CN109836437A - A kind of A-D-A type diazosulfide small molecule and its preparation method and application - Google Patents
A kind of A-D-A type diazosulfide small molecule and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to heterocyclic compound technical field, a kind of A-D-A type diazosulfide small molecule and its preparation method and application is disclosed.By the diazosulfide of different fluorine-containing numbers respectively with electron monomer and catalyst in organic solvent system, under inert gas shielding, first it is protected from light；Column Chromatographic purification is finally used, target product is prepared.The diazosulfide group that the present invention uses has certain rigid planar structure and good carrier transmission characteristics, acceptor-donor-receptor (A-D-A) conjugated structure can be formed with electron donating group simultaneously, obtain lower band gap, widen the spectral absorption with reinforcing material and be applied to construct efficient organic solar battery material.The present invention is conjugated small molecule has preferable absorption, suitable energy level in visible-range, and the donor material being applied in organic photovoltaic cell achieves good device efficiency.Organic solar batteries preparation process is simple, be easily achieved large area manufacture and cost is relatively low.
Description
Technical field
The invention belongs to heterocyclic compound technical field more particularly to a kind of A-D-A type diazosulfide small molecule and its
Preparation method and application.
Background technique
Currently, the immediate prior art: the energy is just always indispensable power in human development progress, to the energy
Development and utilization be also permanency topic, the increasingly increase with the whole world to energy demand, coal, petroleum, natural gas
Equal traditional energies will exhaust, and solar energy is as clean energy resource by people's due to its inexhaustible, nexhaustible the advantages that
Favor.Solar battery is the device for converting the solar into electric energy, it is considered to be most effective and most direct Solar use
Form.
Currently, having been carried out commercialization, but its as the multi-crystal silicon film solar battery that inorganic solar cell represents
It is universal that the unfavorable factors such as high cost and environmental pollution be serious limit it.Organic solar batteries are because of it in recent years
Preparation process is simple, is easily achieved large area manufacture and the advantages that cost is relatively low, be expected to substitute in the near future it is inorganic too
Positive energy battery.
In conclusion problem of the existing technology is: existing inorganic solar cell there are manufacturing cost it is higher and
The problem of be easy to causeing environmental pollution.
Solve the difficulty of above-mentioned technical problem: organic solar batteries there are carrier mobilities low, structural disorder and resistance to
The disadvantages of long property is poor, and the energy transformation ratio of battery is low, the service life is short.
It solves the meaning of above-mentioned technical problem: developing novel organic functional material, the structure of optimization organic photovoltaic devices is
One of research hotspot of organic solar batteries.The research and development of the organic functional material of good properties are beneficial to improve photovoltaic device
Photoelectric conversion efficiency, extend device lifetime, reduce production cost.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of A-D-A type diazosulfide small molecule and its systems
Preparation Method and application.
The invention is realized in this way a kind of A-D-A type diazosulfide small molecule, the A-D-A type diazosulfide
The structural formula of small molecule is Formulas I, Formula II or formula III:
Another object of the present invention is to provide the preparation method of the A-D-A type diazosulfide small molecule described in one kind,
The preparation method of the A-D-A type diazosulfide small molecule include: by different fluorine-containing numbers diazosulfide respectively with to
Electron donating monomer and catalyst are in organic solvent system, under inert gas shielding, are first protected from light；Finally chromatographed using column
Purification, is prepared target product；
The structural formula of the diazosulfide of the fluorine-containing number of difference are as follows:
The molar ratio of formula IV, the compound of structure shown in V, VI and electron monomer is 1:0.2~0.8.
Further, the temperature of reaction is 90~130 DEG C, and the time is 24~72h.
Further, electron monomer is (4,8- bis- (octyloxy) benzo [1,2-B:4,5-B'] Dithiophene -2,6- diyls)
Two (tributyl tins).
Further, catalyst is tetraphenyl phosphine palladium or triphenylphosphine) palladium.
Further, organic solvent is tetrahydrofuran.
Further, the preparation method of the compound of the diazosulfide of the fluorine-containing number of difference includes:
The first step, 4,7- bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles: the two-mouth bottle dry to 25mL
Middle addition 4,7- dibromo benzo [C] [1,2,5] thiadiazoles 291mg, 1mmol, tributyl (4- hexyl -2- thienyl) stannane
1.130g, 2.5mmol, and dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system with nitrogen displaced air three times, so
Afterwards by tetrakis triphenylphosphine palladium Pd (PPh3)450mg, 0.04mmol are added in system, again three times with nitrogen displaced air, heating
It flows back 48 hours to 110 DEG C；After cooling, substance is loaded on silica gel, uses hexane/chloroform 4:1 as mobile phase silicagel column
Chromatography is purified, and 0.256g yellow solid is obtained；
The synthesis of small molecule IV: second step bis- (the 4- hexyl thiophenes of 4,7- is added into the 50mL single port bottle that tinfoil wraps
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles 231mg, 0.495mmol, chloroform 10mL；Under the conditions of 0 DEG C, by N- bromo
Succinimide NBS82mg, 0.495mmol is added several times, each that preceding progress contact plate is added, and takes until occurring two on silica gel plate
When for product, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；It is mentioned with column chromatography chromatography
Pure, resulting pure products are dried, and obtain 0.156g yellow solid；
Third step, the synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2, the 5] thiadiazoles of fluoro- 4, the 7- of 5-: to 25mL
The bromo- 5- fluorobenzene of 4,7- bis- simultaneously [c] [1,2,5] thiadiazoles 310mg, 1mmol, tributyl (4- hexyl-are added in dry two-mouth bottle
2- thienyl) stannane 1.130g, 2.5mmol, and dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system is set with nitrogen
It ventilates three times, then tetrakis triphenylphosphine palladium Pd (PPh3) 450mg, 0.04mmol is added in system, set again with nitrogen
It ventilates three times, is heated to 110 DEG C and flows back 48 hours；After cooling, substance is loaded on silica gel, is made using hexane/chloroform 4:1
It is purified for mobile phase silica gel column chromatography, obtains 0.243g yellow solid；
4th step, the synthesis of small molecule V: into the 50mL single port bottle that tinfoil wraps be added fluoro- 4, the 7- of 5- it is bis- (4- oneself
Base thiophene -2- base) benzo [c] [1,2,5] thiadiazoles 243mg, 0.5mmol, chloroform 10mL；Under the conditions of 0 DEG C, by N- bromine
It is added several times for succinimide NBS 88mg, 0.5mmol, contact plate is carried out before being added every time, until occurring two on silica gel plate
When substitution product, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；It is carried out with column chromatography chromatography
Purification, resulting pure products are dried, and obtain 0.123g yellow solid；
5th step, the synthesis of 5,6- bis- fluoro- bis- (4- hexyl thiophene -2- base) benzo [c] [1,2, the 5] thiadiazoles of 4,7-: to
Bromo- 5,6- difluoro benzo [c] [1,2,5] the thiadiazoles 327mg of 4,7- bis-, 1mmol, tributyl is added in 25mL dry two-mouth bottle
(4- hexyl -2- thienyl) stannane 1.130g, 2.5mmol, and dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system
Three times with nitrogen displaced air, then 4 50mg of tetrakis triphenylphosphine palladium Pd (PPh3), 0.04mmol are added in system, again
Three times with nitrogen displaced air, 110 DEG C are heated to flow back 72 hours；After cooling, substance is loaded on silica gel, using hexane/
Chloroform 4:1 is purified as mobile phase silica gel column chromatography, obtains 0.232g yellow solid；
The synthesis of small molecule VI: 6th step it is bis- that fluoro- 4, the 7- of 5,6- bis- is added into the 50mL single port bottle that tinfoil wraps
(4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles 226mg, 0.45mmol, chloroform 10mL；Under the conditions of 0 DEG C,
N-bromosuccinimide NBS 80mg, 0.45mmol are added several times, contact plate is carried out before being added every time, until on silica gel plate
When there is two substitution products, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；With column chromatography chromatography
Method is purified, and resulting pure products are dried, and obtains 0.142g yellow solid.
Another object of the present invention is to provide a kind of sun prepared by the A-D-A type diazosulfide small molecule
Energy battery device, the solar cell device are as follows:
Glass/ITO substrate is cleaned with detergent, is ultrasonically treated in acetone and isopropanol, and is done in 100 DEG C of baking ovens
It is dry overnight；In glove box, the electro-conductive glass indium oxide that the nano zine oxide of 20mg/mL is spin-coated on after treatment with ultraviolet light
On tin (ITO) anode；Active layer (Polymer:PC71BM=1:1.5wt) blend solution is spin-coated on to the top of PEDOT:PSS
Portion；Device is placed in vacuum chamber (< 10-6Pa in), in the vacuum chamber, the molybdenum trioxide of 7nm thickness and the Ag of 100nm thickness are deposited
On active layer；Obtaining structure is glass/ITO/PEDOT:PSS/Polymer:PC71BM/Ca/Al, and the effective area of battery is
4mm2。
Small molecule is dissolved in chloroform, using the optical property of ultraviolet-ray visible absorbing research small molecule chloroformic solution；Small point
The normalization absorption spectrum of sub- I, II, III in chloroformic solution is as shown in Figure 2.As can be seen from Figure 2: I and II are in chlorine for small molecule
Absorption region in imitative solution is substantially uniform.Small molecule I, II, III have two characteristic peaks in the region of ultraviolet-visible.Small point
The specific data of the absorption peak of sub- I, II, III are as follows: I:386nm, 506nm；II:385nm, 504nm；III:414nm, 483nm.
As the content increase of fluorine-containing donor shows slight blue shift in the absorption of solution.The boundary of small molecule I, II, III absorb
Respectively 622nm, 624nm, 609nm；According to formula Eg optThe available optical band gap of=1240/ λ be respectively 1.99eV,
1.98eV,2.03eV.It can be seen that: as the increase of the fluorine atom containing donor increases, optical band gap is obvious there is no occurring
Variation, fluorinated copolymer band gap is in 2.00eV or so.
The current density voltage curve of small molecule I, II, III are measured, as a result as shown in Figure 4.According to the electric current-of small molecule
Voltage curve obtains three characteristic parameters and energy conversion efficiency of solar battery；The results are shown in Table 1.It can from table
Out: as the number containing fluorine atom increases, the voltage of solar battery is all improved, and degree, between 0.04V, is obtained 0
Beneficial to the introduction of fluorine atom, the decline of HOMO energy level is resulted in.With the increase of fluorine atom amount, decline is presented in short circuit current
Trend, from 9.92mA/cm2Have decreased to 8.62mA/cm2.It may be from increasing in fluorine content, result in the excessive poly- of phase
Collection presents downward trend to short circuit current.Solar battery can be improved in introducing fluorine atom appropriate as can be seen from above
Transfer efficiency.
The photovoltaic parameter of 1 solar battery of table
| Serial number | JSC/mA/cm2 | VOC/V | FF*100 | PCE*100 |
| I | 9.92±0.12(10.04) | 0.61±0.01(0.62) | 60.89±1(61.89) | 3.68±0.18(3.86) |
| II | 9.91±0.18(10.09) | 0.64±0.01(0.65) | 62.2±1.03(63.25) | 3.94±0.34(4.28) |
| III | 8.62±0.22(8.84) | 0.65±0.01(0.63) | 50.3±0.22(50.52) | 2.81±0.25(3.06) |
Another object of the present invention is to provide a kind of unmanned planes for being equipped with the solar cell device.
Another object of the present invention is to provide a kind of automobiles for being equipped with the solar cell device.
In conclusion advantages of the present invention and good effect are as follows:
A-D-A type diazosulfide small molecule provided by the invention, can be dissolved in a variety of organic solvents, as dichloromethane
In the common organic solvents such as alkane, chloroform, tetrahydrofuran, toluene, chlorobenzene, dichloro-benzenes, the processing of solution processing method can be used (as revolved
It applies)；There is preferable absorption, suitable energy level in visible-range, be suitble to do the donor material in organic photovoltaic cell.Too
The absorption spectrum and solar spectrum matching degree, carrier mobility and suitable energy level of positive energy battery material are for obtaining
High device efficiency is most important.The diazosulfide group that the present invention uses has certain rigid planar structure and good
Carrier transmission characteristics, while acceptor-donor-receptor (A-D-A) conjugated structure can be formed with electron donating group, it obtains lower
Band gap, widen the spectral absorption with reinforcing material and be applied to construct efficient organic solar battery material.
The present invention be conjugated small molecule have in visible-range it is preferable absorb, suitable energy level, be applied to it is organic too
Donor material in positive electricity pond achieves good device efficiency.Organic solar batteries preparation process is simple, it is big to be easily achieved
Area manufactures and cost is relatively low.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of A-D-A type diazosulfide small molecule provided in an embodiment of the present invention.
Fig. 2 is the A-D-A type diazosulfide small molecule of the offer of the embodiment of the present invention 1 in CHCl3In ultraviolet-visible inhale
Receive spectrogram.
Fig. 3 is that the ultraviolet-visible of the A-D-A type diazosulfide small molecule of the offer of the embodiment of the present invention 1 in the film is inhaled
Receive spectrogram.
Fig. 4 is that the J-V for the A-D-A type diazosulfide small molecule solar cell device that the embodiment of the present invention 1 provides is bent
Line chart.
Fig. 5 is the A-D-A type diazosulfide small molecule solar cell device structure that the embodiment of the present invention 1~5 provides
Schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The present invention is that solve existing inorganic solar cell higher there are manufacturing cost and be easy to cause environmental pollution
Problem；A kind of A-D-A type diazosulfide small molecule and its preparation method and application is provided, A-D-A type diazosulfide is small
The structural formula of molecule is Formulas I, Formula II or formula III:
Application principle of the invention is explained in detail with reference to the accompanying drawing.
The preparation method of A-D-A type diazosulfide small molecule provided in an embodiment of the present invention includes:
S101: reaction raw materials and reaction condition prepare；Reaction raw materials are as follows: the diazosulfide (structure of different fluorine-containing numbers
Formula is as shown in formula IV, V, VI), electron monomer, catalyst；
S102: it in organic solvent system, under inert gas shielding, is protected from light；
S103: column Chromatographic purification；
S104: target product is prepared.
As the preferred embodiment of the present invention, step S101 is specifically included: the A-D-A type diazosulfide small molecule
Preparation method specifically: as different fluorine-containing numbers diazosulfide (structural formula is as shown in formula IV, V, VI) respectively with electron
Monomer and catalyst are in organic solvent system, under inert gas shielding, are first protected from light, and are finally mentioned using column chromatography
It is pure, target product is prepared (structural formula is as shown in Formulas I, II, III).
The formula IV, V, VI structural formula are as follows:
As the preferred embodiment of the present invention, the temperature of the reaction is 90~130 DEG C, and the time is 24~72h.
As the preferred embodiment of the present invention, the electron monomer is (4,8- bis- (octyloxy) benzo [1,2-B:4,5-
B'] Dithiophene -2,6- diyl) two (tributyl tins).
As the preferred embodiment of the present invention, the catalyst is tetrakis triphenylphosphine palladium.
As the preferred embodiment of the present invention, the organic solvent is tetrahydrofuran.
As the preferred embodiment of the present invention, the compound and the electron monomer of the formula IV, structure shown in V, VI
Molar ratio be 1:(0.2~0.8).
As the preferred embodiment of the present invention, the compound and the electron monomer of the formula IV, structure shown in V, VI
Molar ratio be 1:(0.3~0.5).
As the preferred embodiment of the present invention, the diazosulfide of the fluorine-containing number of difference (structural formula for example formula IV, V,
Shown in VI) compound be prepared by the following method to obtain:
Bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of S1:4,7-: add in the two-mouth bottle dry to 25mL
Enter 4,7- dibromo benzo [C] [1,2,5] thiadiazoles (291mg, 1mmol), tributyl (4- hexyl -2- thienyl) stannane
(1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, system nitrogen displaced air three
It is secondary, then tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) is added in system, uses nitrogen displaced air again
Three times, 110 DEG C are heated to flow back 48 hours；After cooling, substance is loaded on silica gel, uses hexane/chloroform (4:1) as stream
Dynamic phase silica gel column chromatography is purified, and 0.256g yellow solid is obtained；
S2: the bis- (4- hexyl thiophene -2- of 4,7- the synthesis of small molecule IV: are added into the 50mL single port bottle that tinfoil wraps
Base) benzo [c] [1,2,5] thiadiazoles (231mg, 0.495mmol), chloroform (10mL)；Under the conditions of 0 DEG C, by N- bromo
Succinimide (NBS) (82mg, 0.495mmol) is added several times, contact plate is carried out before being added every time, until occurring on silica gel plate
When two substitution products, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.With column chromatography chromatography (stone
Ratio is 10:1 between oily ether and methylene chloride) it is purified, resulting pure products are dried, and it is solid to obtain 0.156g yellow
Body；
The synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of the fluoro- 4,7- of S3:5-: dry to 25mL
Two-mouth bottle in the bromo- 5- fluorobenzene of 4,7- bis- simultaneously [c] [1,2,5] thiadiazoles (310mg, 1mmol), tributyl (4- hexyl -2- is added
Thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, system nitrogen
Tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) three times, is then added in system, uses nitrogen again by displaced air
Gas displaced air three times, is heated to 110 DEG C and flows back 48 hours；After cooling, substance is loaded on silica gel, uses hexane/chloroform
(4:1) is purified as mobile phase silica gel column chromatography, obtains 0.243g yellow solid；
S4: bis- (the 4- hexyl thiophenes of the fluoro- 4,7- of 5- the synthesis of small molecule V: are added into the 50mL single port bottle that tinfoil wraps
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles (243mg, 0.5mmol), chloroform (10mL)；Under the conditions of 0 DEG C, by N- bromine
It is added several times for succinimide (NBS) (88mg, 0.5mmol), contact plate is carried out before being added every time, until occurring on silica gel plate
When two substitution products, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.With column chromatography chromatography (stone
Ratio is 10:1 between oily ether and methylene chloride) it is purified, resulting pure products are dried, and it is solid to obtain 0.123g yellow
Body.
The synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of the fluoro- 4,7- of S5:5,6- bis-: to 25mL
Bromo- 5,6- difluoro benzo [c] [1,2, the 5] thiadiazoles (327mg, 1mmol) of 4,7- bis-, tributyl are added in dry two-mouth bottle
(4- hexyl -2- thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation,
Tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) three times, is then added system with nitrogen displaced air by system
In, again three times with nitrogen displaced air, it is heated to 110 DEG C and flows back 72 hours；After cooling, substance is loaded on silica gel, is made
Purified with hexane/chloroform (4:1) as mobile phase silica gel column chromatography, obtains 0.232g yellow solid；
S6: the synthesis of small molecule VI: into the 50mL single port bottle that tinfoil wraps be added the fluoro- 4,7- of 5,6- bis- it is bis- (4- oneself
Base thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (226mg, 0.45mmol), chloroform (10mL)；Under the conditions of 0 DEG C,
N-bromosuccinimide (NBS) (80mg, 0.45mmol) is added several times, contact plate is carried out before being added every time, until silica gel
When occurring two substitution products on plate, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.Use column chromatography
Chromatography (ratio is 10:1 between petroleum ether and methylene chloride) is purified, and resulting pure products are dried, and obtain
0.142g yellow solid.
Further, the application of A-D-A type diazosulfide small molecule provided in an embodiment of the present invention are as follows: provide one kind too
Positive energy battery device, the solar cell device successively include glassy layer, conductive indium-tin oxide layer, zinc oxide electricity from the bottom to top
Active layer, molybdenum trioxide hole transmission layer and the silver electrode that sub- transport layer, A-D-A type diazosulfide small molecule are mixed with C71
Layer.
Application principle of the invention is further described combined with specific embodiments below.
Embodiment 1
The present invention provides a kind of A-D-A type diazosulfide small molecule, the structural formula of the small molecule is Formulas I, as follows
It is shown:
A-D-A type diazosulfide small molecule Formulas I provided in this embodiment is prepared by the following method to obtain:
By the compound of structure shown in 1mol formula IV and 0.5mol (bis- (octyloxy) benzos [1,2-B:4,5-B'] two of 4,8-
Thiophene -2,6- diyl) two (tributyl tins) are placed in toluene solvant, and using three (2- aminomethyl phenyls), phosphine is as catalyst, lazy
Under property gas shield, controlled at 110 DEG C, it is protected from light 72h, column Chromatographic purification obtains target product Formulas I；1H NMR
(CDCl3,400MHz, δ/ppm): 8.03 (d, 4H), 7.81 (s, 4H), 7.63 (s, 2H), 7.08 (s, 2H), 4.41 (t, 4H),
3.02 (t, 4H), 2.75 (, 4H), 1.75-2.35 (m, 10H), 1.4-1.75 (m, 34H), 0.75-1.75 (m, 30H)；13CNMR
(CDCl3,100MHz, δ/ppm): 154.44,144.87,144.26,142.11,139.75,138.71,133.01,131.15,
130.10,128.99,128.24,126.88,122.56,118.27,75.15,32.98,31.65,30.43,27.62,
23.09,14.69,10.65.The synthetic route of the Formulas I is as follows:
Fig. 1 is that A-D-A type provided in this embodiment is conjugated UV-visible absorption spectrum of the small molecule in CHCl3, figure
2 are conjugated the UV-visible absorption spectrum of small molecule in the film for A-D-A type provided in this embodiment.
The present invention provides a kind of solar cell device, as shown in figure 4, the solar cell device from the bottom to top according to
Secondary includes glass (Glass) layer, tin indium oxide (ITO) conductive layer, zinc oxide (ZnO) electron transfer layer, A-D-A type benzo thiophene two
Azoles small molecule mixes the active layer of (A-D-A type diazosulfide small molecule/PCBM71), the hole molybdenum trioxide (MoO3) with C71
Transport layer and silver-colored (Ag) electrode layer, the structural formula of the A-D-A type diazosulfide small molecule are Formulas I compound represented,
It is prepared by the method that embodiment 1 provides.
The preparation method of the solar cell device does not have special limitation, using it is well known to those skilled in the art too
The technical solution of positive energy battery preparation, in embodiments of the present invention, the preparation method of the solar cell device is preferred
The following steps are included:
S1: the glass that surface sputtering has ITO is successively first subjected to cleaning and UV ozone is handled, obtains clean ITO glass
Glass layer；
S2: again on the processed ito glass layer of step S1 first successively spin coating ZnO and A-D-A type conjugation small molecule/
PCBM71, MoO3 and Ag electrode is successively deposited again, ZnO electron transfer layer, A-D-A type is sequentially formed on the ito glass layer
Diazosulfide small molecule/PCBM71 active layer, MoO3 hole transmission layer and Ag electrode layer, are prepared solar battery device
Part.
Embodiment 2
The present invention provides a kind of A-D-A type diazosulfide small molecule, the structural formula of the small molecule is Formula II, as follows
It is shown:
A-D-A type diazosulfide small molecule Formula II provided in this embodiment is prepared by the following method to obtain: by 1mol
The compound and 0.5mol (bis- (octyloxy) benzo [1,2-B:4,5-B'] Dithiophene -2,6- diyls of 4,8-) of structure shown in formula V
Two (tributyl tins) are placed in toluene solvant, using copper oxide as catalyst, under inert gas protection, controlled at
110 DEG C, it is protected from light 72h, column Chromatographic purification obtains target product Formula II；1HNMR (CDCl3,400MHz, δ/ppm): 8.23
(s, 4H), 7.85 (s, H), 7.75 (s, 3H), 7.53 (s, 3H), 4.26 (t, 4H), 2.91 (t, 4H), 2.63 (t, 4H), 1.51-
2.25 (m, 22H), 0.75-1.51 (m, 52H)；13CNMR (CDCl3,100MHz, δ/ppm): 156.43,146.86,145.27,
141.11,138.76,137.72,134.02,132.25,129.11,127.88,123.56,117.27,77.15,35.98,
34.65,32.41,28.66,24.11,15.63,8.43.The synthetic route of the Formula II is as follows:
The present invention provides a kind of solar cell device, as shown in figure 4, the solar cell device from the bottom to top according to
Secondary includes glass (Glass) layer, tin indium oxide (ITO) conductive layer, zinc oxide (ZnO) electron transfer layer, A-D-A type benzo thiophene two
Azoles small molecule mixes the active layer of (A-D-A type diazosulfide small molecule/PCBM71), the hole molybdenum trioxide (MoO3) with C71
Transport layer and silver-colored (Ag) electrode layer, the structural formula of the A-D-A type diazosulfide small molecule are Formula II compound represented,
It is prepared by the method that embodiment 2 provides.
The preparation method of the solar cell device does not have special limitation, using it is well known to those skilled in the art too
The technical solution of positive energy battery preparation, in embodiments of the present invention, the preparation method of the solar cell device is preferred
The following steps are included:
S1: the glass that surface sputtering has ITO is successively first subjected to cleaning and UV ozone is handled, obtains clean ITO glass
Glass layer；
S2: again on the processed ito glass layer of step S1 first successively spin coating ZnO and A-D-A type conjugation small molecule/
PCBM71, MoO3 and Ag electrode is successively deposited again, ZnO electron transfer layer, A-D-A type is sequentially formed on the ito glass layer
Diazosulfide small molecule/PCBM71 active layer, MoO3 hole transmission layer and Ag electrode layer, are prepared solar battery device
Part.
Embodiment 3
The present invention provides a kind of A-D-A type diazosulfide small molecule, the structural formula of the small molecule is formula III, such as
Shown in lower:
A-D-A type diazosulfide small molecule formula III provided in this embodiment is prepared by the following method to obtain:
By the compound of structure shown in 1mol formula IV and 0.5mol (bis- (octyloxy) benzos [1,2-B:4,5-B'] two of 4,8-
Thiophene -2,6- diyl) two (tributyl tins) are placed in toluene solvant, using tris(dibenzylideneacetone) dipalladium as catalyst,
Under inert gas protection, controlled at 120 DEG C, it is protected from light 70h, column Chromatographic purification obtains target product formula III；
1HNMR(CDCl3, 400MHz, δ/ppm): 8.11 (d, 2H), 7.55 (s, 2H), 7.49 (s, 1H), 7.31 (s, 1H), 7.26 (s,
1H), 7.08 (s, 1H), 4.25 (t, 8H), 2.93 (t, 2H), 2.69 (t, 2H), 1.7-2.3 (m, 26H), 0.55-1.7 (m,
48H)；13CNMR (CDCl3,100MHz, δ/ppm): 157.23,148.76,146.17,142.62,138.76,135.02,
132.25,130.11,128.77,125.64,118.37,78.15,36.77,33.95,33.41,29.56,25.21,17.83,
9.41.The synthetic route of the formula III is as follows:
The present invention provides a kind of solar cell device, as shown in figure 4, the solar cell device from the bottom to top according to
Secondary includes glass (Glass) layer, tin indium oxide (ITO) conductive layer, zinc oxide (ZnO) electron transfer layer, A-D-A type benzo thiophene two
Azoles small molecule mixes the active layer of (A-D-A type diazosulfide small molecule/PCBM71), molybdenum trioxide (MoO with C713) hole
Transport layer and silver-colored (Ag) electrode layer, the structural formula of the A-D-A type diazosulfide small molecule are formula III compound represented,
It is prepared by the method that embodiment 3 provides.
The preparation method of the solar cell device does not have special limitation, using it is well known to those skilled in the art too
The technical solution of positive energy battery preparation, in embodiments of the present invention, the preparation method of the solar cell device is preferred
The following steps are included:
S1: the glass that surface sputtering has ITO is successively first subjected to cleaning and UV ozone is handled, obtains clean ITO glass
Glass layer；
S2: again on the processed ito glass layer of step S1 first successively spin coating ZnO and A-D-A type conjugation small molecule/
PCBM71, MoO3 and Ag electrode is successively deposited again, ZnO electron transfer layer, A-D-A type is sequentially formed on the ito glass layer
It is conjugated small molecule/PCBM71 active layer, MoO3 hole transmission layer and Ag electrode layer, solar cell device is prepared.
Formula IV described in Examples 1 to 3, structure shown in V, VI compound be prepared by the following method to obtain:
Bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of S1:4,7-: add in the two-mouth bottle dry to 25mL
Enter 4,7- dibromo benzo [C] [1,2,5] thiadiazoles (291mg, 1mmol), tributyl (4- hexyl -2- thienyl) stannane
(1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, system nitrogen displaced air three
It is secondary, then tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) is added in system, uses nitrogen displaced air again
Three times, 110 DEG C are heated to flow back 48 hours；After cooling, substance is loaded on silica gel, uses hexane/chloroform (4:1) as stream
Dynamic phase silica gel column chromatography is purified, and 0.256g yellow solid is obtained；
S2: the bis- (4- hexyl thiophene -2- of 4,7- the synthesis of small molecule IV: are added into the 50mL single port bottle that tinfoil wraps
Base) benzo [c] [1,2,5] thiadiazoles (231mg, 0.495mmol), chloroform (10mL)；Under the conditions of 0 DEG C, by N- bromo
Succinimide (NBS) (82mg, 0.495mmol) is added several times, contact plate is carried out before being added every time, until occurring on silica gel plate
When two substitution products, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.With column chromatography chromatography (stone
Ratio is 10:1 between oily ether and methylene chloride) it is purified, resulting pure products are dried, and it is solid to obtain 0.156g yellow
Body；.
The synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of the fluoro- 4,7- of S3:5-: dry to 25mL
Two-mouth bottle in the bromo- 5- fluorobenzene of 4,7- bis- simultaneously [c] [1,2,5] thiadiazoles (310mg, 1mmol), tributyl (4- hexyl -2- is added
Thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, system nitrogen
Tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) three times, is then added in system, uses nitrogen again by displaced air
Gas displaced air three times, is heated to 110 DEG C and flows back 48 hours；After cooling, substance is loaded on silica gel, uses hexane/chloroform
(4:1) is purified as mobile phase silica gel column chromatography, obtains 0.243g yellow solid；
S4: bis- (the 4- hexyl thiophenes of the fluoro- 4,7- of 5- the synthesis of small molecule V: are added into the 50mL single port bottle that tinfoil wraps
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles (243mg, 0.5mmol), chloroform (10mL)；Under the conditions of 0 DEG C, by N- bromine
It is added several times for succinimide (NBS) (88mg, 0.5mmol), contact plate is carried out before being added every time, until occurring on silica gel plate
When two substitution products, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.With column chromatography chromatography (stone
Ratio is 10:1 between oily ether and methylene chloride) it is purified, resulting pure products are dried, and it is solid to obtain 0.123g yellow
Body.
The synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles of the fluoro- 4,7- of S5:5,6- bis-: to 25mL
Bromo- 5,6- difluoro benzo [c] [1,2, the 5] thiadiazoles (327mg, 1mmol) of 4,7- bis-, tributyl are added in dry two-mouth bottle
(4- hexyl -2- thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation,
Tetrakis triphenylphosphine palladium Pd (PPh3) 4 (50mg, 0.04mmol) three times, is then added system with nitrogen displaced air by system
In, again three times with nitrogen displaced air, it is heated to 110 DEG C and flows back 72 hours；After cooling, substance is loaded on silica gel, is made
Purified with hexane/chloroform (4:1) as mobile phase silica gel column chromatography, obtains 0.232g yellow solid；
S6: the synthesis of small molecule VI: into the 50mL single port bottle that tinfoil wraps be added the fluoro- 4,7- of 5,6- bis- it is bis- (4- oneself
Base thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (226mg, 0.45mmol), chloroform (10mL)；Under the conditions of 0 DEG C,
N-bromosuccinimide (NBS) (80mg, 0.45mmol) is added several times, contact plate is carried out before being added every time, until silica gel
When occurring two substitution products on plate, stop that NBS is added.Product carries out vacuum distillation removing solvent and obtains crude product.Use column chromatography
Chromatography (ratio is 10:1 between petroleum ether and methylene chloride) is purified, and resulting pure products are dried, and obtain
0.142g yellow solid.
The compound formula IV, V, VI synthetic route it is as follows:
A-D-A type diazosulfide small molecule provided by the invention, can be dissolved in methylene chloride, chloroform, tetrahydrofuran,
In the common organic solvents such as toluene, chlorobenzene, dichloro-benzenes, solution processing method processing (such as spin coating) can be used；In visible-range
It is interior that there is preferable absorption, suitable energy level, it is suitble to do the donor material in organic photovoltaic cell.The suction of solar cell material
Spectrum and solar spectrum matching degree, carrier mobility and suitable energy level are received for obtaining high device efficiency to pass
Important, the diazosulfide group that the present invention uses has certain rigid planar structure and good carrier transmission characteristics,
Acceptor-donor-receptor (A-D-A) conjugated structure can be formed with electron donating group simultaneously, to obtain lower band gap, open up
Wide and reinforcing material spectral absorption and be applied to construct efficient organic solar battery material.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of A-D-A type diazosulfide small molecule, which is characterized in that the knot of the A-D-A type diazosulfide small molecule
Structure formula is Formulas I, Formula II or formula III:
Formulas I:
Formula II:
Formula III:
2. a kind of preparation method of A-D-A type diazosulfide small molecule as described in claim 1, which is characterized in that described
The preparation method of A-D-A type diazosulfide small molecule include: by different fluorine-containing numbers diazosulfide respectively with electron
Monomer and catalyst are in organic solvent system, under inert gas shielding, are first protected from light；Finally mentioned using column chromatography
It is pure, target product is prepared；
The structural formula of the diazosulfide of the fluorine-containing number of difference are as follows:
The molar ratio of formula IV, the compound of structure shown in V, VI and electron monomer is 1:0.2~0.8.
3. the preparation method of A-D-A type diazosulfide small molecule as claimed in claim 2, which is characterized in that the temperature of reaction
Degree is 90~130 DEG C, and the time is 24~72h.
4. the preparation method of A-D-A type diazosulfide small molecule as claimed in claim 2, which is characterized in that electron list
Body is (bis- (octyloxy) benzo [1,2-B:4,5-B'] Dithiophene -2,6- diyls of 4,8-) two (tributyl tins).
5. the preparation method of A-D-A type diazosulfide small molecule as claimed in claim 2, which is characterized in that catalyst is
Tetraphenyl phosphine palladium or triphenylphosphine) palladium.
6. the preparation method of A-D-A type diazosulfide small molecule as claimed in claim 2, which is characterized in that organic solvent
For tetrahydrofuran.
7. the preparation method of A-D-A type diazosulfide small molecule as claimed in claim 2, which is characterized in that the difference
The preparation method of the compound of the diazosulfide of fluorine-containing number includes:
4,7- bis- (4- hexyl thiophene -2- base) benzo [c] [1,2,5] thiadiazoles: the first step adds in the two-mouth bottle dry to 25mL
Enter 4,7- dibromo benzo [C] [1,2,5] thiadiazoles 291mg, 1mmol, tributyl (4- hexyl -2- thienyl) stannane 1.130g,
2.5mmol, and being dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system with nitrogen displaced air three times, then by four
(triphenylphosphine) palladium Pd (PPh3) 450mg, 0.04mmol adds in system, again three times with nitrogen displaced air, is heated to 110
DEG C reflux 48 hours；After cooling, substance is loaded on silica gel, use hexane/chloroform 4:1 as mobile phase silica gel column chromatography into
Row purifying, obtains 0.256g yellow solid；
The synthesis of small molecule IV: second step the bis- (4- hexyl thiophene -2- of 4,7- is added into the 50mL single port bottle that tinfoil wraps
Base) benzo [c] [1,2,5] thiadiazoles 231mg, 0.495mmol, chloroform 10mL；Under the conditions of 0 DEG C, by N- bromo amber
Acid imide NBS82mg, 0.495mmol is added several times, each that preceding progress contact plate is added, and produces until occurring two substitutions on silica gel plate
When object, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；It is purified with column chromatography chromatography, institute
The pure products obtained are dried, and obtain 0.156g yellow solid；
Third step, the synthesis of bis- (4- hexyl thiophene -2- base) benzo [c] [1,2, the 5] thiadiazoles of fluoro- 4, the 7- of 5-: dry to 25mL
Two-mouth bottle in the bromo- 5- fluorobenzene of 4,7- bis- simultaneously [c] [1,2,5] thiadiazoles 310mg, 1mmol, tributyl (4- hexyl -2- thiophene is added
Pheno base) stannane 1.130g, 2.5mmol, and dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system is replaced empty with nitrogen
Gas three times, then by tetrakis triphenylphosphine palladium Pd (PPh3)450mg, 0.04mmol are added in system, use nitrogen displaced air again
Three times, 110 DEG C are heated to flow back 48 hours；After cooling, substance is loaded on silica gel, uses hexane/chloroform 4:1 as flowing
Phase silica gel column chromatography is purified, and 0.243g yellow solid is obtained；
The synthesis of small molecule V: 4th step bis- (the 4- hexyl thiophenes of fluoro- 4, the 7- of 5- is added into the 50mL single port bottle that tinfoil wraps
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles 243mg, 0.5mmol, chloroform 10mL；Under the conditions of 0 DEG C, by N- bromo amber
Amber acid imide NBS88mg, 0.5mmol is added several times, each that preceding progress contact plate is added, and produces until occurring two substitutions on silica gel plate
When object, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；It is purified with column chromatography chromatography, institute
The pure products obtained are dried, and obtain 0.123g yellow solid；
5th step, the synthesis of 5,6- bis- fluoro- bis- (4- hexyl thiophene -2- base) benzo [c] [1,2, the 5] thiadiazoles of 4,7-: to 25mL
4,7- bis- bromo- 5,6- difluoro benzo [c] [1,2,5] thiadiazoles 327mg, 1mmol, tributyl (4- are added in dry two-mouth bottle
Hexyl -2- thienyl) stannane 1.130g, 2.5mmol, and dissolved with the tetrahydrofuran 15mL after dry and deoxygenation, system is used
Tetrakis triphenylphosphine palladium Pd (PPh3) 450mg, 0.04mmol three times, are then added in system, are used again by nitrogen displaced air
Nitrogen displaced air three times, is heated to 110 DEG C and flows back 72 hours；After cooling, substance is loaded on silica gel, uses hexane/chlorine
Imitative 4:1 is purified as mobile phase silica gel column chromatography, obtains 0.232g yellow solid；
6th step, the synthesis of small molecule VI: be added into the 50mL single port bottle that tinfoil wraps fluoro- 4, the 7- of 5,6- bis- it is bis- (4- oneself
Base thiophene -2- base) benzo [c] [1,2,5] thiadiazoles 226mg, 0.45mmol, chloroform 10mL；Under the conditions of 0 DEG C, by N-
Bromosuccinimide NBS80mg, 0.45mmol is added several times, each that preceding progress contact plate is added, until occurring on silica gel plate
When two substitution products, stop that NBS is added；Product carries out vacuum distillation removing solvent and obtains crude product；With column chromatography chromatography into
Row purification, resulting pure products are dried, and obtain 0.142g yellow solid.
8. a kind of solar cell device prepared by A-D-A type diazosulfide small molecule described in claim 1, feature
It is, the solar cell device successively includes glassy layer, conductive indium-tin oxide layer, zinc oxide electron-transport from the bottom to top
Active layer, molybdenum trioxide hole transmission layer and the silver electrode layer that layer, A-D-A type diazosulfide small molecule are mixed with C71.
9. a kind of unmanned plane for being equipped with solar cell device described in claim 8.
10. a kind of automobile for being equipped with solar cell device described in claim 8.
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