CN104177364A - Organic semiconductor material containing pyrrolopyrrolidone unit and preparation method thereof, and solar cell device - Google Patents
Organic semiconductor material containing pyrrolopyrrolidone unit and preparation method thereof, and solar cell device Download PDFInfo
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- CN104177364A CN104177364A CN201310201445.1A CN201310201445A CN104177364A CN 104177364 A CN104177364 A CN 104177364A CN 201310201445 A CN201310201445 A CN 201310201445A CN 104177364 A CN104177364 A CN 104177364A
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
An organic semiconductor material containing a pyrrolopyrrolidone unit has the following structural formula described in the specification, wherein R represents a C1 to C20 alkyl group. The organic semiconductor material containing the pyrrolopyrrolidone unit is a donor-acceptor type conjugated monomer, and has relatively high hole mobility, high open circuit voltage, relatively good solubility, and relatively good film-forming performance, so that the problem of low efficiency of a solar cell device is solved. The invention also provides a preparation method of the organic semiconductor material containing the pyrrolopyrrolidone unit and the solar cell device using the organic semiconductor material containing the pyrrolopyrrolidone unit.
Description
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of organic semiconductor material containing pyrrolopyrrole alkane ketone unit and preparation method thereof and the solar cell device that uses this containing the organic semiconductor material of pyrrolopyrrole alkane ketone unit.
[background technology]
Body heterojunction solar cell is because its low cost is lightweight, and preparation technology is simple causes extensive concern with being prepared into the advantages such as large area flexible device.Based on conjugated polymers, to body, the highest energy efficiency of conversion of the polymer solar battery of fullerene derivate acceptor has reached 9.2%.Although the highest energy efficiency of conversion of the organic molecule solar cell of solution processable is still lower than corresponding polymkeric substance, but the molecular structure that it is clear and definite, the advantages such as definite molecular weight and high purity make to become new study hotspot based on micromolecular organic solar batteries.
At present, but for organic polymer solar cell, organic molecule solar cell still exists a lot of weak points.The absorbent properties of Molecular regulator, level structure and carrier mobility etc., thereby become the extremely potential organic molecule solar cell material of a class, realize these targets, need to develop more novel conjugated molecular material, wherein, design synthesizing new conjugate unit just seems very important.
[summary of the invention]
Based on this, be necessary the organic semiconductor material containing pyrrolopyrrole alkane ketone unit that provides a kind of energy conversion efficiency higher.
In addition, be also necessary to provide a kind of preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit.
In addition, be also necessary to provide the solar cell device using containing the organic semiconductor material of pyrrolopyrrole alkane ketone unit.
An organic semiconductor material containing pyrrolopyrrole alkane ketone unit, has following structural formula:
wherein, R is C
1～C
20alkyl.
A preparation method who contains the organic semiconductor material of pyrrolopyrrole alkane ketone unit, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R is C
1～C
20alkyl;
In oxygen-free environment, the compd A that is 1:2～1:2.4 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～48 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the organic semiconductor material containing pyrrolopyrrole alkane ketone unit that following structural formula represents:
In a preferred embodiment, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
In a preferred embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4～1:8.
In a preferred embodiment, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20～1:100.
In a preferred embodiment, the temperature of reaction of described Suzuki coupling reaction is 90 ℃～120 ℃, and the reaction times is 24 hours～36 hours.
In a preferred embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
In a preferred embodiment, the mol ratio of the solute in described alkaline solution and compd A is 20:1～50:1.
In a preferred embodiment, also comprise the step that the organic semiconductor material containing pyrrolopyrrole alkane ketone unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methylene dichloride to extract in the solution after Suzuki coupling reaction, merge organic relevant dry after, it is separated that solid that filtration is obtained adopts sherwood oil and ethyl acetate mixture to carry out silica gel column chromatography as leacheate, obtains the organic semiconductor material containing pyrrolopyrrole alkane ketone unit after purifying after vacuum-drying.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A solar cell device, comprises active coating, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6] phenyl-C
71-methyl-butyrate, described electron donor material has the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of following structural formula:
Wherein, R is C
1～C
20alkyl.
The above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is donor-receiver type conjugative monomer, and it has higher hole mobility, high open circuit voltage, and good solubility property and film forming properties, and then solve solar cell device low efficiency problem.
The preparation method of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth material structure is novel, and solubility property is good, and film forming properties is good, applicable to solar cell device.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the solar cell device of an embodiment;
Fig. 2 is the uv-visible absorption spectra figure of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of embodiment 1 preparation;
Fig. 3 is the thermogravimetic analysis (TGA) figure of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of embodiment 1 preparation.
[embodiment]
In order to understand better the content of patent of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein monomer A and monomers B are bought and are obtained from the market.
The organic semiconductor material containing pyrrolopyrrole alkane ketone unit of one embodiment, has following structural formula:
wherein, R is C
1～C
20alkyl.
The above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is donor-receiver type conjugative monomer, and it has higher hole mobility, high open circuit voltage, and good solubility property and film forming properties, and then solve solar cell device low efficiency problem.
The preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of one embodiment, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
wherein, R is C
1～C
20alkyl.
The structural formula of compd B is:
Step S2, preparation contain the organic semiconductor material of pyrrolopyrrole alkane ketone unit.
In oxygen-free environment, the compd A that is 1:2～1:2.4 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～48 hours, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the organic semiconductor material containing pyrrolopyrrole alkane ketone unit that following structural formula represents:
In present embodiment, Suzuki coupling reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).Be appreciated that organic solution also can be used other solvents, as long as can dissolved compound A and compd B.
In present embodiment, organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, and organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl.In the mixture of organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1:4～1:8.Preferably, adopt the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine as catalyzer.Be appreciated that organic palladium, organophosphor ligand are all not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Suzuki coupling reaction.
In present embodiment, in catalyzer, the mol ratio of organic palladium and compd A is 1:20～1:100.The mol ratio that is appreciated that organic palladium and compd A is not limited to 1:20～1:100, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, the temperature of reaction of Suzuki coupling reaction is 70 ℃～130 ℃, and the reaction times is 12 hours～48 hours.Preferably, the temperature of reaction of Suzuki coupling reaction is 90 ℃～120 ℃, and the reaction times is 24 hours～36 hours.The temperature of reaction that is appreciated that Suzuki coupling reaction is not limited to 70 ℃～130 ℃, as long as can make compd A and compd B react; Reaction times is also not limited to 12 hours～and 48 hours, as long as can make compd A and compd B react completely as far as possible.
In present embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, wherein the solute of sodium carbonate solution is sodium carbonate, and the solute of solution of potassium carbonate is that the solute of salt of wormwood and sodium hydrogen carbonate solution is sodium bicarbonate;
In present embodiment, the solute in described alkaline solution and the mol ratio of compd A are 20:1～50:1.
Step S3, separation and purification contain the organic semiconductor material of pyrrolopyrrole alkane ketone unit.
To described compd A and compd B, carry out adding methylene dichloride to extract in the solution after Suzuki coupling reaction, merge organic relevant dry after, it is separated that solid that filtration is obtained adopts sherwood oil and ethyl acetate mixture to carry out silica gel column chromatography as leacheate, obtains the organic semiconductor material containing pyrrolopyrrole alkane ketone unit after purifying after vacuum-drying.
In present embodiment, vacuum-drying condition is: under vacuum, 50 ℃ are dried 24 hours.
The preparation method of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit, synthetic route is comparatively simple, has reduced manufacturing cost.
A kind of solar cell device in one embodiment, comprises active coating, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6] phenyl-C
71-methyl-butyrate, described electron donor material has the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of following structural formula:
Wherein, R is C
1～C
20alkyl.
Be specific embodiment below.
Embodiment 1
The present embodiment disclose the following pyrrolopyrrole alkane ketone of structural formula to acceptor organic semiconductor material (PyPy1): 3,6-bis-(pyrene-2-yl)-2,5-bis-octane base pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone, its structural formula is as follows:
The preparation process of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is as follows:
Under argon shield, by 3,6-bis-(5-bromothiophene-2-yl)-2,5-bis-octane base pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (136mg, 0.2mmol), pyrene-2-boric acid (98mg, 0.4mmol) adds in the flask that fills 10ml toluene solvant, after fully dissolving by salt of wormwood (2mL, 2mol/L) solution joins in flask, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Suzuki coupling reaction 24h.Subsequently, stopped reaction after cooling, stopped reaction cool to room temperature, with dichloromethane extraction three times, merge organic phase, after adopting anhydrous magnesium sulfate drying, be spin-dried for, it is that leacheate is separated through silica gel column chromatography with ethyl acetate that crude product adopts sherwood oil again, and sherwood oil and ethyl acetate volume ratio are 10:1, after being spin-dried for solvent, obtain red crystals, the lower 50 ℃ of dry 24h of vacuum condition obtain product 3,6-bis-(pyrene-2-yl)-2,5-bis-octane base pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone, productive rate 78%.
Above-mentioned preparation is as follows containing the reaction formula of the organic semiconductor material of pyrrolopyrrole alkane ketone unit:
Experimental results is: mass spectrum: m/z924.4(M
++ 1); Ultimate analysis (%) C
62h
56n
2o
2s
2: theoretical value: C80.48, H6.10, N3.03, O3.46, S6.93; Measured value: C80.42, H6.18, N3.07, O3.40, S6.95.
Referring to accompanying drawing 2, be the uv-visible absorption spectra figure of the organic semiconductor material of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm～700nm, have large wider absorption, wherein maximum absorption band is positioned at 525nm.
Referring to accompanying drawing 3, be the thermogravimetic analysis (TGA) figure of the organic semiconductor material of the present embodiment 1 preparation, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T as seen from the figure
d) be 403 ℃.
ITO/PEDOT:PSS/ the present embodiment 1 organic semiconductor material/Au of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination organic semiconductor material, the hole mobility that obtains organic semiconductor material is 5.6 * 10
-4cm
2/ Vs.
Embodiment 2
The present embodiment disclose the following pyrrolopyrrole alkane ketone of structural formula to acceptor organic semiconductor material (PyPy2), that is: 3,6-bis-(pyrene-2-yl)-2,5-diformazan alkyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, its structural formula is as follows:
The preparation process of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 3, 6-bis-(5-bromothiophene-2-yl)-2, 5-diformazan alkyl pyrrolo-[3, 4-c] pyrroles-1, 4 (2H, 5H)-diketone (146mg, 0.3mmol), pyrene-2-boric acid (155mg, 0.63mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, after fully dissolving, add again sodium bicarbonate (3mL, 2mol/L) solution, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Suzuki coupling reaction 48h.Subsequently, after cooling, stop polyreaction, stopped reaction cool to room temperature, with dichloromethane extraction three times, merge organic phase, after adopting again anhydrous magnesium sulfate drying, be spin-dried for, it is that leacheate is separated through silica gel column chromatography with ethyl acetate that crude product adopts sherwood oil, and sherwood oil and ethyl acetate volume ratio are 10:1, obtains red crystals after being spin-dried for solvent, the lower 50 ℃ of dry 24h of vacuum condition obtain product 3,6-bis-(pyrene-2-yl)-2,5-diformazan alkyl pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone.Productive rate is 76%.
Above-mentioned preparation is as follows containing the reaction formula of the organic semiconductor material of pyrrolopyrrole alkane ketone unit:
The uv-visible absorption spectra figure of the organic semiconductor material of preparation in the present embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm～700nm, have large wider absorption, wherein maximum absorption band is positioned at 524nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material of the present embodiment 2 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 417 ℃.
ITO/PEDOT:PSS/ the present embodiment 2 organic semiconductor material/Au of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination organic semiconductor material, the hole mobility that obtains organic semiconductor material is 5.2 * 10
-4cm
2/ Vs.
Embodiment 3
The present embodiment disclose the following pyrrolopyrrole alkane ketone of structural formula to acceptor organic semiconductor material (PyPy3), that is: 3,6-bis-(pyrene-2-yl)-2,5-bis-NSC 62789 base pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, its structural formula is as follows:
The preparation process of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is as follows:
Under nitrogen protection, by 3,6-bis-(5-bromothiophene-2-yl)-2,5-bis-NSC 62789 base pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone (305mg, 0.3mmol), pyrene-2-boric acid (162mg, 0.66mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution leads to after the about 20min of nitrogen purge gas subsequently in flask; Flask is heated to 130 ℃ and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, use dichloromethane extraction three times, merges organic phase, after adopting anhydrous magnesium sulfate drying, be spin-dried for, it is that leacheate is separated through silica gel column chromatography with ethyl acetate that crude product adopts sherwood oil again, and sherwood oil and ethyl acetate volume ratio are 10:1, after being spin-dried for solvent, obtain red crystals, the lower 50 ℃ of dry 24h of vacuum condition obtain product: 3,6-bis-(pyrene-2-yl)-2,5-bis-NSC 62789 base pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone, productive rate is 84%.
Above-mentioned preparation is as follows containing the reaction formula of the organic semiconductor material of pyrrolopyrrole alkane ketone unit:
The uv-visible absorption spectra figure of the organic semiconductor material of preparation in the present embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm～700nm, have large wider absorption, wherein maximum absorption band is positioned at 525nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material of the present embodiment 3 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 383 ℃.
ITO/PEDOT:PSS/ the present embodiment 3 organic semiconductor material/Au of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination organic semiconductor material, the hole mobility that obtains organic semiconductor material is 6.1 * 10
-4cm
2/ Vs.
Embodiment 4
The present embodiment disclose the following pyrrolopyrrole alkane ketone of structural formula to acceptor organic semiconductor material (PyPy4), that is: 3,6-bis-(pyrene-2-yl)-2,5-bis-dodecyl pyrrolo-es [3,4-c] its structural formula of pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone is as follows:
The preparation process of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is as follows:
Under nitrogen protection, by 3,6-bis-(5-bromothiophene-2-yl)-2,5-bis-dodecyl pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone (238mg, 0.3mmol), pyrene-2-boric acid (170mg, 0.69mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Suzuki coupling reaction 36h.Stopped reaction cool to room temperature, use dichloromethane extraction three times, merges organic phase, after adopting anhydrous magnesium sulfate drying, be spin-dried for, it is that leacheate is separated through silica gel column chromatography with ethyl acetate that crude product adopts sherwood oil again, and sherwood oil and ethyl acetate volume ratio are 10:1, after being spin-dried for solvent, obtain red crystals, the lower 50 ℃ of dry 24h of vacuum condition obtain product 3,6-bis-(pyrene-2-yl)-2,5-bis-dodecyl pyrrolo-es [3,4-c] pyrroles-1,4 (2H, 5H)-diketone, productive rate is 82%.
Above-mentioned preparation is as follows containing the reaction formula of the organic semiconductor material of pyrrolopyrrole alkane ketone unit:
The uv-visible absorption spectra figure of the organic semiconductor material of preparation in the present embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm～700nm, have large wider absorption, wherein maximum absorption band is positioned at 523nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material of the present embodiment 4 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 395 ℃.
ITO/PEDOT:PSS/ the present embodiment 4 organic semiconductor material/Au of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination organic semiconductor material, the hole mobility that obtains organic semiconductor material is 6.5 * 10
-4cm
2/ Vs.
Embodiment 5
The present embodiment disclose the following pyrrolopyrrole alkane ketone of structural formula to acceptor organic semiconductor material (PyPy5), that is: 3,6-bis-(pyrene-2-yl)-2,5-bis-normal hexane base pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, its structural formula is as follows:
The preparation process of the above-mentioned organic semiconductor material containing pyrrolopyrrole alkane ketone unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 3, 6-bis-(5-bromothiophene-2-yl)-2, 5-bis-normal hexane base pyrrolo-es [3, 4-c] pyrroles-1, 4 (2H, 5H)-diketone (188mg, 0.3mmol), cumarone-2-boric acid (117mg, 0.72mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (32mg, 0.09mmol) join the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution, pass into after the about 30min of gas mixture air-discharging of nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Suzuki coupling reaction 36h.Stopped reaction cool to room temperature, use dichloromethane extraction three times, merges organic phase, after adopting again anhydrous magnesium sulfate drying, be spin-dried for, it is that leacheate is separated through silica gel column chromatography with ethyl acetate that crude product adopts sherwood oil, and sherwood oil and ethyl acetate volume ratio are 10:1, obtains red crystals after being spin-dried for solvent, the lower 50 ℃ of dry 24h of vacuum condition obtain product 3,6-bis-(pyrene-2-yl)-2,5-bis-normal hexane base pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone.Productive rate is 80%.
Above-mentioned preparation is as follows containing the reaction formula of the organic semiconductor material of pyrrolopyrrole alkane ketone unit:
The uv-visible absorption spectra figure of the organic semiconductor material of preparation in the present embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm～700nm, have large wider absorption, wherein maximum absorption band is positioned at 526nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material of the present embodiment 5 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 408 ℃.
ITO/PEDOT:PSS/ the present embodiment 5 organic semiconductor material/Au of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination organic semiconductor material, the hole mobility that obtains organic semiconductor material is 5.7 * 10
-4cm
2/ Vs.
Embodiment 6
Refer to Fig. 1, a kind of solar cell device 60 comprises substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is for being ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.
Buffer layer 63 is formed at anode 62 away from a side surface of substrate 61.The material of buffer layer 63 is poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (PEDOT:PSS).
Active coating 64 is formed at buffer layer 63 away from a side surface of anode 62.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2, and wherein electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (PC
61bM) or [6,6] phenyl-C
71-methyl-butyrate (PC
71bM), electron donor material is the organic semiconductor material containing pyrrolopyrrole alkane ketone unit prepared by the present invention, in present embodiment, and the PyPy1 of preparation in the embodiment mono-that electron donor material is.
Negative electrode 65 is formed at active coating 64 away from a side surface of buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
Be appreciated that buffer layer 63 can omit, now active coating 64 is directly formed at anode 62 surfaces.
The manufacturing processed of this solar cell device 60 is as follows:
After anode 62 being formed to a side surface of substrate 61, carry out ultrasonic cleaning, and after processing with oxygen-Plasma, on anode 62 surfaces, be coated with the PEDOT:PSS that last layers play modification and form buffer layer 63.
On buffer layer 64, apply one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PC
71bM, the PyPy1 of preparation in the embodiment mono-that electron donor material is.
On active coating 64 surfaces, form negative electrode 65.In present embodiment, the aluminium lamination of negative electrode 65 for being formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this solar cell device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
Adopt the J-V curve of Keithley236 measuring element, and controlled by computer by Labview software.The white light source that is simulated solar irradiation by the filter set cooperation of 500W xenon lamp and AM1.5G, light intensity when device is measured is 100mW/cm
2or 80mW/cm
2.Test result is in Table one.
The photovoltaic performance of organic solar batteries prepared by table one Application Example 1 material
| PyPy:PC 71BM(1:2,w/w) | V oc(V) | J sc(mA/cm 2) | FF(%) | PCE(%) |
| PyPy1 | 0.70 | 4.89 | 47.6 | 1.63 |
When this solar cell device 60 is used, under illumination, light transmission substrate 61 and anode 62, conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produce exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PC
71bM, realizes the separation of electric charge, thereby forms current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to negative electrode 65, transmit and be collected by negative electrode, transmit and collected by anode 62 along electron donor material anode 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. containing an organic semiconductor material for pyrrolopyrrole alkane ketone unit, it is characterized in that thering is following structural formula:
wherein, R is C
1～C
20alkyl.
2. contain a preparation method for the organic semiconductor material of pyrrolopyrrole alkane ketone unit, it is characterized in that, comprise the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R is C
1～C
20alkyl;
In oxygen-free environment, the compd A that is 1:2～1:2.4 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～48 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the organic semiconductor material containing pyrrolopyrrole alkane ketone unit that following structural formula represents:
3. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4～1:8.
5. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20～1:100.
6. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, is characterized in that, the temperature of reaction of described Suzuki coupling reaction is 90 ℃～120 ℃, and the reaction times is 24 hours～36 hours.
7. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
8. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 7, is characterized in that, the solute in described alkaline solution and the mol ratio of compd A are 20:1～50:1.
9. the preparation method of the organic semiconductor material containing pyrrolopyrrole alkane ketone unit according to claim 2, it is characterized in that, also comprise the step that the organic semiconductor material P containing pyrrolopyrrole alkane ketone unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methylene dichloride to extract in the solution after Suzuki coupling reaction, merge organic relevant dry after, it is separated that solid that filtration is obtained adopts sherwood oil and ethyl acetate mixture to carry out silica gel column chromatography as leacheate, after vacuum-drying, obtain the organic semiconductor material containing pyrrolopyrrole alkane ketone unit after purifying.
10. a solar cell device, comprises active coating, it is characterized in that, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6] phenyl-C
71-methyl-butyrate, described electron donor material has the organic semiconductor material containing pyrrolopyrrole alkane ketone unit of following structural formula:
Wherein, R is C
1～C
20alkyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889016A (en) * | 2007-10-09 | 2010-11-17 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, its preparation and purposes |
| CN102388046A (en) * | 2009-04-08 | 2012-03-21 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, their manufacture and use as semiconductors |
| US20120074393A1 (en) * | 2010-09-29 | 2012-03-29 | Basf Se | Semiconductors based on diketopyrrolopyrroles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889016A (en) * | 2007-10-09 | 2010-11-17 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, its preparation and purposes |
| CN102388046A (en) * | 2009-04-08 | 2012-03-21 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, their manufacture and use as semiconductors |
| US20120074393A1 (en) * | 2010-09-29 | 2012-03-29 | Basf Se | Semiconductors based on diketopyrrolopyrroles |
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