CN108727568A - Crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide, preparation method and applications - Google Patents
Crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide, preparation method and applications Download PDFInfo
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Abstract
The invention discloses the crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide, preparation method and applications, composition by adjusting the monomer of olefin-containing key prepares ternary atactic polymer and the high-temperature heat treatment time of different alkene linkage content, it also discloses how to obtain the active layer material with cross-linked structure while keeping high electricity conversion simultaneously, it is expected that the full polymers solar device that the thermal stability for obtaining high-photoelectric transformation efficiency is outstanding, realize the application in organic solar batteries field, in addition, present invention process is simple, resulting materials are applied to compare with general polymeric donor/receptor photovoltaic material active layer on photovoltaic material active layer, show better heat safe thermal stability, therefore, the stability of device can be significantly improved applied to full polymers area of solar cell.
Description
Technical field
The invention belongs to field of photovoltaic materials, especially a kind of organic solar photoelectric material, more particularly one kind can
Crosslinked full polymers solar cell acceptor material based on benzene-naphthalene diimide, preparation method and applications.
Background technology
It is blended as made of photosensitive activity layer p-type conjugated polymer donor material and n-type polymeric acceptor material
All-polymer solar cell (All-PSCs) is widely studied due to good film-forming property, stability good the advantages that.All- at present
The photoelectric conversion efficiency of PSCs has been more than fullerene system battery in a few years, illustrates its great potential.But Quan Ju
The service life of object solar cell is compared with inorganic photovoltaic cell still a certain distance, and is applied to realize, further
The thermal stability for improving full polymers solar device is necessary.Although the photo and thermal stability of the battery of full polymers than fullerene and
Small molecule receptor battery is compared to being greatly improved, but the efficiency for the device reported still can in the short period at high temperature
Decaying, is mainly due to polymeric donor/acceptor active layer and is obtained using physical method, and two macromolecular substances are once mixed
Their entropy contribution will be substantially reduced together, and the degree of disorder increase of polymer chain causes to can not form ideal between receptor
Phase separation size (exciton diffusion length 10nm) to hinder the separation and transmission of charge.The light of full polymers solar cell
To receptor it is macromolecular in quick active layer, if by this two classes macromolecular with covalent in the inierpeneirating network structure of original formation
The mode of key, which is connected, can then make active layer pattern fix to improve the stability (light, heat) of active layer, and be crosslinked be then by
The simple and effective method of one kind that two kinds of macromoleculars are connected.Crosslinking introduces crosslinkable groups in the end group of polymer lateral chain,
Such as：Bromo, ethylene linkage, azido, the crosslinked group of end group generates free radicals under ultraviolet light or heating condition, by certainly
By base coupling mechanism to make generation covalent bond between macromolecular not melted insoluble cross-linked polymer to link together.
Under the background technology, inventor herein is introduced crosslinked group (olefinic double bonds) by the method for ternary polymerization
In the side chain for the efficient polymeric acceptor based on benzene-naphthalene diimide (NDI) reported at present, the polymeric acceptor based on NDI
Photoelectric conversion efficiency can reach 10.1% at present, while use the double bond containing polymer of the side chain reported as donor, will
They, which are combined, is used as active layer, and to receptor, double bond fracture generates free radicals the double bond containing polymer of side chain at high temperature, by certainly
The active layer to receptor inierpeneirating network structure of crosslinked nano-scale separation is obtained by base coupling termination, based on this kind of crosslinked
The fixation of cross-bond of the full polymers device of active layer assembling due to active layer pattern is to effectively improve the stability of device.
Invention content
The case where based on the prior art, the purpose of the present invention is to provide a kind of existing high electricity conversion is again crosslinking
The crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide of the n-type polymeric acceptor material of performance, system
Preparation Method and its application.
In order to realize that above-mentioned technical purpose, the technical solution adopted by the present invention be：
A kind of crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide for polymer and has
The general structure as shown in structural formula 1：
Arbitrary value between the ranging from 0.90-0.99 of wherein x, R1,R2,R3Alkyl selected from C4-C12, D are electron list
Member, the number of repeat unit of n representation polymers, natural number of the value between 10-1000.
Further, the D in structural formula is thiophene unit, selenophen unit, bithiophene unit or connection selenophen unit.
Further, the number-average molecular weight of the polymer is 10000-200000.
A kind of preparation method of the crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide is single
After body A, monomer B and monomer C are mixed, then catalysts and solvents are sequentially added, and the reflow treatment 24-48h in nitrogen atmosphere, so
After be cooled to (cooling before end-capping reagent can be added carry out reaction 6-12h) after, methanol be added carry out precipitating and obtain sediment, then
Sediment is used into methanol, acetone and n-hexane carrying out washing treatment respectively, chloroform is then added and is dissolved and collected chloroform phase, then
Methanol is added and carries out settlement treatment, then after filtering and being dried, you can is made crosslinkable shown in structural formula 1 and is based on naphthalene
The full polymers solar cell acceptor material of imidodicarbonic diamide；
Wherein, the monomer A has the general structure as shown in structural formula 2：
The monomer B has the general structure as shown in structural formula 3：
The monomer C is：2,5- bis- (tin trimethyl) thiophene, 2,5- bis- (tin trimethyl) selenophen, 5,5/- two (front threes
Ji Xi) -2,2/Bithiophene or 5,5/- two (tin trimethyls) -2,2/Join selenophen.
Further, the solvent is toluene, chlorobenzene, dichloro-benzenes, n,N-Dimethylformamide, N, N- dimethylacetamides
Amine.
Further, the A of the conjugate unit of the monomer A, monomer B and monomer C:B:The molar ratio of C is 1:0.90-0.99:
0.01-0.10。
It is further preferred that molecular weight of the number-average molecular weight of the polymer between 10000-50000, it should be understood that change
The cross-linking properties and photoelectric properties of polymer can be optimized by becoming molecular weight.Such as：Lower molecular weight can ensure in polymerization process
It is not easy to be crosslinked, higher molecular weight can ensure that good film forming, the molecular weight distribution of polymer prepared by the present invention refer to
Number can be 1.5-3.5.
A kind of photovoltaic material electroactive layer composition of full polymers solar cell crosslinkable is based on naphthalene two by above-mentioned
Imido full polymers solar cell acceptor material and polymeric donor C-PBDTTTPD-0.10 press 1:1.5 ratio composition,
The polymeric donor is the double bond containing polymeric donor based on benzene thiophene and Thienopyrroles diketone, is had as tied
General structure shown in structure formula 4：
The photovoltaic material electroactive layer composition forms crosslinked to receptor after being heat-treated 1.5h at a high temperature of 150 °
Inierpeneirating network structure.
Further, the number-average molecular weight Mn=11kg/mol, PDI=1.81 of the polymeric donor.
A kind of photovoltaic device, including hole collection layer, electronics collecting layer and set on hole collection layer and electronics collecting layer it
Between photovoltaic material active layer, the photovoltaic material active layer includes above-mentioned crosslinkable complete poly- based on benzene-naphthalene diimide
Object solar cell acceptor material and its by 150 DEG C heat treatment 1.5h.
It is demonstrated experimentally that crosslinkable polymeric acceptor and the present invention based on NDI (benzene-naphthalene diimide) provided by the invention
After the polymeric donor combination of selection, it may be implemented to total between receptor macromolecular using the crosslinking process of 150 ° of heat treatments of high temperature
The connected crosslinking of valence link, the raising that the thermal stability of the full polymers solar device of assembling may be significantly.
Using above-mentioned technical solution, crosslinkable alkene key is introduced by the method for ternary polymerization and is based on by the present invention
In the side chain of the polymeric acceptor material of NDI, crosslinking content regulation and control are 20% hereinafter, therefore can keep original poly- based on NDI
The high photoelectric conversion efficiency for closing object receptor, simultaneously because the introducing of crosslinkable groups (olefinic double bonds) makes polymeric acceptor have
Crosslinking performance and crosslinkable polymeric donor combination after may be used process of thermal treatment obtain have give receptor covalent bond
The active layer of connected crosslinking inierpeneirating network structure is simultaneously applied to full polymers solar device, improves the thermostabilization of corresponding device
Property.
Description of the drawings
The present invention is further elaborated with specific implementation mode with reference to the accompanying drawings of the specification：
Fig. 1 is the chemical reaction flow figure of the embodiment of the present invention 1 and 2 polymer C-PNDI-T-x；Wherein, solvent is first
Benzene：N,N-dimethylformamide (5:1)；
Fig. 2 be polymer c-PNDI-0.05 through Overheating Treatment and without Overheating Treatment through boiling chloroform impregnate after
Uv-visible absorption spectroscopy (measures cross-linking properties)；
Fig. 3 is the chemical reaction flow figure of the embodiment of the present invention 3 and 4 polymer C-PNDI-Se-x；Wherein, solvent is first
Benzene：N,N-dimethylformamide (5:1)；
Fig. 4 is the chemical reaction flow figure of 5 polymer C-PNDI-2T-x of the embodiment of the present invention；Wherein, solvent is toluene：
N,N-dimethylformamide (10:1)；
Fig. 5 is the structural formula of the polymeric donor c-PBDTTTPD-0.10 selected；
Fig. 6 is the crosslinkable polymeric acceptor c-PNDI-0.05 and donor c-PBDTTTPD-0.10 compositions of the present invention
Thermal stability of the device of assembling under 150 ° of high temperature selects one group of polymer composition group for being free of cross-bond as a comparison
Fill the thermal stability under device detection equal conditions.
Specific implementation mode
When describing embodiment of the present invention, for the sake of clarity, specific term has been used.
The routine techniques of the polymer chemistry in art technology can be used in the practice of the present invention.All solvents are by removing
Water process, and react and all carry out under an inert atmosphere of nitrogen, unless otherwise noted, otherwise all solvents are all commercially-available
's.
Embodiment 1
The synthesis of polymer C-PNDI-T-0.05
The chemical reaction flow figure of the present embodiment is as shown in Figure 1, specific reaction step and reaction condition are as follows：
Under nitrogen protection, by 0.01045mmol monomers A (4,9- bis- bromo- 2,7- bis- (2- hexyl certain herbaceous plants with big flowers base)-benzos [lmn]
[3,8] phenanthrolene -1,3,6,8- tetranitros), 0.0055mmol monomers B (4,9- bis- bromo- 2,7- bis- (hendecene base)-benzene
And [lmn] [3,8] phenanthrolene -1,3,6,8- tetranitros, 0.11mmol monomers C (2,5- bis- (tributylestannyl) thiophenes
Pheno) after mixing, then 5mol% catalyst tris(dibenzylideneacetone) dipalladiums (Pd is sequentially added2(dba)3) and 10mol% ligands three
(o-methyl-phenyl) phosphine (P (o-tyl)3) mixed dissolution is in the toluene and N of 3mL, N-dimethylformamide (5:1) mixed solvent
In.Then 0.11mmol phenyl boric acids sealing end is added after allowing reaction solution to be stirred at reflux reaction 48h at 110 DEG C, is further continued for reaction 6h
Afterwards；0.3~0.5mL bromobenzenes sealing end is added, after enabling it react 6h again at 110 DEG C, stops reaction.Wait for that reaction solution is cooled to
After room temperature, reaction solution is slowly dropped into 200mL methanol and is precipitated, filtering gained sediment uses first successively in Soxhlet extractor
Alcohol, acetone, n-hexane elution are finally dissolved with chloroform, in precipitating to methanol, solid are precipitated, filtering drying obtains black-and-blue solid
Body polymer C-PNDI-T-0.05.
Characterization result is as follows：
1H NMR(400MHz,CDCl3)：δ8.97(s,1H),7.46(s,1H),5.81(s,0.04H),4.92(s,
0.08H), 4.15 (s, 2H), 3.15 (s, 1H), 2.02 (s, 4H), 1.25 (dd, J=28.4,22.2Hz, 20H), 0.88-0.64
(m,4H)。
GPC measures molecular weight Mn=26kg/mol, PDI=3.17.
The structural formula that following structural formula is the polymer C-PNDI-T-0.05 obtained by the present embodiment.
Test
Fig. 2 is the uv-visible absorption spectroscopy of polymer C-PNDI-T-0.05, and lines from top to bottom sequentially indicate
For：
Solid line：The spectrogram of thin polymer film before boiling chloroform immersion；
Horizontal dotted line：By spectrogram of the thin polymer film of 150 ° of heat treatment after boiling chloroform impregnates；
Pecked line：Spectrogram of the thin polymer film being heat-treated without 150 DEG C after boiling chloroform impregnates；
Cross-linking properties can be measured according to uv-visible absorption spectrum figure, and chloroform dissolving of being boiled is not easy after crosslinked polymer
Still keep high absorbance.
Embodiment 2
The synthesis of polymer C-PNDI-T-0.03
The chemical reaction flow figure of the present embodiment is as shown in Figure 1, specific reaction step and reaction condition are as follows：
Under nitrogen protection, by 0.1012mmol monomers A (4,9- bis- bromo- 2,7- bis- (2- hexyl certain herbaceous plants with big flowers base)-benzos [lmn]
[3,8] phenanthrolene -1,3,6,8- tetranitros), 0.0088mmol monomers B (4,9- bis- bromo- 2,7- bis- (hendecene base)-benzene
And [lmn] [3,8] phenanthrolene -1,3,6,8- tetranitros and 0.11mmol monomers C (2,5- bis- (tributylestannyl) thiophenes
Pheno) after mixing, 5mol% catalyst tris(dibenzylideneacetone) dipalladiums (Pd is sequentially added2(dba)3) and 10mol% ligands three
(o-methyl-phenyl) phosphine (P (o-tyl)3) mixed dissolution is in the toluene and N of 3mL, N-dimethylformamide (5:1) mixed solvent
In；Then 0.11mmol phenyl boric acids sealing end is added after allowing reaction solution to be stirred at reflux reaction 48h at 110 DEG C, is further continued for reaction 7h
Afterwards；0.3~0.5mL bromobenzenes sealing end is added, after then reacting 4h at 110 DEG C again, stops reaction；Wait for that reaction solution is cooled to
After room temperature, reaction solution is slowly dropped into 200mL methanol and is precipitated, filtering gained sediment uses first successively in Soxhlet extractor
Alcohol, acetone, n-hexane elution are finally dissolved with chloroform, in precipitating to methanol, solid are precipitated, filtering drying obtains black-and-blue solid
Body polymer C-PNDI-T-0.03.
Characterization result is as follows：
11H NMR(400MHz,CDCl3)：δ8.97(s,1H),7.45(s,1H),5.81(s,0.02H),4.92(s,
0.04H), 4.15 (s, 2H), 3.14 (s, 1H), 2.02 (s, 4H), 1.25 (dd, J=28.9,22.1Hz, 20H), 0.83 (dd, J
=15.2,6.8Hz, 4H).
GPC measures molecular weight Mn=15kg/mol, PDI=1.66.
The structural formula that following structural formula is the polymer C-PNDI-T-0.03 obtained by the present embodiment.
Embodiment 3
The synthesis of polymer C-PNDI-Se-0.05
The chemical reaction flow figure of the present embodiment is as shown in figure 3, specific reaction step and reaction condition are as follows：
Under nitrogen protection, by 0.1045mmol monomers A (4,9- bis- bromo- 2,7- bis- (2- hexyl certain herbaceous plants with big flowers base)-benzos [lmn]
[3,8] phenanthrolene -1,3,6,8- tetranitros), 0.0055mmol monomers B (4,9- bis- bromo- 2,7- bis- (hendecene base)-benzene
And [lmn] [3,8] phenanthrolene -1,3,6,8- tetranitros and 0.11mmol monomers C (2,5- bis- (tributylestannyl) selenium
Pheno) after mixing, then 5mol% catalyst tris(dibenzylideneacetone) dipalladiums (Pd is sequentially added2(dba)3) and 10mol% ligands three
(o-methyl-phenyl) phosphine (P (o-tyl) 3) mixed dissolution is in the toluene and N of 3mL, N-dimethylformamide (5:1) mixed solvent
In；Then 0.11mmol phenyl boric acids sealing end is added after enabling reaction solution be stirred at reflux reaction 36h at 110 DEG C, after the reaction was continued 4h；
0.3~0.5mL bromobenzenes sealing end is added, after then reacting 6h at 110 DEG C again, stops reaction；Wait for that reaction solution is cooled to room
Reaction solution is slowly dropped into 200mL methanol and is precipitated by Wen Hou, and filtering gained sediment uses methanol successively in Soxhlet extractor,
Acetone, n-hexane elution, is finally dissolved with chloroform, in precipitating to methanol, solid is precipitated, it is poly- that filtering drying obtains black-and-blue solid
Close object C-PNDI-Se-0.05.
Characterization result is as follows：
11H NMR(400MHz,CDCl3)：:δ9.00(s,1H),7.65(s,1H),,5.81(s,0.04H),4.92(s,
0.07H), 4.15 (s, 2H), 3.11 (s, 1H) 2.02 (s, 4H), 1.33 (d, J=69.2Hz, 20H), 0.84 (d, J=
16.1Hz,4H).
GPC measures molecular weight Mn=11kg/mol, PDI=2.01.
The structural formula that following structural formula is the polymer C-PNDI-Se-0.05 obtained by the present embodiment.
Embodiment 4
The synthesis of polymer C-PNDI-Se-0.10
The chemical reaction flow figure of the present embodiment is as shown in figure 3, specific reaction step and reaction condition are as follows：
Under nitrogen protection, by 0.099mmol monomers A (4,9- bis- bromo- 2,7- bis- (2- hexyl certain herbaceous plants with big flowers base)-benzos [lmn]
[3,8] phenanthrolene -1,3,6,8- tetranitros), 0.011mmol monomers B (4,9- bis- bromo- 2,7- bis- (hendecene base)-benzos
[lmn] [3,8] phenanthrolene -1,3,6,8- tetranitros and 0.11mmol monomers C (2,5- bis- (tributylestannyl) selenium
Pheno) after mixing, 5mol% catalyst tris(dibenzylideneacetone) dipalladiums (Pd is sequentially added2(dba)3) and 10mol% ligands three
(o-methyl-phenyl) phosphine (P (o-tyl) 3) mixed dissolution is in the toluene and N of 3mL, N-dimethylformamide (5:1) mixed solvent
In；Then reaction solution is enabled to be stirred at reflux reaction at 110 DEG C, 0.11mmol phenyl boric acids (0.11mmol), which are added, after 30h blocks, after
Continuous reaction 5h；0.3~0.5mL bromobenzenes sealing end is added, after then reacting 6h at 110 DEG C again, stops reaction；Wait for reaction solution
After being cooled to room temperature, reaction solution is slowly dropped into 200mL methanol and is precipitated, filtering gained sediment in Soxhlet extractor successively
With methanol, acetone, n-hexane elution is finally dissolved with chloroform, in precipitating to methanol, solid is precipitated, filtering drying obtains blue-black
Color solid polymer C-PNDI-Se-0.10.
Characterization result is as follows：
11H NMR(400MHz,CDCl3)：:δ9.00(s,1H),7.65(s,1H),5.81(s,0.1H),4.92(s,
0.2H), 4.15 (s, 2H), 2.02 (s, 1H), 3.11 (s, 4H), 1.33 (d, J=69.2Hz, 20H), 0.84 (d, J=
16.1Hz,4H).
GPC measures molecular weight Mn=21kg/mol, PDI=2.54.
The structural formula that following structural formula is the obtained polymer C-PNDI-Se-0.10 of this implementation
Embodiment 5
The synthesis of polymer C-PNDI-2T-0.10
The chemical reaction flow figure of the present embodiment is as shown in figure 4, specific reaction step and reaction condition are as follows：
Under nitrogen protection, by 0.099mmol monomers A (4,9- bis- bromo- 2,7- bis- (2- hexyl certain herbaceous plants with big flowers base)-benzos [lmn]
[3,8] phenanthrolene -1,3,6,8- tetranitros), 0.011mmol monomers B (4,9- bis- bromo- 2,7- bis- (hendecene base)-benzos
[lmn] [3,8] phenanthrolene -1,3,6,8- tetranitros and 0.11mmol monomers C (5,5/- two (tin trimethyls) -2,2/Join thiophene
Pheno) after mixing, 5mol% catalyst tris(dibenzylideneacetone) dipalladiums (Pd is sequentially added2(dba)3) and 10mol% ligands three
(o-methyl-phenyl) phosphine (P (o-tyl) 3) mixed dissolution is in the toluene and N of 3mL, N-dimethylformamide (10:1) mixed solvent
In；Then 0.11mmol phenyl boric acids sealing end, the reaction was continued 4h are added after enabling reaction solution be stirred at reflux reaction 48h at 110 DEG C；Again
0.3~0.5mL bromobenzenes sealing end is added, then stops reaction after reaction 5h at 110 DEG C；It, will after reaction solution is cooled to room temperature
Reaction solution is slowly dropped into 200mL methanol and is precipitated, filtering gained sediment in Soxhlet extractor successively use methanol, acetone, just
After finally being dissolved with chloroform in precipitating to methanol, solid is precipitated in hexane elution, and filtering drying obtains black-and-blue solid polymer C-
PNDI-2T-0.10。
Characterization result is as follows：
11H NMR(400MHz,CDCl3)：:δ8.80(s,2H),7.55(s,1H),5.80(s,0.08H),4.92(s,
0.16H), 4.15 (s, 2H), 3.08 (s, 1H), 2.02 (s, 4H), 1.33 (d, J=69.2Hz, 20H), 0.84 (d, J=
16.1Hz,4H).
GPC measures molecular weight Mn=31kg/mol, PDI=2.54.
A kind of photovoltaic device, including hole collection layer, electronics collecting layer and set on hole collection layer and electronics collecting layer it
Between photovoltaic material active layer, wherein photovoltaic material active layer includes polymeric acceptor (C-PNDI- made from the present invention program
) and selected polymeric donor (c-PBDTTTPD-0.10, structural formula are as shown in Figure 5) composition T-0.05.
By ito glass after ultrasonic cleaning, is handled with oxygen-Plasma, PEDOT is coated on ITO：PSS, wherein
PEDOT:PSS is poly- 3,4-ethylene dioxythiophene：Polystyrolsulfon acid.Then by the photovoltaic material active layer in the present invention with three
After chloromethanes dissolving is blended in spin coating covering, 150 ° of high temperature is heating of Activated by the time interval difference of 1.5h on heating platform
Layer, and evaporation cathode calcium and aluminum metal respectively, obtain full polymers solar device and test corresponding device performance.In order to right
Than that can also select after the polymeric donor of no crosslinked group and the photovoltaic material active layer of polymeric acceptor combination by same
Assembly device and corresponding device performance is tested after being handled under time and temperature, the solvent of the polymer composition of selection is chlorine
It is imitative.
Wherein, two class devices in 150 ° of device parameter performances changed over time of high temperature are listed in attached drawing 6 (wherein, solid line are
The thermal stability of the device of the polymeric acceptor of the present invention；Dotted line is the thermal stability of comparative device), corresponding opto-electronic conversion effect
Rate is listed in the attenuation curve that heating time changes in Tables 1 and 2, it is found that the light of the polymeric acceptor including the present invention
Volt material active layer active layer after 150 ° of heating of 1.5h crosslinks, and the heat that corresponding device can be significantly increased is steady
It is qualitative.
The device that table 1 is polymeric acceptor C-PNDI-T-0.05 and donor c-PBDTTTPD-0.10 compositions assemble is in height
The lower 150 ° of device parameter performance values changed over time of temperature
Table 2 is that the comparative device of the polymer composition assembling without cross-bond is changed over time at 150 ° at high temperature
Device parameter performance value
The above is the embodiment of the present invention, for the ordinary skill in the art, introduction according to the present invention,
Without departing from the principles and spirit of the present invention all equivalent changes made according to scope of the present invention patent, modification,
Replacement and modification should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide, it is characterised in that：It is poly-
It closes object and there is the general structure as shown in structural formula 1：
Arbitrary value between the ranging from 0.90-0.99 of wherein x, R1,R2,R3Alkyl selected from C4-C12, D are electron unit, n
The number of repeat unit of representation polymer, natural number of the value between 10-1000.
2. a kind of crosslinkable full polymers solar cell receptor material based on benzene-naphthalene diimide according to claim 1
Material, it is characterised in that：D in structural formula is thiophene unit, selenophen unit, bithiophene unit or connection selenophen unit.
3. a kind of crosslinkable full polymers solar cell receptor material based on benzene-naphthalene diimide according to claim 1
Material, it is characterised in that：The number-average molecular weight of the polymer is 10000-200000.
4. a kind of crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide according to claim 1
Preparation method, it is characterised in that：After it is monomer A, monomer B and monomer C mixing, then catalysts and solvents are sequentially added, and
The reflow treatment 24-48h in nitrogen atmosphere after being then cooled to, is added methanol and carries out precipitating acquisition sediment, then will precipitation
Object uses methanol, acetone and n-hexane carrying out washing treatment respectively, then adds chloroform and is dissolved and collected chloroform phase, adds first
Alcohol carries out settlement treatment, then after filtering and being dried, you can is made crosslinkable sub- based on two acyl of naphthalene shown in structural formula 1
The full polymers solar cell acceptor material of amine；
Wherein, the monomer A has the general structure as shown in structural formula 2：
The monomer B has the general structure as shown in structural formula 3：
The monomer C is：2,5- bis- (tin trimethyl) thiophene, 2,5- bis- (tin trimethyl) selenophen, 5,5/- two (tin trimethyls)-
2,2/Bithiophene or 5,5/- two (tin trimethyls) -2,2/Join selenophen.
5. a kind of crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide according to claim 4
Preparation method, it is characterised in that：The solvent is toluene, chlorobenzene, dichloro-benzenes, n,N-Dimethylformamide, N, N- diformazans
Yl acetamide.
6. a kind of crosslinkable full polymers solar cell acceptor material based on benzene-naphthalene diimide according to claim 4
Preparation method, it is characterised in that：The A of the conjugate unit of the monomer A, monomer B and monomer C:B:The molar ratio of C is 1:
0.90-0.99:0.01-0.10。
7. a kind of photovoltaic material electroactive layer composition of full polymers solar cell, it is characterised in that：It is by claim 1 to 6
One of described in crosslinkable full polymers solar cell acceptor material and polymeric donor C- based on benzene-naphthalene diimide
PBDTTTPD-0.10 presses 1:1.5 ratio composition, the polymeric donor are double bond containing based on benzene thiophene and thieno
The polymeric donor of pyrroledione has the general structure as shown in structural formula 4：
The photovoltaic material electroactive layer composition forms crosslinked to receptor interpenetrating after being heat-treated 1.5h at a high temperature of 150 °
Network structure.
8. a kind of photovoltaic material electroactive layer composition of full polymers solar cell according to claim 7, feature exist
In：The number-average molecular weight Mn=11kg/mol, PDI=1.81 of the polymeric donor.
9. the crosslinkable full polymers solar cell receptor based on benzene-naphthalene diimide according to one of claim 1 to 6
The application of material, it is characterised in that：Including photovoltaic device, the photovoltaic device includes crosslinkable being based on naphthalene two by described
Solar cell made of imido full polymers solar cell acceptor material.
10. a kind of photovoltaic device, including hole collection layer, electronics collecting layer and set between hole collection layer and electronics collecting layer
Photovoltaic material active layer, it is characterised in that：The photovoltaic material active layer include described in one of claim 1 to 6 can
The crosslinked full polymers solar cell acceptor material based on benzene-naphthalene diimide and its by 150 DEG C heat treatment 1.5h.
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