CN109096163A - Organic molecule material and its synthetic method and application as hole transmission layer - Google Patents
Organic molecule material and its synthetic method and application as hole transmission layer Download PDFInfo
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Abstract
The invention belongs to organic functional material technical fields, it is related to organic molecule material and its synthetic method and the application as hole transmission layer, the invention discloses organic molecule materials and preparation method and application that molecule both ends symmetry connects bis- (4- (methyl mercapto) phenyl) amine, and structural formula is as shown in formula I or formula II.They have good dissolubility in common organic solvent, can use the film of solution spin coating method preparation high quality.F1, F2 organic molecule material are applied in positive perovskite solar battery as hole transmission layer, and energy conversion efficiency can achieve 12.28% and 3.96% respectively, and F1 organic molecule material, which is applied to energy conversion efficiency in inverted device, can achieve 15.04%.
Description
Technical field
The invention belongs to organic functional material technical fields, and in particular to molecule both ends symmetry connects bis- (4- (first sulphur
Base) phenyl) amine organic molecule material and its synthetic method and the application as hole transport layer material.
Background technique
In the utilization of solar energy, other than photothermal conversion, most important thinking is solar power generation (PV).In recent years,
Organic and inorganic perovskite solar battery (PSCs) is quickly grown, and Japanese Scientists Tsutomu Miyasaka in 2009 is for the first time
It was found that perovskite is similar to dyestuff, has the function of absorbing sunlight, apply it in solar battery, achieve 3.8%
Energy conversion efficiency (PCE) (A.Kojima, K.Teshima, Y.Shiral, T.Miyasaka,
J.Am.Chem.Soc.2009,131:6050-6051).In time less than 10 years, scientists pass through to perovskite solar energy
Battery deepens continuously ground exploratory development, the type battery PCE more than 20% (W.S.Yang, J.H.Noh, N.J.Jeon,
Y.C.Kim,S.Ryu,J.Seo,S.I.Seok,Science,2015,348:1234-1237).Not only high-efficient, perovskite is too
It is positive battery but also low cost to be had both, solution processable and excellent photoelectric conversion performance；Perovskite material has suction simultaneously
Receive strong, mobility is high, and carrier lifetime is long, controllable band gap and the advantages that various ways processing can be used, therefore becomes most
It is hopeful to substitute the solar battery technology of inorganic silion cell.In high performance PSCs, hole mobile material (HTM) play from
Perovskite material expects the key effect to electrode extraction and transporting holes.Applied to the hole transport in perovskite solar battery
Material can substantially be divided into three classes.The first kind is inorganic matter and organo-metallic compound；Second class is conjugatd polymers, he
There is relatively high hole transport performance and good film forming, so can also be used as hole mobile material applied to PSCs
In, it can be roughly divided into two types applied to the conjugatd polymers in PSCs, one kind is to be applied to organic solar batteries
The higher donor polymer of hole mobility, one kind are to be made exclusively for being total to containing triphenylamine units of hole mobile material design
Conjugated polymer；Third class, and opposite research be most widely solution can spin coating organic molecule hole mobile material.Organic point
The advantages of there is sub- material polymer can be processed with solution, spin coating preparation, structure diversification, while being kept away again because of structure determination
Batch wise differences are exempted from, purification is convenient, and repeatability is high.Organic molecule HTM according to bulk of molecule and configuration, and can substantially be drawn
It is divided into Spiro- type organic molecule hole mobile material, star-like organic molecule hole mobile material and linear organic molecular hole pass
Defeated material.Most widely used organic molecule hole mobile material is based on two fluorenyl of spiral shell in perovskite solar battery at present
Bulky molecule Spiro-OMeTAD, the mesoporous perovskite solar battery peak efficiency based on this material under dopant states can be with
Reach 20.8% (D.Bi, W.Tress, M.Gratzel, A.Hagfeldt et al.Sci.Adv.2016,2:e1501170).
A large amount of organic molecule HTM is synthesized and is applied in PSCs, and final goal is the material for seeking to substitute Spiro-OMeTAD
Material meets efficient meanwhile, it is capable to meet that synthesis cost is low, and the requirement of corresponding device stability can be improved.
Summary of the invention
It is an object of the present invention to provide the organic molecule materials that molecule both ends symmetry connects bis- (4- (methyl mercapto) phenyl) amine
F1, F2 and preparation method thereof.
The general structure of organic molecule material F1 provided by the present invention is as shown in formula I, the general structure of F2 such as II institute of formula
Show:
In formula I or II, R is the straight chained alkyl that the total number of carbon atoms is 6.
The method of organic molecule material shown in preparation formula I includes the following steps: in tris(dibenzylideneacetone) dipalladium (0),
Under the catalytic action of tetrafluoro boric acid tri-tert-butylphosphine and sodium tert-butoxide, compound shown in compound shown in formula III and formula IV is carried out
Buchwald-Hartwig reaction, carries out back flow reaction after mixing as in toluene solution, obtains containing organic molecule shown in formula I
The solution of material obtains organic molecule material shown in formula I after purification.
In formula III, R is the straight chained alkyl that the total number of carbon atoms is 6.
In the above method, the molar ratio of compound shown in compound shown in formula III and formula IV is 1:2-2.2, preferably 1:
2.2。
The molar ratio of compound shown in the tris(dibenzylideneacetone) dipalladium (0) and formula III is 0.01~0.02:
1, preferably 0.02:1.
The molar ratio of compound shown in the tetrafluoro boric acid tri-tert-butylphosphine and formula III is 0.015~0.03:1, excellent
Select 0.03:1.
The molar ratio of compound shown in the sodium tert-butoxide and formula III is 2~3:1, preferably 3:1.
Reaction time is 12-48 hours, preferably 12 hours.
The above method further includes following purification step: the solution containing organic molecule material shown in formula I is cooled to
Room temperature, extraction merge organic phase, are then washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate is dry, are evaporated in vacuo solvent
Afterwards, it uses ethyl acetate and petroleum ether volume ratio to cross chromatographic column purification for the mixed solvent of 1:20 (v:v), obtains formula I and be shown with
Machine molecular material.
The method of organic molecule material shown in preparation formula II is similar with the method for preparation formula I, includes the following steps: three
(dibenzalacetone) two palladium (0), under the catalytic action of tetrafluoro boric acid tri-tert-butylphosphine and sodium tert-butoxide, by chemical combination shown in formula IV
Compound shown in object and formula V carries out Buchwald-Hartwig reaction, carries out flowing back after mixing as in toluene solution anti-
It answers, obtains the solution containing organic molecule material shown in formula II, obtain organic molecule material shown in formula II after purification.
In formula V, the definition of R is the same as formula I and II.
In the above method, the molar ratio of compound shown in compound shown in formula V and formula IV is 1:2-2.2, preferably 1:
2.2。
The molar ratio of compound shown in the tris(dibenzylideneacetone) dipalladium (0) and formula V is 0.01~0.02:
1, preferably 0.02:1.
The molar ratio of compound shown in the tetrafluoro boric acid tri-tert-butylphosphine and formula V is 0.015~0.03:1, excellent
Select 0.03:1.
The molar ratio of compound shown in the sodium tert-butoxide and formula V is 2~3:1, preferably 3:1.
The reflux time is 12~48 hours, preferably 12 hours.
The above method further includes following purification step: the solution containing organic molecule material shown in formula II is cooled to
Then room temperature extracts, merge organic phase, then washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate is dry, is evaporated in vacuo molten
After agent, uses methylene chloride and petroleum ether volume ratio to cross chromatographic column purification for the mixed solvent of 1:3 (v:v), obtain shown in formula II
Organic molecule material.
The present invention also provides a kind of method of monomer shown in preparation formula IV, comprise the following steps that Formula IV, Formula VII institute
The compound and tris(dibenzylideneacetone) dipalladium shown, 1,1'- bis- (diphenylphosphine) ferrocene (DPPF), sodium tert-butoxide and dry
Dry good toluene is mixed in reactor, then under nitrogen protection 90 DEG C~110 DEG C (preferably 90 DEG C) reflux 12~24 hours it is (excellent
Select 12 hours), reaction mixture is obtained, room temperature is cooled to, is then dissolved in methylene chloride, saturated sodium-chloride water solution is then used
It washes, anhydrous magnesium sulfate is dry, after being evaporated in vacuo solvent, crosses chromatography using ethyl acetate/petroleum ether (1/15, V/V) mixed liquor
Column purification, obtaining yellow solid is compound shown in formula IV.Wherein reaction raw materials mol ratio is VI compound of formula: VII institute of formula
Compound=1:1~1.2 shown, preferably 1:1.2.
Organic molecule material shown in above-mentioned formula I or formula II is preparing perovskite solar battery as hole mobile material
In application, the especially application in the hole transmission layer for preparing perovskite solar battery, wherein I organic molecule conduct of formula
Hole transmission layer preparation forward direction and/or reversed photovoltaic device；II organic molecule of formula prepares positive photovoltaic device as hole transmission layer
Part.
Beneficial effects of the present invention:
The present invention by the design and synthesis of methyl mercapto unit application to solution processable organic molecule hole mobile material,
The organic molecule hole mobile material that molecule both ends symmetry connects bis- (4- (methyl mercapto) phenyl) amine is synthesized.They are common
Organic solvent (such as methylene chloride, chloroform, toluene, chlorobenzene) in have good dissolubility, solution methods system can be used
The film of standby high quality；And the available very high material of purity compared with polymer material.Meanwhile these molecules have conjunction
Suitable HOMO and lumo energy.It is prepared for by hole transmission layer of this organic molecule based on CH3NH3PbI3The perovskite sun
Energy battery, the highest energy transfer efficiency after optimization can be more than 15%.
Detailed description of the invention
Fig. 1 is synthetic route chart provided by the invention.
Fig. 2 is the absorption spectrum of solid film prepared by F1 and F2.
Fig. 3 is the structural schematic diagram of perovskite solar battery；It is hole transmission layer that wherein Fig. 3 (a), which is using F1 or F2,
Positive perovskite solar battery structure, Fig. 3 (b) be using F1 be hole transmission layer reversed perovskite solar battery knot
Structure.
Fig. 4 is the current -voltage curve figure of perovskite solar battery；Wherein, Fig. 4 (a) is the F1 system based on 15mg/L
The current -voltage curve of the positive perovskite solar battery of standby hole transmission layer, it is hole transmission layer that Fig. 4 (b), which is based on F1,
Reversed perovskite solar battery current -voltage curve, Fig. 4 (c) be the F2 based on 10mg/L prepare hole transmission layer
The current -voltage curve of positive perovskite solar battery.
Fig. 5 is the cyclic voltammogram of compound film, wherein Fig. 5 (a) is the cyclic voltammogram based on F1 film, Fig. 5
It (b) is the cyclic voltammogram based on F2 film.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
The synthesis (compound of formula IV) of embodiment 1, bis- (4- (methyl mercapto) phenyl) amine
By 4- amino thioanisole (formula VII, 3.34g, 24mmol), tert-butyl sodium alkoxide (2.69g, 28mmol), three (two Asias
Benzylacetone) two palladiums (0.366g, 0.4mmol), bis- (diphenylphosphine) ferrocene (DPPF) (0.332g, 0.6mmol) of 1,1'- and
20ml toluene mixes, and stirs 30min under 60 DEG C of constant temperature.Again be added 4.06g 4- bromophenyl sulfide (formula VI, 4.06g,
20mmol), then under nitrogen protection 90 DEG C flow back 12 hours.Reaction mixture is cooled to room temperature, deionized water, second is added
Acetoacetic ester extracts three times, merges organic phase, is then washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate is dry, and vacuum evaporation is fallen
After solvent, chromatographic column purification is crossed using ethyl acetate/petroleum ether (1/15, V/V), it is bis- ((methyl mercapto) to obtain 3.64g yellow solid
Phenyl) amine, yield: 69.73%.GC/MS:261(M+)。
Structural identification data is as follows:1H NMR (500MHz, acetone-d6)δ(ppm):8.22(s,1H),7.21(m,4H),
7.02(m,4H),2.41(s,6H)。
Embodiment 2,9,9- dihexyl-N2,N2,N7,N7- four (4- (methyl mercapto) phenyl) -9H- fluorenyl -2,7- diamines (F1)
Synthesis (in formula I, R=C6H13)
20ml toluene is added into flask, takes bis- (4- (methyl mercapto) phenyl) amine (formula IV, 2.30g, 8.8mmol), 2,7-
Two bromo- 9,9- hexyl fluorenes (formula III, 2g, 4mmol), tris(dibenzylideneacetone) dipalladium (73.2mg, 0.08mmol), tetrafluoro boric acid
Tri-tert-butylphosphine (34.8mg, 0.12mmol) and sodium tert-butoxide (1.152g, 12mmol) are added in flask, are stirred in oil bath pan
Mix reaction 12h.After solution is cooling, deionized water, methylene chloride extraction is added three times, merges organic phase, uses saturated sodium-chloride
Aqueous cleaning organic phase is twice.It is dry that anhydrous magnesium sulfate is added, with neutral alumina column chromatography, eluent 20:1
(v/v) petrol ether/ethyl acetate.Obtained product is dissolved in acetone, and again with methanol is recrystallized, and collects product F1, is greenish yellow
Color solid (2.20g, 64.6%).Compound is characterized as below using mass spectrum and nuclear-magnetism.MALDI-TOF:m/z 850.2.
Calculated C53H60N2S4Mass-to-charge ratio be 850.3.
Structural identification data is as follows:1H NMR (500MHz, acetone-d6)δ(ppm):7.68(d,2H),7.27-7.24(m,
8H),7.18(d,2H),7.07-7.04(m,8H),7.02-7.00(q,2H),2.50(s,12H),1.88-1.85(m,4H),
1.32-1.17(m,4H),1.13-1.11(m,8H),0.87(t,6H),0.77-0.72(m,4H).13C NMR (acetone-d6,
500MHz)δ(ppm):153.10,147.30,146.45,137.42,132.80,129.18,125.09,124.42,121.16,
120.18,55.96,40.81,32.39,30.55,30.40,30.37,30.24,30.09,24.75,23.32,16.57,
14.49.
The compound dissolves well in chloroform, the common solvents such as toluene and chlorobenzene.
The absorption spectrum of the organic molecule material F1 solid film of example preparation is shown in Fig. 2.Compound F1 film is by F1
It is dissolved in organic solvent, obtains F1 solution, then formed a film on quartz plate using the method for solution spin coating, F1 compound film
Absorption is concentrated mainly on 305-430nm, absorbs limit in 427nm or so, corresponding optical band gap is 2.90eV.
Fig. 5 (a) is the cyclic voltammogram based on F1 film.Using Ag/AgCl as reference electrode, F1 is directly dissolved in hexafluoro
It is measured in phosphoric acid 4-butyl amine acetonitrile solution.It is 0.18V. then by formula HOMO=-e that initial oxidation potential is obtained from figure
(Eox onset+ 4.71) (eV)=- 4.89eV, LOMO=(Eg opt+ HOMO) (eV)=- 1.99eV.
Embodiment 3, tetra- hexyl-N of 4,4,9,9-2,N2,N7,N7- four (4- (methyl mercapto) benzene) -4,9- dihydro-s- double fluorene bases
[1,2-b:5,6-b'] and double thiophene -2,7- diamines (F2) synthesis (in formula II, R=C6H13)
20ml toluene is added into flask, takes bis- (4- (methyl mercapto) phenyl) amine (formula IV, 1.49g, 5.72mmol), 2,7-
Two bromo- 4,4,9,9- tetra- hexyls-double fluorene base [1,2-b:5,6-b'] and double thiophene (formula V, 2g, 2.6mmol), three (dibenzylidenes
Acetone) two palladiums (47.6mg, 0.052mmol), tetrafluoro boric acid tri-tert-butylphosphine (22.6mg, 0.078mmol) and sodium tert-butoxide
(0.749g, 7.8mmol) is added in flask, and 12h is stirred to react in oil bath pan.After solution is cooling, addition deionized water,
Methylene chloride extracts three times, merges organic phase, and saturated sodium-chloride water solution cleans organic phase twice.It is dry that anhydrous magnesium sulfate is added
Dry, with neutral alumina column chromatography, eluent is 3:1 (v/v) petroleum ether/methylene chloride.Obtained product is dissolved in acetone
In, again with methanol is recrystallized, and product F2 is collected, and is buff color solid (1.58g, 54.2%).Using mass spectrum to chemical combination
Object is characterized.C68H84N2S6Exact Mass(1120.52),MS(MADI-TOF)(1122.3)。MALDI-TOF:m/z
1122.3. calculated C68H84N2S6Mass-to-charge ratio be 1120.52.
Structural identification data is as follows:1H NMR (500MHz, acetone-d6)δ(ppm):7.11(d,10H),7.03(d,10H),
2.57(t,8H),2.46(s,12H),1.60(m,8H),1.36(m,24H),0.90(t,12H).
The compound dissolves well in chloroform, the common solvents such as toluene and chlorobenzene.
The absorption spectrum of the organic molecule hole mobile material F2 solid film of example preparation is shown in Fig. 2.F2 film be by
F2 is dissolved in organic solvent, obtains F2 solution, is then formed a film on quartz plate using the method for solution spin coating, compound F2 is thin
Film has wide absorption between 307~460nm, absorbs limit in 450nm or so, corresponding optical band gap is 2.75eV.
The film absorption of the compound absorbs width and broadens, absorb position red shift compared with F1 film absorption.
Fig. 5 (b) is the cyclic voltammogram based on F2 film.The chloroform soln of F2 is coated on glass-carbon electrode, with Ag/
AgCl is reference electrode, waits to dry film forming and be placed in hexafluorophosphoric acid 4-butyl amine acetonitrile solution measuring.It is originated from figure
Oxidizing potential and initial reduction current potential are 0.23V. then by formula HOMO=-e (Eox onset+ 4.71) (eV)=- 4.94eV,
LOMO=(Eg opt+ HOMO) (eV)=- 2.19eV.
Embodiment 4, based on the forward direction that F1 or F2 are hole transmission layer, reversed perovskite that F1 is hole mobile material too
The Photovoltaic Properties of positive energy battery
CH is based on by hole transmission layer preparation of F1 or F23NH3PbI3Perovskite solar cell device.Fig. 3 is positive respectively
To the schematic diagram with reversed perovskite solar cell device structure.
Positive device architecture is FTO/ densification TiO2/CH3NH3PbI3/ non-impurity-doped F1 or F2/Au.
Inverted device structure is ITO/ non-impurity-doped F1/CH3NH3PbI3/PC61BM/Al
Positive device the preparation method is as follows: FTO glass successively uses deionized water, ethyl alcohol, acetone supersound washing 15min, then
10min is cleaned with oxygen plasma.FTO glass immersion is in 200mM TiCl4It is placed in 1 in 70 DEG C of drying box in solution and FTO
Hour, FTO glass is cleaned with deionized water and ethyl alcohol again later, then FTO is placed into 1h in 100 DEG C of drying box and dried.
Weigh 0.228g CH3NH3I and 0.663g PbI2It is dissolved in the mixed solution of the DMAC and NMP of 1.2ml (DMAC:NMP=5:1)
CH is made with 60 DEG C of temperature stirring and dissolvings in glove box3NH3PbI3Spin coating precursor liquid, acquired solution are filtered with 0.20um PTFE
It is used after device filtering.There is bl-TiO2The FTO glass of layer is put into glove box, with low speed 1000rpm (15s) and high speed 6000rpm
(55s) spin coating CH3NH3PbI3Precursor liquid, the chlorobenzene solution of fast drop 500ul in high speed 25s, stalling are removed at 100 DEG C
At a temperature of anneal 5min.Room temperature is dropped to FTO sheet glass, then with 5000rpm (30s) spin coating hole mobile material, hole transport
Material is dissolved in the chlorobenzene of 1ml.Finally 1.0 × 10-4Upper one layer is deposited in cavitation layer by thermal evaporation under Pa pressure
The gold electrode of 80nm thickness.Here it is the preparation flow of positive perovskite battery, the maximum effective area of battery is 0.07cm2.?
Fill N2Glove box in use xenon lamp solar simulator AM1.5G intensity (100mW/cm2) under to prepared solar-electricity
These three parameters of open-circuit voltage, short circuit current and the fill factor of pond device are tested, the xenon lamp solar simulator
Silicon diode (there is KG5 Vis filter) correction is used in National Renewable Energy Laboratory (NREL).
Inverted device is dry the preparation method is as follows: ito glass successively uses dish washing liquid, ethyl alcohol, acetone supersound washing 15min
Air blow drying, UVO handle 20min.Again with 5000rpm (40s) spin coating hole mobile material, hole mobile material is dissolved in 1ml
Chlorobenzene in.100 DEG C of annealing 5min in subsequent glove box.With 3500rpm spin coating PdI2, CH is added dropwise after 20s3NH3I, operation terminate
90 DEG C of annealing 8min afterwards.The PC for being 7mg/mL by 1500rpm spin coating solubility61BM chloroform soln.Finally 1.0 × 10- 4The aluminium electrode of upper one layer of 80nm thickness is deposited under Pa pressure in cavitation layer by thermal evaporation.Here it is entire perovskite batteries
Preparation flow, the maximum effective area of battery are 0.07cm2.In filling N2Glove box in using xenon lamp solar simulator
AM1.5G intensity (100mW/cm2) under to the open-circuit voltage of prepared solar cell device, short circuit current and filling because
These three sub parameters are tested, and the xenon lamp solar simulator uses silicon in National Renewable Energy Laboratory (NREL)
Diode (there is KG5 Vis filter) correction.
Fig. 4 (a) and (b) are respectively the current -voltage curve of positive device and inverted device based on F1.Based on different dense
The positive device of F1 preparation is spent, the open-circuit voltage of best device (F1 of 15mg/mL) is 0.95V, short circuit current 18.39mA/
cm2, fill factor 70.27%, energy conversion efficiency 12.28%；The open-circuit voltage of inverted device is 1.04V, short circuit electricity
Stream is 21,18mA/cm2, fill factor 68%, energy conversion efficiency 15.04%.(c) forward direction based on various concentration F2
The open-circuit voltage of the current -voltage curve of device, best device (F2 of 10.00mg/ml) is 0.9V, and short circuit current is
11.62mA/cm2, fill factor 37.72%, energy conversion efficiency 3.96%.
The present invention is described referring to specific embodiment and embodiment.However, the present invention be not limited to it is only described
Embodiment and embodiment.It will be appreciated by those of ordinary skill in the art that teaching herein is based on, without departing from claim
Many changes and substitution can be carried out under the scope of the present invention defined by book.
Claims (7)
1. organic molecule material, which is characterized in that the structural formula of organic molecule material chemical combination as shown in formula I or formula II
Object:
In formula I or formula II, R is the straight chained alkyl that the total number of carbon atoms is 6.
2. a kind of synthetic method of organic molecule material, which is characterized in that the synthetic method is following step:
In tris(dibenzylideneacetone) dipalladium (0), under the catalytic action of tetrafluoro boric acid tri-tert-butylphosphine and sodium tert-butoxide, by formula III
Or compound shown in compound shown in formula V and formula IV carries out Buchwald-Hartwig reaction, as mixes in toluene solution
After carry out back flow reaction, obtain the solution containing organic molecule material shown in formula I or formula II, obtained shown in formula I or formula II after purification
Organic molecule material；
In formula III or formula V, R is the straight chained alkyl that the total number of carbon atoms is 6.
3. the synthetic method of organic molecule material according to claim 2, it is characterised in that: V shownization of the formula III or formula
The molar ratio for closing compound shown in object and formula IV is 1:2~2.2；
The molar ratio of compound shown in the tris(dibenzylideneacetone) dipalladium (0) and formula III or formula V be 0.01~
0.02:1；
The molar ratio of compound shown in the tetrafluoro boric acid tri-tert-butylphosphine and formula III or formula V is 0.015~0.03:1；
The molar ratio of compound shown in the sodium tert-butoxide and formula III or formula V is 2~3:1；
The reflux time is 12~48 hours.
4. the synthetic method of organic molecule according to claim 2, which is characterized in that the purification step are as follows: will be described
Solution containing organic molecule hole mobile material shown in formula I or formula II is cooled to room temperature, extraction, merges organic phase, then uses
Saturated sodium-chloride water solution is washed, and anhydrous magnesium sulfate is dry, after being evaporated in vacuo solvent, crosses chromatographic column purification using mixed solvent,
Obtain organic molecule material shown in formula I or formula II；Wherein, it is using ethyl acetate and petroleum ether volume that formula I, which crosses chromatographic column purification,
Than the mixed solvent for 1:20；It is to use methylene chloride and petroleum ether volume ratio molten for the mixing of 1:3 that formula II, which crosses chromatography,
Agent.
5. the synthetic method of organic molecule material according to claim 2, it is characterised in that: IV compound represented of formula
Synthetic method, be following step: Formula VI, formula VII and the tris(dibenzylideneacetone) dipalladium that will be shown below, 1,
Bis- (diphenylphosphine) ferrocene (DPPF) of 1'-, sodium tert-butoxide and dried toluene are mixed in reactor, are then protected in nitrogen
It is warming up to 90 DEG C~110 DEG C under shield, flows back 12~24 hours, obtains reaction mixture, be cooled to room temperature, extracts, merges organic phase,
It is then washed with saturated sodium-chloride water solution, anhydrous magnesium sulfate is dry, after being evaporated in vacuo solvent, using ethyl acetate and petroleum ether
The mixed liquor that volume ratio is 1:15 crosses chromatographic column purification, and obtaining yellow solid is compound shown in formula IV；Wherein reaction raw materials
Mol ratio is VI compound of formula: VII compound represented of formula=1:1~1.2；
6. organic molecule material is preparing the application in photovoltaic device as hole transmission layer according to claim 1, wherein
I organic molecule of formula prepares positive and/or reversed photovoltaic device as hole transmission layer；II organic molecule of formula is as hole transmission layer
Prepare positive photovoltaic device.
7. application according to claim 6, it is characterised in that: the photovoltaic device is based on CH3NH3PbI3Perovskite
Solar battery.
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| CN115819457A (en) * | 2022-12-06 | 2023-03-21 | 厦门大学 | Carbazole organic micromolecule hole transport material containing phosphonic acid and methylthio, and preparation method and application thereof |
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