group-6-alkoxyl phenanthridines unit so that polymer solar cells Open-circuit voltage is improved, and reaches 0.9V, and optimizes the interaction between polymer chain, improves the mobility of material； Improve the spectrum stability of Organic Light Emitting Diode and the excitation of blue light.
Accompanying drawing explanation
Fig. 1 is chloroformic solution and the film absorption spectrum of polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88 Figure.
The cyclic voltammogram of Fig. 2 polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88.
Fig. 3 is solar cell device J-V curve prepared by polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88 Figure.
Fig. 4 is the hole diode component J of PDBTPO and PDBTPO881/2-V characteristic curve diagram.
Fig. 5 is absorption and the emission spectrum figure of the opposed polarity solution of polymer P FPO and thin film.
Fig. 6 is the cyclic voltammogram of polymer P FPO.
Fig. 7 is the opposed polarity solution of polymer P FPO88 and film absorption and emission spectrum figure.
Fig. 8 is the cyclic voltammogram of polymer P FPO88.
Fig. 9 is the light emitting diode performance diagram of polymer P FPO.
Figure 10 is polymer P FPO current efficiency curve chart.
Figure 11 is the light emitting diode performance diagram of polymer P FPO88.
Figure 12 is polymer P FPO88 current efficiency curve chart.
Detailed description of the invention
Following specific embodiment is expanded on further the present invention, is only to help every reader to be better understood from the present invention's Content, specifically includes materials synthesis, characterizes and prepare with device, but these specific embodiments limit the present invention never in any form Protection domain.
In the practice of the present invention, all solvents are AG or chromatographic grade, and reaction is carried out under an ar atmosphere.As do not pointed out, Agents useful for same is all by being either commercially available.
Embodiment 1, the bromo-6-of 3,8-bis-((2-octyldodecyl) epoxide) phenanthridines (referred to as Br2-PO) synthesis
Chemical reaction flow process is shown below, and concrete reactions steps and reaction condition are as follows:
Wherein, (I) chromic acid, glacial acetic acid, 60 DEG C of (II) sodium azides, concentrated sulphuric acids, ice bath 4 hours；(III) 2-octyl group ten Dioxane bromine, potassium carbonate, DMF, refluxes 12 hours.
(1) by 2,7 dibromo fluorenes (19.5g, 60mmol) are dissolved in 400ml glacial acetic acid stirring, add chromic acid (18.1g, 180mmol) post-heating to 60 DEG C, reaction overnight, is poured in trash ice in second day, is washed filter cake 3 after filtration with water by reaction Secondary, dry filter cake and obtain yellow solid (compound 1,19.1g, productivity 95%).Raw material 2,7 dibromo fluorenes is ordered from Aldrich Purchase.
(2) by 2,7-dibromo fluorenone (compound 1,2.36g, 7mmol) is dissolved in 50ml concentrated sulphuric acid, in ice bath in batches Add sodium azide 600mg, 10mmol altogether.Reaction is stirred 4 hours after adding at 0 DEG C by sodium azide.Reaction will after terminating Reactant liquor is poured in trash ice, product is collected by filtration, obtains brown solid (compound 2,1.95g, productivity 76%) after washing product.
(3) under argon shield, compound 2 (3.53g, 10mmol) is dissolved in 50ml DMF, and adds grinding Potassium carbonate powder (2.76g, 20mmol).After reaction system is heated to 110 DEG C, it is slowly added in reaction system with syringe 2-octyldodecyl bromine (3.61g, 10mmol), reacts 12 hours in 110 DEG C after addition.After completion of the reaction system is cooled down To room temperature, pour ethyl acetate 100ml into, wash 3 times with saline, after being dried organic facies with anhydrous magnesium sulfate, be spin-dried for, gained solid With petroleum ether as eluant, post crossed by silica gel, obtains Br2-PO, 2.76g, productivity 43%.
Embodiment 2,3,8-bis-bromo-2,9-dioctyl-6-((2-octyldodecyl) epoxide) phenanthridines (referred to as Br2- PO88) synthesis
Wherein, (I) ethylene glycol, trimethyl orthoformate, toluene, p-methyl benzenesulfonic acid, backflow；(II) n-octane bromide, magnesium chips, Oxolane, Ni (dppf) Cl2, it is heated to reflux two days, 2M HCl；(III) bromine, iron powder, chloroform；(IV) Hydrazoic acid,sodium salt, dense sulfur Acid；(V) 2-octyldodecyl bromide, potassium carbonate, DMF, refluxes 12 hours.
(1) 3,6 dibromo fluorenes raw material fluorenes are ordered from Aldrich.
(2) synthesis of compound 4 [3,6 dibromo spiral shells [fluorenes 9,2'[1,3] dioxolanes]
By compound 3 (10g, 30mmol), ethylene glycol 8ml, p-methyl benzenesulfonic acid 0.05g is dissolved in the toluene of 200ml, logical Add trimethyl orthoformate 9g after argon 10min, be heated to reflux one day.It is 10% that reactant liquor is used mass fraction by second day After sodium hydroxide solution washs three times, after being dried organic facies with anhydrous magnesium sulfate, it is spin-dried for, obtains product 10.6g, productivity 93%.
(3) synthesis of compound 5 [3,6 dioctyl Fluorenone]
5g magnesium chips is dispersed in 200ml anhydrous and oxygen-free THF, is slowly added to n-octane bromide (40g, 207mmol) and causes Reaction.It is heated to the 4h that refluxes after addition, obtains Grignard reagent.Additionally prepare compound 4 (34.36g, 90mmol) in 200ml THF is dissolved in an other flask, adds Ni (dppf) Cl22.5g.Grignard reagent is poured in substrate by ice bath, then It is heated to reflux two days.Adding 100ml 2M hydrochloric acid solution cancellation reaction two days later, stirring at normal temperature adds dichloromethane extraction after half a day Take third-order reaction liquid.After organic facies mixing, addition anhydrous magnesium sulfate is dried and is spin-dried for, with petroleum ether: dichloromethane=5:1 crosses silica gel Post.Crude product ethyl alcohol recrystallization, obtains product 22.9g, productivity 63%.
(4) synthesis of compound 6 [the bromo-3,6 dioctyl Fluorenones of 2,7-bis-]
Compound 5 (4.04g, 10mmol) is dissolved in 100ml chloroform, adds 0.2g reduced iron powder.In ice bath past Reaction system is slowly added to 3.52g bromine.Add stirring at normal temperature 4h after bromine.Reaction rear sodium sulfite and dichloro completely Methane extraction product.After organic facies mixing, addition anhydrous magnesium sulfate is dried and is spin-dried for, with petroleum ether: dichloromethane=5:1 crosses silica gel Post, obtains product 4.38g, productivity 78%.
(5) synthesis of compound 7 [3,8 dibromo 2,9 dioctyl phenanthridines 6 (5H) ketone]
Compound 6 (2.81g, 5mmol) is dissolved in 50ml concentrated sulphuric acid, ice bath is dividedly in some parts Hydrazoic acid,sodium salt altogether 650mg, it can be observed that have gas to release during reaction.After ice bath stirring 4h, then release without gas, by reaction system It is poured slowly in trash ice, filters, be washed with deionized filter cake three times, after drying, directly carry out next step reaction.Obtain product 1.73g, productivity 60%.
(6) synthesis of Br2-PO88 [3,8 dibromo 2,9 dioctyl 6 ((2 octyldodecyl) epoxide) phenanthridines]
Compound 7 (2g, 3.46mmol) is dissolved in 25mlDMF, adds 1.38g potassium carbonate, 0.3g tetra-n-butyl iodine Change ammonium, be heated to backflow under nitrogen protection, the most slowly instill 2-octyldodecyl bromide (1.8g, 5mmol).Reflux 12 little Shi Hou, extracts three times with ethyl acetate 50ml with saturated aqueous common salt, and after organic facies mixing, addition anhydrous magnesium sulfate is dried and is spin-dried for, Cross silicagel column with petroleum ether, obtain product 1.21g, productivity 41%.
Embodiment 3, the synthesis of polymer P DBTPO
Polyreaction flow process is shown below, and concrete steps and reaction condition are as follows:
Wherein, (I) chlorobenzene, Pd2(dba)3, P (o-tol)3, microwave reaction, 140 DEG C, 45 minutes.
Weigh monomer Br2-PO (61.3mg, 0.1mmol), monomer DBT (88.2mg, 0.1mmol) in microwave reaction pipe, Add chlorobenzene (3mL), logical argon 20 minutes.It is subsequently added catalyst Pd2(dba)3(3mg) and part P (o-tol)3(7mg), logical Argon makes to be full of in reaction tube argon, builds lid, carries out microwave reaction, reacts 45 minutes in 140 DEG C.Reaction terminates, will be anti- Answer drop to enter precipitation polymer in methanol, then polymer methanol, acetone, normal hexane are washed in apparatus,Soxhlet's, mistake Filter, finally dries polymer in vacuum drying oven, finally gives 89mg polymer (PDBTPO), productivity 87%.With height The molecular weight that temperature GPC (polystyrene is standard specimen) records is Mn=15.1kDa, PDI=1.6.
Embodiment 4, the synthesis of polymer P DPPPO
Polyreaction flow process is shown below, and concrete steps and reaction condition are as follows:
Wherein (I) chlorobenzene, Pd2(dba)3, P (o-tol)3, potassium phosphate, A336, water, 100 DEG C, 2 days.
Weigh monomer Br2-PO (61.3mg, 0.1mmol), monomer DPP (77.6mg, 0.1mmol), in reaction tube, add Chlorobenzene (3mL), potassium phosphate 42.4mg, water 0.5ml, A3361 drip, and lead to argon 20 minutes.It is subsequently added catalyst Pd2(dba)3 (3mg) and part P (o-tol)3(7mg), logical argon makes to be full of in reaction tube argon, builds lid, and oil bath is heated, in 100 DEG C React two days.Reaction terminates, and reactant liquor instills precipitation polymer in methanol, then by polymer methanol, acetone, normal hexane Apparatus,Soxhlet's washs, filtering head, finally polymer is dried in vacuum drying oven, finally give 82mg polymer (PDBTPO), productivity 87%.The molecular weight recorded with high temperature GPC (polystyrene is standard specimen) is Mn=21.1kDa, PDI= 2.3。
Embodiment 5, the synthesis of polymer P FPO
Polyreaction flow process is shown below, and concrete steps and reaction condition are as follows:
Wherein (I) chlorobenzene, Pd2(dba)3, P (o-tol)3, 20% tetraethyl ammonium hydroxide, 100 DEG C, 120 minutes.
Weigh monomer Br2-PO (12.3mg, 0.02mmol), Br2-FO (43.7mg, 0.08mmol), pin2-FO (64.2mg, 0.1mmol), in reaction tube, adds chlorobenzene (3mL), and mass concentration is the tetraethyl ammonium hydroxide 1ml of 20%, logical Argon 20 minutes.It is subsequently added catalyst Pd2(dba)3(3mg) and part P (o-tol)3(7mg), logical argon makes to fill in reaction tube Full argon, builds lid, is heated to 100 DEG C and reacts 120 minutes.Reaction terminates, and reactant liquor instills precipitation polymer in methanol, Then polymer methanol, acetone, normal hexane are washed in apparatus,Soxhlet's, filtering head, finally polymer is done in vacuum Dry case is dried, finally gives 68mg polymer (PFPO), productivity 86%.Record with high temperature GPC (polystyrene is standard specimen) Molecular weight is Mn=85.1kDa, PDI=2.6.
Embodiment 6, the synthesis of polymer P DBTPO88, PFPO88 and PDPPPO88
Polymer P DBTPO88, PFPO88 are prepared with embodiment 5 method by embodiment 3, embodiment 4 with PDPPPO8.With height The PDBTPO88 molecular weight that temperature GPC (polystyrene is standard specimen) records is Mn=34.1kDa, PDI=1.7；PFPO88 is Mn= 62.1kDa, PDI=2.1.PDPPPO88 molecular weight is Mn=26.1kDa, PDI=1.4.
Fig. 1 is chloroformic solution and the film absorption spectrum of polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88 Figure, it can be seen that the solution of PDBTPO, PDBTPO88 polymer shows similar absworption peak to thin film, about 410 Nanometer, 530 nanometers, ABSORPTION EDGE is 620 nanometers, is 2eV for this its optical band gap.The solution of PDPPPO and PDPPPO88 polymer Show similar absworption peak, about 660 nanometers, 720 nanometers to thin film, ABSORPTION EDGE is 760 nanometers, for this its optical band gap is 1.63eV.The acromion that absorbs of thin film has stronger absorption acromion relative to solution.Prove the accumulation of the polymer molecular chain of thin film More tight, this is conducive to the transmission of carrier.Wherein prefix is that S represents solution, and F represents thin film.
Fig. 2 is the cyclic voltammogram of polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88.Calculate poly-from formula The HOMO energy level of compound PDBTPO, PDBTPO88 is about-5.8eV, and lumo energy is about-3.66eV.PO unit can make polymer Obtain deep HOMO energy level, and LOMO energy level moves down the most simultaneously.The HOMO of PDPPPO and PDPPPO88 is with lumo energy respectively It is about-5.21eV and-3.5eV.
Fig. 3 is solar cell device J-V curve prepared by polymer P DBTPO, PDBTPO88, PDPPPO and PDPPPO88 Figure.Device architecture is inverted structure: ITO/PFN-OX/Polymer:PC71BM/MoO3/Al.After adding the CB of 5%, polymerization Thing and PC71When the mass ratio of BM is 1:2, the short circuit current (Jsc) of the material (PDBTPO) that efficiency is the highest and open-circuit voltage (Voc) It is respectively 7.95mA/cm2And 0.91V, energy conversion efficiency is 3.77%.Detailed data is shown in Table 1.
Fig. 4 is the hole diode component J of embodiment 3, embodiment 4 resulting polymers PDBTPO Yu PDBTPO881/2-V is special Levy curve chart.According to formula J=(9/8) ε0εrμ((V2)/(d3)) hole mobility that can calculate PDBTPO is 4.7 × 10- 5cm2V-1s-1, the hole mobility of PDBTPO88 is 1.8 × 10-5cm2V-1s-1。
Fig. 5 is embodiment 5 resulting polymers PFPO at opposed polarity solution and film absorption spectrum and emission spectrum figure, from It can be seen that polymer absworption peak in toluene solution is 387 nanometers in figure, chloroform, chlorobenzene solution are 391 nanometers； Absworption peak in the film is 395 nanometers；ABSORPTION EDGE is 420 nanometers, is 2.95eV for this its optical band gap.Additionally polymer exists Fluorescence emission peak in toluene solution is 414 nanometers, and chloroform is 417 nanometers with the emission peak of chlorobenzene solution, the emission peak of thin film Being 429 nanometers, the edge of the fluorescence emission spectrum of thin film is in 500 nanometers, it can be seen that PFPO is that a kind of excitation is the highest Blue light emitting material.
Fig. 6 is the cyclic voltammogram of embodiment 5 resulting polymers PFPO.The HOMO energy level of polymer P FPO is calculated to obtain from formula It is respectively-2.70eV for-6.26eV, LOMO energy level, can carry as-3.26eV.
Fig. 7 is absorption spectrum and the emission spectrum figure of embodiment 5 resulting polymers PFPO88 different solutions and thin film, from figure In it can be seen that polymer toluene solution absworption peak is about 384 nanometers, chloroform and chlorobenzene solution are 387 nanometers；The absorption of thin film Peak is 391 nanometers；ABSORPTION EDGE is 416 nanometers, is 3.00eV for this its optical band gap.Additionally the fluorescence of polymer toluene solution is sent out Penetrating peak is 411 nanometers, and the emission peak of chloroform and chlorobenzene solution is 414 nanometers, and the emission peak of thin film is 426 nanometers, thin film glimmering The edge of optical emission spectroscopy is in 500 nanometers, it can be seen that PFPO88 is also the blue light emitting material that a kind of excitation is the highest.
Fig. 8 is the cyclic voltammogram of embodiment 6 resulting polymers PFPO88.The HOMO of polymer P FPO88 is calculated to obtain from formula Energy level is-6.26eV, and LOMO energy level is respectively-2.52eV, can carry as-3.44eV.
Fig. 9 is the light emitting diode performance diagram of polymer P FPO.It can be seen that polymer P FPO thin film device It is 3.6V that part starts voltage, and when voltage is 7.9V, high-high brightness is 1880cd/m2.Polymer P FPO+PVK thin-film device opens Galvanic electricity pressure is 5.4V, and when voltage is 11.2V, high-high brightness is 2685cd/m2。
Figure 10 is polymer P FPO current efficiency curve chart.After with the addition of PVK, the device luminous efficiency of polymer P FPO Device than pure PFPO is low, and this is likely due to the addition of caused by the device hole excess of PVK.
Figure 11 is the light emitting diode performance diagram of polymer P FPO88.As can be seen from Figure, polymer P FPO88 It is 3.4V that thin-film device starts voltage, and when voltage is 7.9V, high-high brightness is 3439cd/m2.Polymer P FPO88+PVK is thin It is 5.1V that membrane module starts voltage, and when voltage is 11.2V, high-high brightness is 4578cd/m2。
Figure 12 is polymer P FPO88 current efficiency curve chart.After with the addition of PVK, the device lumen effect of polymer P FPO The rate device than pure PFPO88 is low, and this is likely due to the addition of caused by the device hole excess of PVK.
Polymer solar cells device fabrication process is as follows: first, spin coating one layer 5～10nm on cleaned ITO PFN-OX thin film, subsequently in 150 DEG C of heat cross-linkings 25 minutes.Then by the polymeric material prepared in advance and PC71BM (adds quality to divide Number is for 5%CB) chloroformic solution get rid of on PFN-OX thin film by spin-coating film, then wet film is dried, until film Till Gan Zaoing.MoO finally by thermal evaporation evaporation 10nm3With the Al of 90nm as anode.The effective area of device is 0.16cm2.In atmospheric environment, performance test is carried out after device is encapsulated.The energy conversion efficiency of device and electric current (J)-voltage (V) characteristic curve obtains under AM 1.5G solar simulator.The power of simulated solar lamp uses standard silicon solar cell before testing Demarcate, for 100mW cm-2。
Concrete solar cell device efficiency (device architecture: ITO/PFN-OX/PDBTPO:PC as shown in table 171BM(1:2) (CF+5%DCB) (90nm)/MoO3/ Al), it may be seen that by using the present invention, successfully by 6-(2 octyldodecyl) oxygen Base phenanthridines unit introduces polymer, and the open-circuit voltage of polymer is the highest, up to 0.91V, and illustrate the present invention can Row and the organic semiconducting materials containing 6-(2 octyldodecyl) epoxide phenanthridines are at the application potential of organic photovoltaic cell.
Table 1
Polymer PCE (%) Jsc(mA/cm2) Voc(V) FF (%)
PDBTPO88 2.24 6.02 0.87 42.79
PDBTPO 3.77 7.95 0.91 52.24
PDPPPO88 1.29 4.07 0.81 39.37
PDPPPO 1.54 4.47 0.78 44.12
Polymer light-emitting device manufacturing process is as follows: the PEDOT thin film of spin coating one layer 5～10nm on cleaned ITO, Subsequently in 120 DEG C of heat cross-linkings 20 minutes.Then the xylene solution of the polymeric material prepared in advance is passed through spin-coating film Get rid of on PEDOT thin film, then wet film is dried, till film is dried.It is deposited with 1.5nm finally by thermal evaporation Cesium fluoride and the Al of 110nm as anode.
Concrete organic light emitting diode device efficiency (device architecture: ITO/PEDOT/EMITTER/CsF/ as shown in table 2 Al), it will be seen that by using the present invention, successfully 6-(2 octyldodecyl) epoxide phenanthridines unit is introduced polymerization Thing, has made efficient organic light emitting diode device,
Table 2
Illustrate the feasibility of the present invention and contain the organic semiconducting materials of 6-(2 octyldodecyl) epoxide phenanthridines organic The application potential of light emitting diode.

Claims (7)

1. one kind contains 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, it is characterised in that described organic half Conductor material structure formula is as shown in Equation 1:
Wherein, x, y are respectively in described organic semiconducting materials 2,9-dialkyl group-6-alkoxyl phenanthridines unit and aromatic group Ar Relative amount；M is the number of π unit；R1It it is the alkyl of 1 to 30 carbon numbers；R2Former for hydrogen atom or 1 to 30 carbon The alkyl of subnumber；N is the degree of polymerization of described organic semiconducting materials；
Described 0 < x < 1,0 < y < 1, x+y=1；M is the natural number of 0 to 10000；N is the natural number of 1 to 10000.
Ar is for replacing or unsubstituted group, and wherein, substituted radical is ethenylidene, ethynylene, monocycle arlydene, dicyclo Arlydene, three rings and the arlydene of above ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and the heteroarylidene of above ring, With the group formed by singly linked 2-6 arlydene；Ar is the conjugation list of electron deficiency conjugate unit or electron rich Unit, wherein, electron deficiency conjugate unit is diazosulfide, benzotriazole, naphtho-thiadiazoles, aphthotriazoles, pyrrolopyrrole Diketone, indigo, bioxindol, quinoxaline, benzene-naphthalene diimide, imidodicarbonic diamide, thieno acid imide or quinoxaline, being total to of electron rich Yoke unit is benzene, naphthalene, anthracene, phenanthrene, pyrene, aphthacene, Benzo[b, fluorenes, spiral shell fluorenes, indane fluorenes, pyrroles, benzopyrrole, diphenylamines, three The double thiophene of aniline, carbazole, indole carbazole, thiophene, bithiophene, three bithiophenes, benzothiophene, thieno hexichol, benzo, furan, Benzofuran or benzo Coumarin；
π is connection 2, the conjugate unit of 9-dialkyl group-6-alkoxyl phenanthridines unit and aromatic group Ar, for benzene, naphthalene, thiophene and Thiophene, selenophen, tellurium fen, furan, pyrroles, thiophene are coughed up, thiazole, oxazole, triazole or containing carbon-carbon double bond, the conjugate unit of carbonnitrogen bond In any one.
One the most according to claim 1 contain 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, its It is characterised by, described R1For straight chain, side chain or the cyclic alkyl chain of 1-30 carbon atom, wherein one or more carbon atom quilts Oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group, nitro replace, one or more hydrogen atoms Replaced by halogen atom, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro；R2For hydrogen Atom or the straight chain of 1-30 carbon atom, side chain or cyclic alkyl chain, wherein one or more carbon atoms are by oxygen atom, alkene Base, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, and one or more hydrogen atoms are former by halogen Son, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace.
One the most according to claim 1 contain 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, its Being characterised by, described Ar is any one in following structural formula:
R in structure above is the alkyl of hydrogen or 1-30 carbon atom, and wherein one or more carbon atoms are by oxygen atom, alkene Base, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, and one or more hydrogen atoms are former by halogen Son, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace.
One the most according to claim 1 contain 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit, its Being characterised by, described π is the one in following arbitrary structures formula:
R in structure above is the alkyl of hydrogen or 1-30 carbon atom, and wherein one or more carbon atoms are by oxygen atom, alkene Base, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace, and one or more hydrogen atoms are former by halogen Son, oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace.
5. the preparation a kind of organic partly leading containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit described in any one of claim 1-4 The method of body material, it is characterised in that comprise the steps:
1) there is isomerization in the compound shown in formula 2 and the compound shown in formula 3 under the effect of inorganic base, obtains shown in formula 4 Compound；
Wherein, X is hydrogen atom, halogen atom, pyrovinic acid base, toluenesulfonic acid base, boric acid base group, borate group or trialkyl Tin group；R3Definition be equal to R1；
2) by the monomer with metal coupling reactive functional containing Ar or π-Ar-π and formula 4 compound at metal catalytic React under agent, obtain containing 2, the organic semiconducting materials of 9-dialkyl group-6-alkoxyl phenanthridines unit.
A kind of organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit the most according to claim 5 Preparation method, it is characterised in that described halogen atom is Br or I.
7. a kind of organic semiconducting materials containing 2,9-dialkyl group-6-alkoxyl phenanthridines unit described in claim 1 is organic Application in photoelectric device.
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CN106866938A (en) * 2017-01-17 2017-06-20 华南理工大学 A kind of conjugated polymer based on naphthalene two and indenes fluorenes unit and preparation method and application
CN107674183A (en) * 2017-10-20 2018-02-09 华南协同创新研究院 Containing naphthalene [1,2 c;5,6 c] two [1,2,5] thiadiazoles conjugated polymer and preparation method and application
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CN107698744A (en) * 2017-10-23 2018-02-16 华南协同创新研究院 A kind of preparation method and applications of polymeric acceptor material
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