CN102391480B - Liquid crystal conjugated polymer of crosslinkable, fluorobenzene end cap-containing, and carbazolyl and bithienyl substitution-based difluorobenzothiadiazole, and application of liquid crystal conjugated polymer to solar cell - Google Patents
Liquid crystal conjugated polymer of crosslinkable, fluorobenzene end cap-containing, and carbazolyl and bithienyl substitution-based difluorobenzothiadiazole, and application of liquid crystal conjugated polymer to solar cell Download PDFInfo
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Abstract
A kind of application based on carbazole with pair liquid crystal conjugated polymer of the difluoro diazosulfide of thienyls substitution and its in solar cells of the crosslinkable sealing end containing fluorobenzene, it is characterized in that having following structure formula:
Polymer HOMO energy level can be effectively reduced in conjugated polymer of the present invention, its absorption spectrum is more matched with the emission spectrum of solar energy, and there is liquid crystal liquid crystal property, inducing action enhances the order of active layer, improves charge carrier transport efficiency and electrode to the collection efficiency of carrier; The both hole and electron transmission rate of active layer is high, and energy conversion efficiency is up to 7.4%. In addition, active layer structure is stablized, the stability and service life of device are improved, the efficiency after 40 days remains to reach 7.2%.
Description
Technical field
The present invention relates to a kind of liquid crystal conjugated polymers of the crosslinkable difluoro diazosulfide that replaces based on carbazole and two thienyls that contains the fluorobenzene end-blocking and the application in solar cell thereof.
Background technology
Along with the year by year increase of global energy demand, energy problem becomes the matter of utmost importance that the countries in the world Economic development runs into.Sun power is the maximum energy that can develop in the world at present, and clean without dirty, day by day becomes the first-selection of green energy resource.Be compared to cost height, heavy-polluted inorganic solar cell, polymer solar battery is with low cost, the designability of photovoltaic material molecular structure, snappiness is good, preparation technology is simple, environmental friendliness, light portable, has become in recent years the focus of research both at home and abroad.Be the business-like key issue of this type of battery of restriction but electricity conversion is low, and the principal element that affects efficient comprise that the absorption spectrum of semiconducting organic polymer and solar radiation spectrum do not mate, the order of active coating microscopic appearance is relatively poor, the poor stability of device always.For above problem, people develop many new polymkeric substance in recent years, especially narrow band gap D-A type conjugated polymers, people can pass through to change the proportion of electrophilic group in polymer architecture, thereby realize the modulation of HOMO and LUMO level of energy, and then obtain energy level coupling and the less polymer materials of bandwidth, such as PCDT BT [Nature Photonics, 2009,3,297-302], PFDCN [J. Am. Chem. Soc., 2009,131,13886-13887], PSiF-DBT [Appl. Phys. Lett., 2008,92,033307], PSB-TBT [J. Am. Chem. Soc., 2008,130,16144-16145], this type conjugated polymers can be widened light abstraction width, and the absorption spectrum of polymer materials and the emmission spectrum of sunlight are mated more, and absorbancy improves.In addition, people are when the synthetic photoactive layer material of design, and its microscopic appearance is optimized in control, strengthens its order, for formation and the migration of current carrier provides good interface and passage, are beneficial to its collection of electrode pair.But because the uncompatibility between component in the low second-order transition temperature of polymkeric substance and the active coating, the heat that solar radiation produces easily causes device performance to reduce, and the work-ing life of the solar cell take these narrowband gap conjugated polymers as photoactive layer and stability all remain further to study and improve.In addition; research is found with fluorine-containing end-capping reagent conjugated polymers to be carried out end-functionalization protection [Adv. Mater. 2010; 22; 1355 – 1360]; can impel the surface energy of polymkeric substance close to the PCBM surface energy, reach the Uniform Dispersion between polymkeric substance and PCBM, and can suppress the too fast gathering of PCBM; form the micron-scale phase separation of optimizing, thereby improve the both hole and electron transmission rate of active coating.
In research process, we introduce crosslinkable units at carbazole, with itself and the difluoro diazosulfide copolymerization that two thienyls replace, with containing the fluorobenzene end-capping reagent its end group are carried out functionalization, obtain a series of D-A type narrow band gap liquid crystal conjugated polymers.The light abstraction width of this narrowband gap conjugated polymer is wide, and has liquid crystal characteristic, the order of its inducing action enhanced activity layer, the collection effciency of raising carrier mobility efficient and electrode pair current carrier.The introducing of crosslinkable units can obtain crosslinked, constitutionally stable active layer material, improves stability and the work-ing life of device.The conjugated polymers of this structure is applied to solar cell, up to the present, there is no pertinent literature and patent report both at home and abroad.
Summary of the invention
The invention provides a kind of liquid crystal conjugated polymers of the crosslinkable difluoro diazosulfide that replaces based on carbazole and two thienyls that contains the fluorobenzene end-blocking and the application in solar cell thereof.Introduce crosslinkable units at carbazole, with its difluoro diazosulfide copolymerization with two thienyls replacements, with containing the fluorobenzene end-capping reagent its end group is carried out functionalization, obtain a series of D-A type narrowband gap conjugated polymer, study simultaneously it as the application of solar cell active coating.
The present invention is achieved by the following technical solutions.
1. the invention provides a kind of crosslinkable liquid crystal conjugated polymers that contains the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking, it is characterized in that it has following structural formula:
In the formula:
In the formula, R
1And R
2For identical or different with the one or more side chain in two keys, oxygen fourth ring, the bromo.
R
3, R
4, R
5, R
6For identical or different hydrogen, carbonatoms are that alkyl, the carbonatoms of 1 to 20 straight chain or branched chain is that 3 to 20 cycloalkyl, carbonatoms are 1 to 20 straight chain or the alkoxyl group of branched chain, carbonatoms is 1 to 20 straight chain or the alkoxyphenyl radical of branched chain, or comprises the aryl of one or more aromatic nucleus.
Ar
1, Ar
2For containing fluorobenzene end-blocking blocking group; Ar
1, Ar
2Can be identical or different functional groups, be preferably in the following functional group any one.
Function base 1:
The single fluorobenzene of function base 2():
Function base 3(difluorobenzene):
Function base 4(trifluoro-benzene):
Function base 5(tetra fluoro benzene):
Function base 6(penta fluoro benzene):
2. with the liquid crystal conjugated polymers of the described crosslinkable difluoro diazosulfide that replaces based on carbazole and two thienyls that contains the fluorobenzene end-blocking active coating as solar cell, preparation polymer solar battery.
This solar cell device structure as shown in Figure 1, the 1st, the host glass material, the 2nd, the ito anode layer, the 3rd, poly-(3,4-two oxidative ethane thiophene)/(poly-(styrene sulfonate) be the anode modification layer (PEDOT/PSS), its thickness is 30-50 nm, the 4th, crosslinkable liquid crystal conjugated polymers and 1-(3-methoxycarbonyl) propyl group-1-phenyl [6 that contains the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking, 6]-the blend film layer of C-61 (PCBM), its thickness is 60-200 nm, the 5th, LiF cathodic modification layer, the 6th, Al metallic cathode layer; The described crosslinkable liquid crystal conjugated polymers that contains the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking is used for the photoactive layer (being active coating) of solar cell.
Described crosslinkable the as follows as the preparation method of solar cell with the liquid crystal conjugated polymers of the difluoro diazosulfide of two thienyls replacements based on carbazole of fluorobenzene end-blocking that contain.
To use successively washing composition through the good ito glass of salt acid etch, deionized water, Virahol difference ultrasonic cleaning ten minutes, thoroughly be put under the ultraviolet lamp after the cleaning and shone ten minutes, then under atmospheric atmosphere at the aqueous solution of its surperficial spin coating PEDOT/PSS to prepare the thick PEDOT/PSS film of about 30-50 nm, subsequently it is put in 120
o C heats 20 min, then the ITO/PEDOT/PSS film is moved in the glove box of nitrogen filling, the spin coating mass ratio be 1:3 contain liquid crystal conjugated polymers and 1-(3-methoxycarbonyl) propyl group-1-phenyl [6 of the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking with chlorobenzene dissolving crosslinkable, 6]-mixing solutions of C-61 (PCBM) prepares active coating, the active coating gauge control is at 60-200 nm, with the gained active coating under nitrogen environment in 50
oAfter C heated 10 min, then UV-irradiation 30 min put into the vacuum plating unit chamber, are evacuated to 4 * 10
-4Below the Pa, evaporation LiF and Al electrode, control its thickness and be respectively about 1 nm and 100 nm, obtain the polymer solar battery take the liquid crystal conjugated polymers of the crosslinkable difluoro diazosulfide that replaces based on carbazole and two thienyls that contains the fluorobenzene end-blocking as donor material.
Beneficial effect of the present invention: fluorine is introduced the difluoro diazosulfide that two thienyls replace, can effectively reduce polymkeric substance HOMO energy level, improve open circuit voltage, as being subjected to body unit, select the high large conjugation of condensed ring of this cloud density of carbazole, the coplanar tectonic element of rigidity is to body unit, the D-A type narrowband gap conjugated polymer absorption spectrum of preparation and the emmission spectrum of sun power mate more, and has liquid crystal liquid crystal property, the order of its inducing action enhanced activity layer, improve the collection effciency of carrier mobility efficient and electrode pair current carrier, and utilize fluorine-containing end-capping reagent that its end group is carried out functionalization, can promote the Uniform Dispersion between polymkeric substance and PCBM, improve the both hole and electron transmission rate of active coating, effectively improved device performance, energy conversion efficiency is up to 7.4%.In addition, the introducing of crosslinkable units can obtain crosslinked, constitutionally stable active layer material, improves stability and the work-ing life of device, and the efficient after 40 days still can reach 7.2%.
Description of drawings
Fig. 1 is the structural representation of polymer solar battery.The 1st, the host glass material, the 2nd, the ito anode layer, the 3rd, poly-(3,4-two oxidative ethane thiophene)/(poly-(styrene sulfonate) be the anode modification layer (PEDOT/PSS), the 4th, crosslinkable liquid crystal conjugated polymers and 1-(3-methoxycarbonyl) propyl group-1-phenyl [6 that contains the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking, 6]-and the blend film layer of C-61 (PCBM), the 5th, LiF cathodic modification layer, the 6th, Al metallic cathode layer.
Fig. 2 is embodiment 3 does the polymer solar battery of donor material with poly-[2,7-N (17-1,16-diene-9-yl) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, the 3-diazosulfide] of pentafluorophenyl group end-blocking voltage-to-current curve.
Fig. 3 is that embodiment 3 is with poly-[2,7-N (17-1, the 16-diene-9-yl) carbazole-5 of pentafluorophenyl group end-blocking, 6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, 3-diazosulfide] do the polymer solar battery of donor material crosslinked before with crosslinked after the device performance stability diagram.
Embodiment
The present invention will be described further by following examples.
Embodiment 1: the preparation of poly-[2,7-N (17-1,16-diene-9-yl) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, 3-diazosulfide] alternating copolymer of pentafluorophenyl group end-blocking, implementation step is as follows.
With 2,7-dibromo carbazole (7.5 g, 23.1 mmol), 17-1,16-diene-9-base-tosylate (10.3 g, after 25.4 mmol), 4-butyl ammonium hydrogen sulfate (0.15g) is dissolved in 150 mL acetone, add potassium hydroxide (5.1 g, 92 mmol), stirring and refluxing 2 h, be cooled to room temperature, after filtering, concentrating, extraction, dry organic phase, recrystallization obtains product
1, [2,7-, two bromo-N (17-1,16-diene-9-yl) carbazole].
With 2,7-, two bromo-N (17-1,16-diene-9-yl) carbazoles (6.7g, 12 mmol), two valeryl two boron (7.3 g, 28.8mmol), Pd (dppf) Cl
2(0.6 g, 1.78mmol), KOAc (8.2 g, 84mmol), the mixture of dioxane (130 mL) are under argon atmosphere 90
oC stirring reaction 8 h.Be cooled to filtering and concentrating after the room temperature, use again silica dioxide gel column purification product after, recrystallization obtains product
2[N (17-1,16-diene-9-yl) carbazole-2, the two boric acid esters of 7-].
Compound
3[two (the 5-bromo-2-thiophene)-5 of 4,7-, 6-two fluoro-2,1,3-diazosulfide], with reference to Angew. Chem. 2011,123, the disclosed method of 3051-3054 is synthetic.N (17-1,16-diene-9-yl) carbazole-2, the two boric acid esters of 7-and two (the 5-bromo-2-thiophene)-5 of 4,7-, 6-two fluoro-2,1,3-diazosulfide add function base end-blocking again through the Suzuki coupling, obtain conjugated polymers
4
With N (17-1,16-diene-9-yl) carbazole-2, the two boric acid esters (0.41 mmol) of 7-, 5,6-two fluoro-4, two (the 5-bromo-2-thiophene)-2 of 7-, 1,3-diazosulfide (0.40 mmol), methyl tricapryl ammonium chloride (20 wt% of amount of monomer) add in the polymerization bottle of 50 mL dryings, add again treated toluene 8 mL, after all monomers all dissolve, add again wet chemical 0.66 mL of 2 mol/L, install prolong, pass into argon gas, with the air displacement in the polymerization bottle three times.Under argon atmosphere, add catalyzer tetrakis triphenylphosphine palladium (0.002 mmol), substitution gas is three times again.Heated solution back flow reaction 72 h.Five bromofluorobenzenes that add 0.2 times of molar weight continue reaction 12 hours.After stopped heating is cooled to room temperature, with reaction solution sedimentation in methyl alcohol.With the polymerisate again sedimentation in methanol/water (10:1) that obtains, filter, the product of collecting is used acetone, normal hexane, toluene, methylene dichloride, chloroform extracting successively in apparatus,Soxhlet's, chloroform is proposed drawing liquid again sedimentation in methanol/water (10:1) after concentrating, filter, drying obtains poly-[2 of pentafluorophenyl group end-blocking, 7-N (17-1,16-diene-9-yl) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2 of 7-, 1,3-diazosulfide] alternating copolymer
4
Embodiment 2: the preparation of poly-[2,7-N (13-1,13-, two bromo-7-yls) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, 3-diazosulfide] alternating copolymer of pentafluorophenyl group end-blocking, be similar to embodiment 1, and implementation step is as follows.
With 2,7-dibromo carbazole (7.5 g, 23.1 mmol), 13-1, after 13-two bromo-7-base-tosylates (13.0 g, 25.4 mmol), 4-butyl ammonium hydrogen sulfate (0.15g) are dissolved in 150 mL acetone, add potassium hydroxide (5.1 g, 92 mmol), stirring and refluxing 2 h are cooled to room temperature, after filtering, concentrating, extraction, dry organic phase, recrystallization obtains product 2,7-two bromo-N (13-1,13-, two bromo-7-yls) carbazole.
With 2,7-, two bromo-N (13-1,13-, two bromo-7-yls) carbazole (7.9g, 12 mmol), two valeryl two boron (7.3 g, 28.8mmol), Pd (dppf) Cl
2(0.6 g, 1.78mmol), KOAc (8.2 g, 84mmol), the mixture of dioxane (130 mL) are under argon atmosphere 90
oC stirring reaction 8 h.Be cooled to filtering and concentrating after the room temperature, use again silica dioxide gel column purification product after, recrystallization obtains product N (13-1,13-, two bromo-7-yls) carbazole-2, the two boric acid esters of 7-.
With N (13-1,13-two bromo-7-yls) carbazole-2, the two boric acid esters (0.41 mmol) of 7-, 5,6-two fluoro-4, two (the 5-bromo-2-thiophene)-2 of 7-, 1,3-diazosulfide (0.40 mmol), methyl tricapryl ammonium chloride (20 wt% of amount of monomer) add in the polymerization bottle of 50 mL dryings, add again treated toluene 8 mL, after all monomers all dissolve, add again wet chemical 0.66 mL of 2 mol/L, install prolong, pass into argon gas, with the air displacement in the polymerization bottle three times.Under argon atmosphere, add catalyzer tetrakis triphenylphosphine palladium (0.002 mmol), substitution gas is three times again.Heated solution back flow reaction 72 h.Five bromofluorobenzenes that add 0.2 times of molar weight continue reaction 12 hours.After stopped heating is cooled to room temperature, with reaction solution sedimentation in methyl alcohol.With the polymerisate again sedimentation in methanol/water (10:1) that obtains, filter, the product of collecting is used acetone, normal hexane, toluene, methylene dichloride, chloroform extracting successively in apparatus,Soxhlet's, chloroform is proposed drawing liquid again sedimentation in methanol/water (10:1) after concentrating, filter, dry, obtain poly-[2 of pentafluorophenyl group end-blocking, 7-N (13-1,13-, two bromo-7-yls) carbazole-2, the two boric acid esters-5 of 7-, 6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, the 3-diazosulfide] alternating copolymer.
Embodiment 3: the preparation of polymer solar cell device.
Poly-[2 of 10 mg pentafluorophenyl group end-blockings, 7-N (17-1,16-diene-9-yl) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, the 3-diazosulfide] mix with 30 mg PCBM, add 2 mL chlorobenzene solutions, preparing film by the spin coating mode through the ito glass of PEDOT:PSS modified, then vacuum evaporation lithium fluoride and aluminium are prepared negative electrode.
Device performance is: standard analog sunlight (AM 1.5 G, 100 mW/cm2) irradiation is lower, open circuit voltage=0.87 V; Short-circuit current=13.15 mA/cm2; Packing factor=65%; Energy conversion efficiency=7.4%.Its current-voltage curve as shown in Figure 2, its crosslinked before with crosslinked after device performance stability as shown in Figure 3.
Embodiment 4: the preparation of polymer solar cell device.
Poly-[2 of 10 mg pentafluorophenyl group end-blockings, 7-N (13-1,13-two bromo-7-yls) carbazole-5,6-two fluoro-4, two (the 2-thienyls)-2,1 of 7-, the 3-diazosulfide] mix with 30 mg PCBM, add 2 mL chlorobenzene solutions, preparing film by the spin coating mode through the ito glass of PEDOT:PSS modified, then vacuum evaporation lithium fluoride and aluminium are prepared negative electrode.
Device performance is: standard analog sunlight (AM 1.5 G, 100 mW/cm2) irradiation is lower, open circuit voltage=0. 78 V; Short-circuit current=13.61 mA/cm2; Packing factor=68%; Energy conversion efficiency=7.2%.
Claims (2)
1. crosslinkable liquid crystal conjugated polymers that contains the difluoro diazosulfide that replaces based on carbazole and two thienyls of fluorobenzene end-blocking is characterized in that having following structural formula:
In the formula:
Representative is to body,
Represent acceptor; N is the repetition number of main polymer chain unit, is natural number 1-100;
In the formula, R
1And R
2For identical or different with the one or more side chain in two keys, oxygen fourth ring, the bromo;
R
3, R
4, R
5, R
6For identical or different hydrogen, carbonatoms are that alkyl, the carbonatoms of 1 to 20 straight chain or branched chain is that 3 to 20 cycloalkyl, carbonatoms are 1 to 20 straight chain or the alkoxyl group of branched chain, carbonatoms is 1 to 20 straight chain or the alkoxyphenyl radical of branched chain, or comprises the aryl of one or more aromatic nucleus;
Ar
1, Ar
2For containing fluorobenzene end-blocking blocking group; Ar
1, Ar
2Can be identical or different functional groups, be in the following functional group any one:
Single fluorobenzene:
Difluorobenzene:
Trifluoro-benzene:
Tetra fluoro benzene:
Penta fluoro benzene:
2. liquid crystal conjugated polymers claimed in claim 1, it is characterized in that the liquid crystal conjugated polymers of the described crosslinkable difluoro diazosulfide that replaces based on carbazole and two thienyls that contains the fluorobenzene end-blocking active coating as solar cell, preparation polymer solar battery.
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