CN105348274B - A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application - Google Patents
A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application Download PDFInfo
- Publication number
- CN105348274B CN105348274B CN201510857159.XA CN201510857159A CN105348274B CN 105348274 B CN105348274 B CN 105348274B CN 201510857159 A CN201510857159 A CN 201510857159A CN 105348274 B CN105348274 B CN 105348274B
- Authority
- CN
- China
- Prior art keywords
- compound
- benzotriazole
- bound
- singly
- molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *C=CCc1cc([Fl])ccc1N=N Chemical compound *C=CCc1cc([Fl])ccc1N=N 0.000 description 4
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application, belong to field of photovoltaic materials.For the compounds of this invention using benzotriazole as core, triphenylamine is end group and respectively using thiophene and singly-bound, C=C or C ≡ C as connecting key.The initial oxidation current potential of material is improved in benzotriazole after the larger fluorine atom of introducing electronegativity.Using triphenylamine as end group, not only strengthen electron donation, the lifting hole transport performance of molecule, and the dissolubility of increase compound is cooperateed with the alkyl on benzotriazole.Introduce C=C in molecule, the broadening absorption region of compound；Singly-bound or C ≡ C are introduced, can effectively reduce HOMO energy levels.The singly-bound or C ≡ C introduced in molecule cooperates with the V for improving device with single fluorine benzotriazoleOC.The PCE of synthetic material of the present invention is above 1.70%, up to 4.77%, possesses the potential as efficient organic molecule photovoltaic donor material.
Description
Technical field
The present invention relates to a kind of benzotriazole organic molecule photovoltaic material and preparation method thereof and use the benzene a pair of horses going side by side three
Nitrogen azole organic molecule is the solar cell device of donor material, belongs to organic photoelectrical material field.
Background technology
In recent years, solution processes organic molecule solar cell material with molecular structure because being easy to modify, being easy to point
From purification, element manufacturing low cost and other advantages, study hotspot is increasingly becoming.At present, organic small point of the solution processes of document report
The electricity conversion (PCE) of sub- area of solar cell is up to 10.10% so that the research tool to small molecule photovoltaic material
There is important theory and actual application value.But relative to polymerization species solar cell device, based on micromolecular compound
Whole efficiency for the solar cell device of donor is still relatively low.In order to enrich the research model of organic molecule photovoltaic material
Enclose, need design synthesizing new organic micromolecule compound badly.
Research shows, for the organic molecule photovoltaic material of donor-receiver conjugated structure, the electrophilic in molecular structure
Unit is most important for designing and developing high performance solar batteries material.Because the electrophilic unit in molecular skeleton influences material
Highest occupied molecular orbital (HOMO) energy level, and then determine material open-circuit voltage (VOC).In recent years, benzotriazole unit is because of tool
There is preferable flatness and be easy to be widely used in the features such as carrying out structural modification the research and development of multifunctional material, it is such as electroluminescent
Discoloration and photovoltaic material field.Containing two strong electron-withdrawing imine structure (C=N) in benzotriazole unit, therefore its
Derivative shows relatively low HOMO energy levels, so the solar cell device using such compound as donor is easy to show
Higher VOC.Meanwhile containing a N-H key for being easy to alkylation in benzotriazole structure, can not only raising after alkylation
The dissolubility of compound, and beneficial to the charge recombination reduced in charge transfer process.At present, it is different for benzotriazole class body
The research of matter knot photovoltaic material focuses primarily upon polymeric material, and the PCE of solution processes polymer solar cell device is
Through more than 7.0%.Therefore, benzotriazole unit can be efficient applied to research and development as a kind of good electrophilic unit
Organic molecule donor material.However, compared with polymeric material, it is related to grinding for benzotriazole organic micromolecule compound
It is generally relatively low to study carefully more scarcity, the PCE of corresponding solar cell device.
The content of the invention
In order to solve the above problems, the invention is intended to enrich the research model of benzotriazole organic micromolecule photovoltaic material
Enclose, to promote the research of efficient benzotriazole micromolecular donor material to establish certain theory and experiment basis.
The invention provides a kind of benzotriazole organic micromolecule compound, its structure are as follows：
Wherein, Q is C1~C20 alkyl selected from singly-bound, C=C or C ≡ C, R as connecting key.
Another object of the present invention is to provide a kind of synthesis of above-mentioned benzotriazole organic micromolecule photovoltaic material
Method, its preparation process comprise the following steps：
Under nitrogen protection, by compound A and compound D according to mol ratio 1:The reactant of 2.2~2.5 input palladium chtalysts
In system, cross-coupling reaction occurs at 70~110 DEG C, the reaction time is 24~36 hours, and crude product must have after separating-purifying
Machine small molecule F.
Following representation compound D and compound A are provided：
Compound D is：Compound A is：
(1) when Q represents singly-bound, by compound D and compound A according to mol ratio 2.2:1 adds using sodium carbonate as alkali, four
(triphenyl phosphorus) palladium is the Suzuki coupling reaction systems of catalyst.Sodium carbonate and compound A mol ratio are 1:40, catalyst
Mol ratio with compound A is 1:10.Reactant mixture flows back 24 hours in 110 DEG C.Crude by column chromatography method purifies, and obtains
Orange compound F1, its structural formula are as follows：
(2) when Q represents C=C, by compound D and compound A according to mol ratio 2.5:1 input is using palladium as catalysis
Agent, the Heck coupling reaction systems that TBAB (TBAB) is part, sodium acetate is alkali.Palladium is rubbed with compound A's
You are than being 1:10, TBAB and compound A mol ratio is 1:2.5, sodium acetate and compound A mol ratio are 2.5:1.Reaction is mixed
Compound flows back 36 hours in 100 DEG C.Orange red compound F2 is obtained after crude by column chromatography separating-purifying, its structural formula is such as
Under：
(3) when Q represents C ≡ C, by compound D and compound A according to mol ratio 2.2:1 input is with two (triphenyl phosphorus)
The Sonogashira coupling reaction systems that palladium chloride is catalyst, cuprous iodide is co-catalyst, triethylamine is alkali.Catalysis
Agent and compound A mol ratio are 1:40, co-catalyst and compound A mol ratio are 1:20, the mol ratio of alkali and compound A
For 1:1.70 DEG C are reacted on to flow back 24 hours.Crude by column chromatography method separating-purifying, obtain orange compound F3, its structural formula
It is as follows：
The benzotriazole class compound can as the donor material of organic molecule solar cell device, it with by
Body material [6,6]-phenyl-C61- methyl butyrates (PC61BM) mixing is used as active layer, applied to solution processes body heterojunction too
Positive energy field of batteries.
Compared with existing inventive technique, the present invention has advantages below and beneficial effect：
(1) present invention has synthesized a kind of benzotriazole organic micromolecule first, and it can be applied to as donor material
Solution processes organic molecule solar cell field.
(2) the larger fluorine atom of electronegativity is introduced on the benzotriazole unit of organic molecule of the present invention, to strengthen it
It is electron-withdrawing, and then lift the initial oxidation current potential of molecule；Multiple thiophene units and singly-bound, C=C or C are introduced in molecular skeleton
≡ C, to extend the conjugate length of molecule, improve intramolecular charge transmission (ICT) process as connecting key.The introducing profit of thiphene ring
In the energy gap (E for reducing materialg), increase the light abstraction width of material.Comparatively, after introducing C=C in molecule, chemical combination
The absorption region of thing substantially broadens；After introducing singly-bound or C ≡ C, the HOMO energy levels of material effectively reduce.The singly-bound introduced in molecule
Or C ≡ C cooperate with the V for improving device with single fluorine benzotriazoleOC。
(4) organic molecule of the invention is using triphenylamine units as end group, not only facilitate strengthen in molecule to
The electron supplying capacity of electronic section, the hole transport performance of the whole molecule of lifting, and the alkyl with being introduced on benzotriazole
The dissolubility of collaboration increase compound.
(5) under conditions of without any post processing, using benzotriazole class compound in the present invention as the photovoltaic of donor
Device, its optimal result are as follows：JSCFor 13.50mAcm-2, VOCFor 0.98V, fill factor, curve factor (FF) is 0.36, PCE 4.77%.
This illustrates that the compound possesses the potential as efficient organic molecule photovoltaic material, for design synthesizing new, high-efficiency photovoltaic
Material has widened Research Thinking.
Brief description of the drawings
Fig. 1 is F1 normalized ultraviolet visible absorption spectras in chloroformic solution and film-forming state in embodiment 1；
Fig. 2 be embodiment 1 in F1 0.1mol/L tetrafluoro boric acid tetrabutyl ammonia/dichloromethane (Bu4NBF4/CH2Cl2)
Cyclic voltammetry curve in solution；
Fig. 3 is F1 and PC in embodiment 161BM is 1 in mixed proportion:The current-voltage of device when 2 (w/w, 12mg/mL)
Curve；
Fig. 4 is F2 normalized ultraviolet visible absorption spectras in chloroformic solution and film-forming state in embodiment 2；
Fig. 5 be embodiment 2 in F2 0.1mol/L Bu4NBF4/CH2Cl2Cyclic voltammetry curve in solution；
Fig. 6 is F2 and PC in embodiment 261BM is 1 in mixed proportion:The current-voltage of device when 2 (w/w, 12mg/mL)
Curve；
Fig. 7 is F3 normalized ultraviolet visible absorption spectras in chloroformic solution and film-forming state in embodiment 3；
Fig. 8 be embodiment 3 in F3 0.1mol/L Bu4NBF4/CH2Cl2Cyclic voltammetry curve in solution；
Fig. 9 is F3 and PC in embodiment 361BM is 1 in mixed proportion:The current-voltage of device when 2 (w/w, 12mg/mL)
Curve.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Compound A synthesis carry out according to the document reported (DyesPigm., 2015,118,37-44；
Synth.Met.,2012,162,630-635；J.Am.Chem.Soc., 2012,134,2599-2612), its step is as follows：Change
With hydrated stannous chloride reduction reaction generation 4- fluoro- 1 occurs in ethanol and hydrochloride aqueous solution for fluoro- 2 nitroanilines of compound 5-,
2- phenylenediamines；Fluoro- 1, the 2- phenylenediamines of 4- react in glacial acetic acid with natrium nitrosum, generate 5- fluoro- 1,2,3- benzotriazoles；5-
Fluoro- 1, with R-Br nucleophilic substitution occurs in methanol solution for 2,3- benzotriazoles, obtains parallel three nitrogen of 2- alkyl -5- fluorobenzene
Azoles；2- alkyl -5- fluorine benzotriazole passes through double bromo-reactions with bromine in aqueous solution of hydrogen bromide, generates 2- alkyl -4,7-
Two bromo- 5- fluorine benzotriazoles；In the Suzuki reaction systems of palladium chtalyst, the bromo- 5- fluorine benzotriazole of 2- alkyl -4,7- bis-
2- alkyl -4,7- two (2- thienyls) -5- fluorine benzotriazoles are generated in tetrahydrofuran solution with 2- thienyl boric acids；In room temperature
Under the conditions of lucifuge, (2- the thienyls) -5- fluorine benzotriazole of 2- alkyl -4,7- bis- is with N- bromo-succinimides (NBS) in chlorine
Reaction generation compound A1 in imitative solution.By compound A1 and 2- thienyl boric acid molten as the toluene of alkali using 2mol/L sodium carbonate
The Suzuki coupling reactions of palladium catalyst, generation compound A2 occur in liquid.Finally, compound A2 and NBS is sent out in ice-water bath
Raw bromo-reaction obtains orange compound A.The synthetic route of above-mentioned reaction is as follows：
Wherein, R is C1~C20 alkyl；
Compound D synthesis carries out (Chem.Commun., 2012,48,10627-10629 according to the document reported；
J.Mater.Chem.C, 2014,2,4019-4026), its step is as follows：With NBS bromo-reaction occurs in ice-water bath for triphenylamine
Generate 4- bromine triphenylamines.Q represents that compound D is to pass through palladium chtalyst by 4- bromines triphenylamine and connection pinacol borate during singly-bound
The reaction synthesis of Miyaura borations.Q represents that compound D is synthesized in two steps during C ≡ C：4- bromines triphenylamine and trimethyl silicon substrate first
The Sonogashira coupling reactions of palladium chtalyst occur for acetylene, obtain midbody compound N- (4- (trimethyl silicon substrate) acetenyl) benzene
Base-N- phenylanilines, then the intermediate elimination reaction occur in methanol and tetrahydrofuran mixed solution obtain compound D.
Triphenylamine occurs formylation reaction with POCl3 in DMF solution and obtains compound 4- (N, N- diphenyl amino) benzaldehyde.Q
Represent that compound D is that phosphonium ylide occurs by 4- (N, N- diphenyl amino) benzaldehydes and iodide triphenylphosphine salt during C=C
React and obtain.
The synthetic route of above-mentioned reaction is as follows：
Embodiment 1
Present embodiment discloses organic molecule donor material F1 specific building-up process, comprise the following steps：
Under nitrogen protection, by compound A (147mg, 0.2mmol), N, N- diphenyl -4- (4,4,5,5- tetramethyls -
[2,1,3] C oxa- ring pentaboranes base) aniline, i.e. Q represent singly-bound when D (186mg, 0.5mmol), sodium carbonate (848mg,
8.0mmol) and four (triphenyl phosphorus) palladiums (22mg, 0.02mmol) are dissolved in toluene (8mL), deionized water (4mL) and ethanol (2mL)
Mixed solution, and in 110 DEG C flow back 24 hours.Question response liquid is cooled to room temperature, is poured into 20mL deionized waters and divides
Liquid, extracted with dichloromethane.With anhydrous sodium sulfate drying organic phase.Revolving removes organic solvent, and crude product is with petroleum ether/dichloro
Methane (v:V, 5:1) it is solvent, is purified by column chromatography, it is orange solids to obtain target product, yield 85%.
Above-mentioned prepare compound F1 reaction equation is as follows：
It is compound F1 normalized ultravioletvisible absorptions under chloroformic solution and film-forming state in embodiment 1 referring to Fig. 1
Spectrogram.As seen from the figure, under chloroformic solution and film-forming state, compound F1 is in the range of 300~600nm in embodiment 1
Reveal 3 obvious absworption peaks, two shorter absworption peaks of wavelength are the longer wavelengths of suctions caused by the π-π transition of intramolecular
It is as caused by the ICT processes between electron donating group and electron withdraw group to receive peak.In chloroformic solution, compound F1 maximum
Absworption peak (λmax sol) at 484nm.Due to packing of molecules under solid-state, absorption regions of the compound F1 under film-forming state is bright
It is aobvious to broaden, and there is obvious acromion, but the maximum absorption band (λ under film-forming state in 550nm or somax film) slightly blue shift.
Its optical bandwidth (E can be calculated in the absorption edge of film-forming state from compound F1g opt) it is 2.09eV.
Referring to Fig. 2, be in embodiment 1 compound F1 in 0.1mol/L Bu4NBF4/CH2Cl2The circulation measured in solution
Volt-ampere curve.As seen from the figure, compound F1 initial oxidation current potential is 0.34V, and initial reduction current potential is -1.78V, accordingly
HOMOCVFor -5.05eV, LUMOCVFor -2.93eV, by HOMOCV-LUMOCVEnergy level difference calculates to obtain energy gap (Eg CV) be
2.12eV。
It is with compound F1 and PC in embodiment 1 referring to Fig. 361BM is according to mass ratio 1:Photovoltaic of 2 mixing as active layer
The current -voltage curve of device.Test result shows, under conditions of without any post processing, the J of deviceSCFor 8.80mAcm-2, VOCFor 0.82V, fill factor, curve factor (FF) is 0.34, PCE 2.47%.
Embodiment 2
Present embodiment discloses organic molecule donor material F2 specific building-up process, comprise the following steps：
By compound A (147mg, 0.2mmol), 4- (N, N- diphenyl amino) styrene is D when Q represents C=C
(136mg, 0.5mmol), sodium acetate (410mg, 5mmol), palladium (4mg, 0.02mmol) and TBAB (26mg, 0.08mmol)
It is dissolved in 12mL DMF solution, and is flowed back 36 hours in 100 DEG C.Question response liquid pours into after being cooled to room temperature
In 50mL deionized waters, gained organic phase is washed with a large amount of deionized waters after being extracted with dichloromethane, and is done with anhydrous sodium sulfate
Dry organic phase.Revolving removes organic solvent, and crude product is with petroleum ether/dichloromethane (v:V, 3:1) it is solvent, passes through column chromatography
Method purifies, and it is Orange red solid to obtain target product, yield 42%.
Above-mentioned prepare compound F2 reaction equation is as follows：
It is compound F2 normalized ultravioletvisible absorptions under chloroformic solution and film-forming state in embodiment 2 referring to Fig. 4
Spectrogram.As seen from the figure, in the range of 300~600nm, between the π-π transition and electron and electron withdraw group due to intramolecular
ICT, compound F2 shows two obvious absworption peaks under solution and film-forming state in embodiment 2.With embodiment 1 and in fact
Two compound phase ratios in example 3 are applied, because the conjugation degree increase of molecule, flatness strengthen after C=C introducings, compound
F2 ultraviolet-ray visible absorbing widest range, λmax solAnd λmax filmIt is maximum.Calculated by compound F2 absorption edges under film-forming state
Obtain Eg optFor 2.00eV.
Referring to Fig. 5, be in embodiment 2 compound F2 in 0.1mol/L Bu4NBF4/CH2Cl2The circulation measured in solution
Volt-ampere curve.As seen from the figure, compound F2 initial oxidation current potential is 0.29V, and initial reduction current potential is -1.76V, accordingly
HOMOCVFor -5.00eV, LUMOCVFor -2.95eV, Eg CVFor 2.05eV.With the electricity of two kinds of compounds in embodiment 1 and embodiment 3
Test chemical result is compared, in molecule C=C introducing advantageously reduce the E of materialg CV。
It is with compound F2 and PC in embodiment 2 referring to Fig. 661BM is according to mass ratio 1:Photovoltaic of 2 mixing as active layer
The current -voltage curve of device.Test result shows, under conditions of without any post processing, the J of deviceSCFor 7.50mAcm-2, VOCFor 0.72V, FF 0.33, PCE 1.79%.With the device detection knot of two compounds in embodiment 1 and embodiment 3
Fruit is compared, V relatively low compound F2 in embodiment 2OCIt is worth HOMO higher corresponding theretoCVEnergy level value is relevant.
Embodiment 3
Present embodiment discloses organic molecule donor material F3 specific building-up process, comprise the following steps：
By compound A (147mg, 0.2mmol), 4- (N, N- diphenyl amino) phenylacetylene is D when Q represents C ≡ C
(134mg, 0.5mmol), two (triphenyl phosphorus) palladium chlorides (4mg, 0.005mmol) and cuprous iodide (2mg, 0.01mmol) are molten
In the mixed solution of 20mL tetrahydrofurans and 15mL triethylamines, flowed back 24 hours in 70 DEG C.It will be cooled to the reaction solution of room temperature
Pour into 50mL deionized waters, extracted with dichloromethane, the organic phase anhydrous sodium sulfate drying after merging.Revolving removes organic
Solvent, crude product is with petroleum ether/dichloromethane (v:V, 5:1) it is solvent, is purified by column chromatography, obtaining target product is
Orange solids, yield 45%.
Above-mentioned prepare compound F3 reaction equation is as follows：
It is compound F3 normalized ultravioletvisible absorptions under chloroformic solution and film-forming state in embodiment 3 referring to Fig. 7
Spectrum.As seen from the figure, with two compound phase ratios in embodiment 1 and embodiment 2, compound F3 is in chloroformic solution and film-forming state
When absorption region relative narrower, λmax filmRed shift amount is maximum.Under film-forming state, compound F3 shows most strong this explanation
ICT.E is calculated to obtain by compound F3 absorption edges under film-forming stateg optFor 2.10eV.
Referring to Fig. 8, be in embodiment 3 compound F3 in 0.1mol/L Bu4NBF4/CH2Cl2The circulation measured in solution
Volt-ampere curve.As seen from the figure, compound F3 initial oxidation current potential is 0.46V, and initial reduction current potential is -1.72V, accordingly
HOMOCVFor -5.17eV, LUMOCVFor -2.99eV, Eg CVFor 2.18eV.With two compound phases in embodiment 1 and embodiment 2
Than compound F3 HOMO in embodiment 3CVAnd LUMOCVEnergy level value is minimum, because the C ≡ C tools introduced in molecular structure
Have it is electron-withdrawing, be advantageous to lifted compound initial oxidation current potential and initial reduction current potential；Meanwhile compound in the present embodiment
F3 HOMOCVThe degree of reduction is significantly greater than LUMOCV, therefore the E of compoundg CVIncrease.
It is with compound F3 and PC in embodiment 3 referring to Fig. 961BM is according to mass ratio 1:Photovoltaic of 2 mixing as active layer
The current -voltage curve of device.Test result shows, under conditions of without any post processing, the J of deviceSCFor
13.50mAcm-2, VOCFor 0.98V, FF 0.36, PCE 4.77%.This is that current benzotriazole class solution processes are organic small
The highest numerical value of biomolecule ontology heterojunction solar battery device.The higher J of the deviceSCWith being showed in its ultraviolet-ray visible absorbing
V relevant, higher the preferable ICT that goes outOCThe then HOMO relatively low with itCVEnergy level value is consistent.
The optical physics of synthesized compound, electrochemistry and photovoltaic data are listed in Table 1 below in embodiment 1~3.
From table 1, compound F E in the embodiment of the present inventiong optWith Eg CVIt is basically identical；Comparatively, draw in molecule
After entering C=C, the absorption region of compound substantially broadens；After introducing singly-bound or C ≡ C, the HOMO energy levels of compound effectively reduce,
And then improve the V of batteryOC；Compared to existing literature (Synth.Met., 2012,162,630-635), the change synthesized with the present invention
Compound shows the Photovoltaic Properties more protruded, the small molecule particularly using compound F3 as donor for the photovoltaic device of donor
Device, its PCE are up to 4.77%.The result is electric for the small molecule list based on benzotriazole class solution processes reported at present
The peak efficiency that pond is reached.
Claims (5)
1. a kind of benzotriazole organic micromolecule photovoltaic material, there is following structural formula：
Wherein, Q is connecting key, is C1~C20 alkyl selected from singly-bound or C ≡ C, R.
2. the preparation method of benzotriazole organic micromolecule photovoltaic material as claimed in claim 1, it is characterised in that bag
Include following steps：
Reaction scheme is as follows：
Wherein：Q is connecting key, is C1~C20 alkyl selected from singly-bound or C ≡ C, R；
Under nitrogen protection, by compound A and compound D according to mol ratio 1:The reaction system of 2.2~2.5 input palladium chtalysts
In, cross-coupling reaction occurs at 70~110 DEG C, the reaction time is 24~36 hours, and crude product obtains organic after separating-purifying
Small molecule F.
3. the preparation method of benzotriazole organic micromolecule photovoltaic material according to claim 2, it is characterised in that
When Q represents singly-bound in compound D, it is to urge that compound D and compound A, which is added by alkali, four (triphenyl phosphorus) palladiums of sodium carbonate,
The Suzuki coupling reaction systems of agent；The mol ratio of compound A and sodium carbonate is 1:40；Mole of catalyst and compound A
Than for 1:10.
4. the preparation method of benzotriazole organic micromolecule photovoltaic material according to claim 2, it is characterised in that
When in compound D Q represent C ≡ C when, by compound D and compound A input using two (triphenyl phosphorus) palladium chlorides as catalyst,
The Sonogashira coupling reaction systems that cuprous iodide is co-catalyst, triethylamine is alkali；Mole of catalyst and compound A
Than for 1:40, co-catalyst and compound A mol ratio are 1:20, alkali and compound A mol ratio are 1:1.
5. benzotriazole organic micromolecule photovoltaic material as claimed in claim 1 is preparing solar energy as donor material
Application in terms of battery device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510857159.XA CN105348274B (en) | 2015-11-27 | 2015-11-27 | A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510857159.XA CN105348274B (en) | 2015-11-27 | 2015-11-27 | A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105348274A CN105348274A (en) | 2016-02-24 |
| CN105348274B true CN105348274B (en) | 2018-01-30 |
Family
ID=55324357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510857159.XA Expired - Fee Related CN105348274B (en) | 2015-11-27 | 2015-11-27 | A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105348274B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629047B (en) * | 2017-09-18 | 2020-04-14 | 大连理工大学 | Asymmetric organic small-molecule photovoltaic material based on benzothiadiazole unit and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006041221A1 (en) * | 2004-10-15 | 2006-04-20 | Hitachi Chemical Co., Ltd. | New luminescent compositions and their uses |
| CN102850526A (en) * | 2011-06-30 | 2013-01-02 | 海洋王照明科技股份有限公司 | Organic semiconductor material, its preparation method and organic solar cell |
| CN103562323A (en) * | 2011-09-26 | 2014-02-05 | 日东电工株式会社 | Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency |
-
2015
- 2015-11-27 CN CN201510857159.XA patent/CN105348274B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006041221A1 (en) * | 2004-10-15 | 2006-04-20 | Hitachi Chemical Co., Ltd. | New luminescent compositions and their uses |
| CN102850526A (en) * | 2011-06-30 | 2013-01-02 | 海洋王照明科技股份有限公司 | Organic semiconductor material, its preparation method and organic solar cell |
| CN103562323A (en) * | 2011-09-26 | 2014-02-05 | 日东电工株式会社 | Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency |
Non-Patent Citations (3)
| Title |
|---|
| Benzotriazole-Containing D–p–A Conjugated Organic Dyes for Dye-Sensitized Solar Cells;Yung-Sheng Yen，等;《Chem. Asian J.》;20130207;第8卷;809-816 * |
| Synthesis and photovoltaic properties of a solution-processable organic molecule containing dithienylbenzotriazole and triphenylamine;Bo Liu，等;《Synthetic Metals》;20120322;第162卷;630-635 * |
| 不对称有机小分子光伏材料的合成与性质研究;高航;《大连理工大学硕士学位论文》;20150715;17-22,31 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105348274A (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yao et al. | Recent progress in chlorinated organic photovoltaic materials | |
| Ans et al. | Development of fullerene free acceptors molecules for organic solar cells: a step way forward toward efficient organic solar cells | |
| Ans et al. | Designing dithienothiophene (DTT)-based donor materials with efficient photovoltaic parameters for organic solar cells | |
| CN104557968B (en) | A D A conjugated molecules based on dithieno indacene and its preparation method and application | |
| Yousaf et al. | Isatin-derived non-fullerene acceptors for efficient organic solar cells | |
| CN101875716B (en) | Block conjugated polymer, preparation method thereof and use thereof | |
| US10062854B2 (en) | Organic material and photoelectric conversion element | |
| Sun et al. | Understanding the halogenation effects in diketopyrrolopyrrole-based small molecule photovoltaics | |
| CN107057044A (en) | Heteroatom-substituted benzothiadiazole-based polymer donor material and preparation method and application thereof | |
| Haid et al. | Synthesis and Structure–Property Correlations of Dicyanovinyl‐Substituted Oligoselenophenes and their Application in Organic Solar Cells | |
| CN103788111A (en) | Solution-processable two-dimensional conjugated organic molecule photovoltaic material, preparation method and application thereof | |
| EP2562197B1 (en) | Copolymer comprising anthracene and benzoselenadiazole, preparing method and uses thereof | |
| CN108586496A (en) | Zigzag type middle width strip gap small molecule electron donor materials based on the different chromene of thieno and its application | |
| CN104211926B (en) | Polymerization single polymerization monomer for the donor material of polymer solar battery and donor material | |
| Zhou et al. | Isomeric small molecule acceptors based on perylene diimide and spirobifluorene for non-fullerene organic solar cells | |
| CN106674491A (en) | D-A type polymer photovoltaic material based on thieno-isobenzopyran asymmetric donor unit and application thereof | |
| Adnan et al. | Molecular modelling of fused heterocycle-based asymmetric non-fullerene acceptors for efficient organic solar cells | |
| CN107652282B (en) | A-pi-A' -pi-A type receptor photovoltaic material based on diazosulfide unit and preparation method and application thereof | |
| Abdi et al. | Bipodal dyes with bichromic triphenylamine architectures for use in dye-sensitized solar cell applications | |
| CN105348274B (en) | A kind of benzotriazole organic micromolecule photovoltaic material and its preparation method and application | |
| Yu et al. | New Conjugated Molecules with Two and Three Dithienyldiketopyrrolopyrrole (DPP) Moieties Substituted at meta Positions of Benzene toward p‐and n‐Type Organic Photovoltaic Materials | |
| CN108192083B (en) | Conjugated polymer containing trifluoromethyl as well as preparation method and application thereof | |
| CN105669954A (en) | Side chain functionalized conjugated polymer donors and additives as well as preparation method and application of side chain functionalized conjugated polymer additives | |
| CN105237524B (en) | Linear (the D- π-A- π) of the unit containing benzotriazole2- D type organic molecule photovoltaic materials and its preparation and application | |
| CN103880834A (en) | Organic solar cell material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180130 Termination date: 20201127 |