CN103022361B - Manufacturing method of photovoltaic cell - Google Patents

Manufacturing method of photovoltaic cell Download PDF

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CN103022361B
CN103022361B CN201210473601.5A CN201210473601A CN103022361B CN 103022361 B CN103022361 B CN 103022361B CN 201210473601 A CN201210473601 A CN 201210473601A CN 103022361 B CN103022361 B CN 103022361B
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sulfo
alkyl
amido
manufacture method
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CN103022361A (en
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张俊
丛国芳
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LIYANG PRODUCTIVITY PROMOTION CENTER
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a manufacturing method of a photovoltaic cell. The method comprises preparing a substrate, an anode, an active layer, an electronic transmission layer and a cathode successively, wherein the electronic transmission layer is a polymer with a structure of the general formula (I), and the polymerization degree n thereof is any integer between 1 and 300. The manufacturing method of the polymer comprises the following steps of: firstly, carrying out decarboxylative nitration on a compound 1 to obtain a compound 2, and reducing the compound 2 to a compound 3, then carrying out diazotization, and reacting with potassium ethyl xanthate to generate a compound 4; secondly, diazotizing an aromatic amine 5, and reacting with sodium iodide to synthesize an aromatic iodide 6; and thirdly, reducing the compound 4 to thiophenol 7, and then dissolving the thiophenol 7 with an aromatic chloride compound 8 or the aromatic iodide compound 6, to obtain a compound of the general formula I under the action of a base catalyst. The photovoltaic cell manufactured by using the material as the electronic transmission layer has a relatively high open circuit voltage and good device performance.

Description

A kind of manufacture method of photovoltaic cell
Technical field
The present invention relates to a kind of manufacture method of photovoltaic cell.
Background technology
Along with the increase year by year of global energy requirements, the disposable energy such as oil, coal day by day exhausted, people have dropped into more concern and research to the renewable resource such as wind energy, solar energy, are wherein one of focuses wherein based on the photovoltaic cell of photovoltaic effect.
At present, photovoltaic cell ripe on market is mainly the inorganic photovoltaic cell such as based single crystal silicon, polysilicon, amorphous silicon, GaAs, indium phosphide and polycrystalline film compound semiconductor, wherein, polysilicon and amorphous silicon photovoltaic cell are occupied an leading position on civilian photovoltaic cell market.Through the development in more than 50 years, the photoelectric conversion efficiency of inorganic monocrystalline Silicon photrouics is by 6% at the beginning of invention, bring up to current peak efficiency and can reach more than 30%, but because inorganic semiconductor photovoltaic cell is very high to the requirement of material purity, and expensive, therefore its application is very limited.
Kodak introduces first to body and acceptor material in same device, forms hetero-junction solar cell conversion efficiency and reaches 1%, indicate that photovoltaic device prepared by organic semiconductor makes a breakthrough.People are by furtheing investigate different compound systems afterwards, demonstrate the existence of Photo-induced electron transfer.The discovery of Photoinduced Charge fast energy transfer phenomena is the important breakthrough of polymer photovoltaic cell theoretical side, for the raising of polymer photovoltaic cell efficiency provides theories integration.The people such as Yu Gang are by blended by electron donor material and acceptor material, and obtain the photovoltaic cell of conjugated polymer MEH-PPV and carbon 60 inierpeneirating network structure, its energy conversion efficiency reaches 2.9%, the photovoltaic cell that Here it is it has often been said.
Bulk heterojunction concept produces the fault of construction overcoming individual layer, bilayer/multilayer device.Due to electron donor and the network-like continuous phase of each self-forming of electron acceptor, the electronics that photoinduction produces and hole respectively respective mutually in transport and be collected on corresponding electrode, photo-generated carrier is reduced by the probability of compound again greatly arriving before corresponding electrode, thus improves photoelectric current.Like this, bulk heterojunction structure just can significantly improve photovoltaic energy conversion efficiency.Nowadays, bulk heterojunction concept has been widely used in the photovoltaic cell based on polymer, and energy conversion efficiency can reach more than 5%, and it has tempting developing direction.
But the open circuit voltage of current organic photovoltaic battery generally can only reach about 0.60 ~ 0.80eV, distance commercialization also has one section of larger distance.Therefore, how obtaining high efficiency higher, the organic photovoltaic battery that performance is more stable, realize it and commercially produce, be applied to all spectra that current inorganic photovoltaic cell is applied, is the very large challenge that those skilled in the art face.
Summary of the invention
The invention discloses a kind of manufacture method of photovoltaic cell, this photovoltaic cell has higher open circuit voltage and device performance.
Photovoltaic cell manufacture method of the present invention comprises the steps: to prepare substrate, anode, active layer and negative electrode successively, the method is also included between active layer and negative electrode prepares electron transfer layer, electron transfer layer is for having the polymer of general formula (I) structure, its polymerization degree n is the arbitrary integer of 1 ~ 300, and the manufacture method of this polymer comprises the steps:
The first, obtain compound 2 by compound 1 decarboxylative nitration, restore into compound 3, and then diazotising, with ehtyl potassium xanthate reacting generating compound 4;
The second, by aromatic amine 5 diazotising, then iodo product 6 fragrant with sodium iodide Reactive Synthesis;
Three, first compound 4 is reduced into benzenethiol 7, under being then dissolved in base catalyst effect with fragrant chlorinated compound 8 or fragrant iodo compound 6, obtains compound of Formula I;
Wherein, A is selected from substituted-phenyl that 4-nitro shown in formula II replaces, the 4-alkoxyl shown in formula II I replaces substituted-phenyl, the substituted heterocycle shown in structural formula IV or the substituted heterocycle shown in structural formula V;
Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18independently be selected from hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl, nitro, amide groups, haloalkyl, acyl group, aldehyde radical, carboxyl, alkoxy carbonyl group or acyloxy, and R 5, R 6, R 7, R 8be asynchronously hydrogen;
R 9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y are independently selected from nitrogen, oxygen or sulphur;
Wherein said alkyl is 1-6 carbon atom alkyl; Described alkoxyl is alkyl oxy or the oxygen base alkyl of 1-6 carbon atom; Described haloalkyl is by the alkyl of 1-6 carbon atom of F, Cl or Br replacement; Alkoxy carbonyl group is the alkoxy carbonyl group of 1-6 carbon atom.
The actual conditions of preparation compound of Formula I is as follows:
The reaction temperature of the decarboxylative nitration in step one is 0-100 DEG C; Reduction reaction reducing agent used can be zinc powder, iron powder, magnesium powder, and acid can be acetic acid, hydrochloric acid, and reducing agent also can be palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, iron powder/hydrazine hydrate, palladium carbon/hydrogen etc., and reaction temperature is 0-100 DEG C; In diazotation step, reagent can be natrium nitrosum, potassium nitrite, nitrobutane, and acid can be hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, and reaction temperature is-20-10 DEG C; Dithiocarbonic acids salinization reagent can be various alkyl xanthate, and reaction temperature is 0-120 DEG C;
Diazotation step in step 2 can use tetrahydrochysene lithium aluminium/oxolane reduction, and also can be hydrolyzed with sodium hydrate aqueous solution, reaction temperature is 0-100 DEG C; And the reaction dissolvent of iodide reaction can be ethanol, methyl alcohol, isopropyl alcohol, the alcohol such as ethylene glycol, benzene, toluene, acetone, oxolane, dioxane, DMF, pyridine, methyl-sulfoxide, carrene, chloroform, dichloroethanes etc.
In step 3, base catalyst used is for being selected from inorganic alkaline compound, and as potash, sodium carbonate, NaOH, potassium hydroxide, sodium hydride etc., reaction temperature is 0-200 DEG C.
Preferably, the material of substrate is glass, flexible macromolecule or metal base.
Preferably, the material of anode is metal oxide or the metal oxide containing alloy, is formed by vapour deposition or sputter.
Preferably, active layer comprises the electron donor material and electron acceptor material that are laminated, wherein electron donor material is conjugated polymer or Organic micromolecular semiconductor material, electron acceptor material is carbon 60 and derivative thereof or carbon 70 and derivative thereof or inorganic semiconductor nano particle, is coated in hole transmission layer surface forms by the solution formed by above-mentioned material.
Preferably, the material of negative electrode is light tight metal, and its preparation method is vapour deposition method deposition etc.
Accompanying drawing explanation
Fig. 1 is the structural representation comprising the photovoltaic cell of electron transfer layer and hole transmission layer of the present invention.
Embodiment
In order to make those skilled in the art more clearly understand the present invention, describe its technical scheme in detail below by embodiment.
Photovoltaic cell of the present invention comprises the substrate 1, anode 2, active layer 4 and the negative electrode 5 that stack gradually, has electron transfer layer 6, as shown in Figure 1 between active layer 4 and negative electrode 5.
Wherein, the material of electron transfer layer 6 is polymer that a kind of monomer has structural formula (I), and its polymer n is the arbitrary integer between 1 ~ 300,
（I）
A is selected from substituted-phenyl that 4-nitro shown in formula II replaces, the 4-alkoxyl shown in formula II I replaces substituted-phenyl, the substituted heterocycle shown in structural formula IV or the substituted heterocycle shown in structural formula V;
Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18independently be selected from hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl, nitro, amide groups, haloalkyl, acyl group, aldehyde radical, carboxyl, alkoxy carbonyl group or acyloxy, and R 5, R 6, R 7, R 8be asynchronously hydrogen;
R 9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y are independently selected from nitrogen, oxygen or sulphur;
Wherein said alkyl is 1-6 carbon atom alkyl; Described alkoxyl is alkyl oxy or the oxygen base alkyl of 1-6 carbon atom; Described haloalkyl is by the alkyl of 1-6 carbon atom of F, Cl or Br replacement; Alkoxy carbonyl group is the alkoxy carbonyl group of 1-6 carbon atom.
When described A is substituted-phenyl II, wherein R 1, R 2, R 3, R 4separately refer to hydrogen, halogen, hydroxyl, amido, methyl, ethyl.Described R 1, R 2, R 3and R 4in preferably have one at least for hydroxyl or amido, described hydroxyl or amido are replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative further.
When described A is substituted-phenyl III, wherein R 5, R 6, R 7, R 8separately refer to hydrogen, halogen, hydroxyl, amido, methyl, ethyl, benzyl, alkoxyl, nitro, acyloxy or amide groups, and R 5, R 6, R 7, R 8be asynchronously hydrogen.Described R 5, R 6, R 7and R 8in preferably have one at least for hydroxyl or amido, described hydroxyl or amido are replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative further.
When described A is substituted heterocycle IV or substituted heterocycle V, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18independently be selected from hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl.
Described compound of Formula I is selected from following compound:
3,4,5-trimethoxy-1-[(3-amino-4-nitrobenzophenone) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-acetamido-4-nitrobenzophenone) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-nitro-4-methoxyphenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-amino-4-methoxyl phenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(the fluoro-4-methoxyphenyl of 3-) sulfo-] benzene,
3,4,5-trimethoxy-1-[(4-ethoxyl phenenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-benzyloxy-4-methoxyphenyl) sulfo-] benzene,
5-trifluoromethyl-2-[(3,4,5-trimethoxyphenyl) sulfo-] pyridine,
3-[(3,4,5-trimethoxyphenyl) sulfo-] benzothiophene-2-methyl formate,
2-fluorenes methoxy amide groups-3-acetoxyl group-N-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide,
2-amino-3-hydroxy-n-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide,
3,4,5-trimethoxy-1-[(3-hydroxyl-4-methoxyphenyl) sulfo-] benzene.
The manufacture method of photovoltaic cell of the present invention comprises each layer prepared electron transfer layer He stack gradually photovoltaic cell.
The manufacture method of electron transfer layer of the present invention comprises the steps:
The first, obtain compound 2 by compound 1 decarboxylative nitration, restore into compound 3, and then diazotising, with ehtyl potassium xanthate reacting generating compound 4;
The second, by aromatic amine 5 diazotising, then iodo product 6 fragrant with sodium iodide Reactive Synthesis;
Three, first compound 4 is reduced into benzenethiol 7, under being then dissolved in base catalyst effect with fragrant chlorinated compound 8 or fragrant iodo compound 6, obtains compound of Formula I;
Wherein, the structure of A is described above.
In order to prepare the CA4 derivative of the Sulfide-containing Hindered bridge chain in compound of Formula I, actual conditions is as follows:
The reaction temperature of the decarboxylative nitration in step one is 0-100 DEG C; Reduction reaction reducing agent used can be zinc powder, iron powder, magnesium powder, and acid can be acetic acid, hydrochloric acid, and reducing agent also can be palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, iron powder/hydrazine hydrate, palladium carbon/hydrogen etc., and reaction temperature is 0-100 DEG C; In diazotation step, reagent can be natrium nitrosum, potassium nitrite, nitrobutane, and acid can be hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, and reaction temperature is-20-10 DEG C; Dithiocarbonic acids salinization reagent can be various alkyl xanthate, and reaction temperature is 0-120 DEG C;
Diazotation step in step 2 can use tetrahydrochysene lithium aluminium/oxolane reduction, and also can be hydrolyzed with sodium hydrate aqueous solution, reaction temperature is 0-100 DEG C; And the reaction dissolvent of iodide reaction can be ethanol, methyl alcohol, isopropyl alcohol, the alcohol such as ethylene glycol, benzene, toluene, acetone, oxolane, dioxane, DMF, pyridine, methyl-sulfoxide, carrene, chloroform, dichloroethanes etc.
In step 3, base catalyst used is for being selected from inorganic alkaline compound, and as potash, sodium carbonate, NaOH, potassium hydroxide, sodium hydride etc., reaction temperature is 0-200 DEG C.
The specific embodiment of the above-mentioned electron transfer layer of some preparations is described below in detail:
Embodiment 1
Preparation O-ethyl-S-(3,4,5-trimethoxyphenyl) dithiocarbonate (ZLM-1)
Be dissolved in 30.5mL concentrated hydrochloric acid and 250mL water by 3,4,5-trimethoxy-aniline (22.3g), ice bath is chilled to about 0 DEG C, slowly drips NaNO under stirring 2the aqueous solution (9.2g), temperature control is no more than 5 DEG C, drips Bi Jixu and reacts 15min, then add AcONa (20.0g).This diazonium salt solution is slowly dropped to (48.7g is dissolved in 120mL water) in the KS2COEt aqueous solution of about 80 DEG C, in 70-80 DEG C of reaction 1h.Reaction terminates, and be chilled to room temperature, EA extracts 100mL × 3, merges organic phase.Add anhydrous sodium sulfate drying again.Suction filtration, obtains filtrate, revolves desolventizing, obtains 30.4g brown-red oil, and silicagel column is separated, and obtains 11.8g yellowish white sticky solid, productive rate 34%. 1h NMR (400MHz, CDCl 3): δ 1.34 (t, J=7.2Hz, 3H), 3.84 (s, 3H), 3.85 (s, 6H), 3.88 (s, 3H), 4.61 (dd, J=7.2,7.2Hz, 1H), 6.73 (s, 1H).
Embodiment 2
Preparation 3,4,5-trimethoxy-1-[(3-amino-4-nitrobenzophenone) sulfo-] benzene (ZLM-2)
Be dissolved in THF (66mL) by O-ethyl-S-(3,4,5-trimethoxyphenyl) dithiocarbonate ZLM-1 (4.0g), slow gradation adds LiAlH 4(2.11g), backflow 1h, is chilled to room temperature, is adjusted to pH=5 with 10%HCl, then extract 100mL × 3 with EA, merges organic phase, adds anhydrous sodium sulfate drying 1h, then suction filtration, obtain filtrate, revolve desolventizing and namely obtain 3,4,5-trimethoxy benzenethiol.Under nitrogen protection, first by K 2cO 3(5.8g) add in 50mL bis-neck bottle with 5-chloro-2-nitroaniline (1.2g), again by upper step gained 3,4,5-trimethoxy benzenethiol is dissolved in DMF (23.7mL) and adds in reaction bulb, in 120 DEG C of backflows, TLC monitors (solvent: PE: EA=4: 1).Raw material disappears, and stops reaction, is chilled to room temperature, adds the dilution of 200mL water, extracts 200mL × 4 with EA, merge organic phase, add anhydrous sodium sulfate drying 1h.Suction filtration, obtains filtrate, revolves desolventizing, and silicagel column is separated, and obtains 1.2g yellow solid, productive rate 51%, mp168.1-170.2 DEG C. 1h NMR (400MHz, CDCl 3): δ 3.86 (s, 6H), 3.91 (s, 3H), 6.09 (br, 2H), 6.33 (d, J=1.6Hz, 1H), 6.43 (dd, J=7.2,2.0Hz, 1H), 6.79 (s, 2H), 7.99 (d, J=9.6Hz, 1H). 13c NMR (400MHz, CDCl3): δ 56.3,61.0,112.2,113.5,114.9,124.1,126.6,129.7,139.3,144.9,149.8,153.9.MS (EI) m/z:336 (M +).
Embodiment 3
Preparation 3,4,5-trimethoxy-1-[(3-acetamido-4-nitrobenzophenone) sulfo-] benzene (ZLM-3)
3,4,5-trimethoxy-1-[(3-amino-4-nitrobenzophenone) sulfo-] benzene ZLM-2 (50mg) is added in the mixed solvent of aceticanhydride (17 μ L) and acetic acid (9 μ L), in 85-90 DEG C of backflow 2h.Pressure reducing and steaming low-boiling point material, obtains 61mg yellow solid, productive rate 93%, mp 168.1-170.2 DEG C. 1h NMR (400MHz, CDCl 3): δ 2.26 (s, 3H), 3.87 (s, 6H), 3.92 (s, 3H), 6.73 (dd, J=7.2,1.8Hz, 1H), 6.81 (s, 2H), 8.07 (d, J=8.8Hz, 1H), 8.61 (d, J=6.0Hz, 1H), 10.48 (s, 1H). 13c NMR (400MHz, CDCl3): δ 25.7,56.3,61.0,112.2,117.6,119.8,123.7,126.2,132.9,135.2,139.6,151.4,154.0,168.9.MS (EI) m/z:378 (M +).
Embodiment 4
Preparation 3-nitro-4-methoxyl group iodobenzene (ZLM-4)
3-nitro-4-aminoanisole (860mg) is dissolved in watery hydrochloric acid (0.5mL concentrated hydrochloric acid adds the dilution of 9mL water), is chilled to 0 DEG C, starts to drip NaNO 2the aqueous solution (424mg), then 20min is reacted at this temperature, obtain diazonium salt solution.Then this diazonium salt solution is slowly dropped in the NaI aqueous solution (921mg) in 0 DEG C, drip and finish, rise to stirring at room temperature 12h.EA extracts 50mL × 3, merges organic phase, adds anhydrous sodium sulfate drying 1h, then suction filtration, obtain filtrate, revolve desolventizing, and silicagel column is separated, and obtains 573mg yellow solid, productive rate 40%, mp 95.8-97.3 DEG C (literature value: 97-99 DEG C).
Embodiment 5
Preparation 3-fluoro-4-methoxyl group iodobenzene (ZLM-5)
By embodiment 4, replace 3-nitro-4-aminoanisole with the fluoro-4-aminoanisole (600mg) of 3-, obtain 549mg faint yellow solid, productive rate 56%, mp 32.8-34.1 DEG C (literature value: 34 DEG C).
Embodiment 6
Preparation 5-trifluoromethyl-2-[(3,4,5-trimethoxyphenyl) sulfo-] pyridine ((ZLM-13)
With reference to the synthesis of ZLM-2, substitute 5-chloro-2-nitroaniline with 2-chloro-5-trifluoromethylpyridine (127mg), and reduce reaction temperature to 80 DEG C, obtain 206mg white solid, productive rate 59.7%, mp83.8-84.5 DEG C. 1H NMR(400MHz，CDCl 3)：δ3.86(s，6H)，3.91(s，3H)，6.85(s， 2H)，6.94(d，J＝8.8Hz，1H)，7.66(dd，J＝6.4，2.0Hz，1H)，8.67(s，1H). 13C NMR(400MHz，CDCl 3)：δ56.6，61.3，112.8，120.1，122.7，123.0，123.7，125.3，133.8，133.9，139.9，146.6，146.7，154.3，167.6.MS(EI)m/z：345(M +)。
Embodiment 7
Preparation 3-[(3,4,5-trimethoxyphenyl) sulfo-] benzothiophene-2-methyl formate (ZLM-14)
With reference to the synthesis of ZLM-2, substitute 5-chloro-2-nitroaniline with 3-chloro thiophene-2-carboxylic acid (100mg), and reduce reaction temperature to 80 DEG C, obtain 45mg yellow solid, productive rate 25.7%. 1HNMR(400MHz，CDCl 3)：δ3.69(s，6H)，3.79(s，3H)，3.95(s，3H)，6.47(s，2H)，7.35(t，J＝7.8Hz，1H)，7.47(t，J＝7.6Hz，1H)，7.81(d，J＝8.4Hz，1H)，7.86(d，J＝8.0Hz，1H). 13C NMR(400MHz，CDCl 3)：δ52.6，56.1，60.9，106.1，122.7，125.1，125.4，127.5，130.6，131.6，139.7，139.8，153.4，162.2.MS(EI)m/z：390(M +)。
Embodiment 8
Preparation 2-fluorenes methoxy amide groups-3-acetoxyl group-N-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide (ZLM-15)
Under nitrogen protection, by 3, 4, 5-trimethoxy-1-[(3-amino-4-methoxyl phenyl) sulfo-] benzene ZLM-7 (140mg) and O-acetyl group-N-Fmoc-L-serine (148mg) is dissolved in 5mL anhydrous methylene chloride, add DCC (82mg) and HOBt (56mg) again, stirring at room temperature 24h, revolve desolventizing, add 20mL acetic acid ethyl dissolution again, suction filtration, filter residue ethyl acetate washing several, merge organic phase, wash reactant liquor with water for several times, anhydrous sodium sulfate drying organic phase, suction filtration, obtain filtrate, revolve desolventizing and obtain 365mg yellowish-brown grease.(benzinum: ethyl acetate=1: 1), obtains 277mg white solid to silica gel column chromatography, productive rate 80.6%. 1H NMR(400MHz，CDCl 3)：δ2.09(s，3H)，3.78(s，6H)，3.82(s，3H)，3.83(s，3H)，4.24(t，J＝6.8Hz，1H)，4.33(t，J＝5.2Hz，1H)，4.41-4.53(m，3H)，4.64(d，J＝4.0Hz，1H)，5.73(d，J＝6.8Hz，1H)，6.57(s，2H)，6.83(d，J＝8.4Hz，1H)，7.13(dd，J＝2.2，6.4Hz，1H)，7.31-7.33(m，2H)，7.39-7.42(m，2H)，7.60(d，J＝6.8Hz，2H)，7.71(d，J＝7.6Hz，2H)，8.44(s，1H)，8.49(d，J＝2.4Hz，1H)。
Material and the preparation method of other layer of photovoltaic cell are respectively:
The material of substrate 1 can be glass, plastics or metal base.Substrate 1 can be hard material, as glass or quartz, also can be flexible material, as flexible macromolecule, flexible high molecular material includes but not limited to: Polyethylene Naphthalate, polyethylene terephthalate, polyamide, polymethyl methacrylate, Merlon and/or polyurethane.Substrate 1, except above-mentioned insulating material, also can use electric conducting material, the metals such as such as titanium, aluminium, copper, nickel.
The material of anode 2 is metal oxide or the metal oxide containing alloy (doped), preferential oxidation indium tin (ITO), tin oxide, fluorine doped tin oxide etc.Anode can be formed by any traditional method, such as vapour deposition, sputter etc.
Active layer 4 comprises the electron donor material and electron acceptor material that are laminated, wherein electron donor material is conjugated polymer or Organic micromolecular semiconductor material, and electron acceptor material is carbon 60 and derivative thereof or carbon 70 and derivative thereof or inorganic semiconductor nano particle.
The material of negative electrode 5 is preferably light tight metal, such as Al, Ca/Al, Mg/Al, Mg/Ag, Cu, Au etc.The method manufacturing negative electrode 5 can be vapour deposition method deposition etc.
The embodiment stacking gradually each layer of photovoltaic cell of the present invention is as follows:
Some with lot number ITO Conducting Glass, specification is 15 millimeters × 15 millimeters, and the thickness of ITO is about 130 nanometers, and its square resistance is about 20 ohm/.Use acetone, micron order semiconductor special purpose detergent, deionized water, the ultrasonic process of isopropyl alcohol 10 minutes clean ITO substrate surfaces successively, leave standstill 4 hours at putting into constant temperature oven 80 DEG C subsequently and dry.
ITO substrate after oven dry oxygen plasma treatment 4 minutes, organic attachment film of removing ITO surface attachment and organic pollution, proceed to anhydrous and oxygen-free by the substrate obtained by said method subsequently, be full of the special gloves case of high pure nitrogen (manufacture of VAC company of the U.S.).Under this glove box inert atmosphere, by polymer donor material and electron acceptor material, carbon 60 derivative-[6,6]-phenyl-C61-methyl butyrate (PCBM) is placed in clean sample bottle respectively, with conventional organic solvent (as chlorobenzene, toluene etc.) dissolve be mixed with solution, be placed on heating mixing platform on stir, obtain clear filtrate with 0.45 micrometer polytetrafluoroethylene (PTFE) membrane filtration.Then according to a certain percentage by polymer donor material and electron acceptor material mixing, be placed on heating mixing platform and stir.
Electron transport layer materials of the present invention can provide ohmic contact to high-work-function metal; be placed in clean bottle; proceed in nitrogen protection film forming special gloves case; the solution being made into 0.01-1.5% is dissolved in the methyl alcohol being added with a small amount of acetic acid; be placed on mixing platform and stir, filter to obtain settled solution with 0.45 micron membrane filter.The preparation of active layer is obtained by the solution of coated polymer donor material on substrate and electron acceptor material mixing.For this reason, first just the negative-pressure adsorption that produced by mechanical pump of ITO substrate is on sol evenning machine, instillation polymer donor material and electron acceptor material mixing molten after, obtain through high speed spin coating (600-6000 rev/min), generally speaking, require that obtained active layer thickness is in 20-500 nanometer, preferred film thickness is 70-200 nanometer.Thickness controls by regulating the concentration of the rotating speed of sol evenning machine and control polymer donor material and electron acceptor material mixed solution.
Polymer donor material and electron acceptor material mixed solution are after ITO/PEDOT:PSS substrate film forming, after drying, instil above-mentioned electron transport layer materials more in the above, and through high speed spin coating (600-6000 rev/min), the thickness of the electron transfer layer of acquisition is in 0.5-50 nanometer.Subsequently, device is proceeded in Vacuum Deposition chamber, open mechanical pump and molecular pump, when reaching 3 × 10 in plating chamber -4after the high vacuum of Pa, start AM aluminum metallization film (100 nanometer) as extraction electrode.By mask frame, each electrode and active layer are made the pattern designed.The region that the light-emitting zone of device is covered alternately by mask and ITO is defined as 0.15 square centimeter.
All preparation process of the present invention are all carried out in the glove box providing nitrogen inert atmosphere or in vacuum.In order to make above-mentioned vacuum thermal evaporation metallic film process, the growth rate of settling and total deposit thickness of film are controlled by the thermal power applied, and are monitored in real time by quartz crystal oscillator film thickness monitor (STM-100 type, Sycon company manufactures).The uv-visible absorption spectroscopy of active layer or polymer-electronics donor material is recorded by HP8453A type diode array formula ultraviolet-visible spectrophotometer, wave-length coverage 190 nanometer ~ 1100 nanometer of test.
The measuring process of the photoluminescence spectra of polymer-electronics donor material is as follows: according to the test result of its absorption spectrum, chooses suitable excitaton source.The light path above-mentioned film substrate being placed in Jobin Yvon Spex Fluorolog-3 double-grating fluorescence spectrophotometer can test photoluminescence spectra.In addition, also available discrete light sources excites, and spectra collection INSTASPEC IV type grating beam splitting CCD (charge coupled device) spectrometer has come.The excitation source that can for select has: He-Cd gas laser, exportable 325 nanometers, 442 nanometer exciting lines; The exportable 405 nanometer exciting lines of semiconductor diode laser; Argon ion laser, exportable 488 nanometers, 515 nanometer equal excitation spectral lines.
Photovoltaic cell is energy conversion device, solar energy is converted to electric energy, so the mensuration of any photovoltaic cell device performance parameter, will take all finally sunlight as testing standard.The radiant illumination of AM1.5G measurement standard conventional in laboratory is 100 milliwatts/square centimeter.When carrying out polymer photovoltaic cell performance test with solar simulation light, first with the irradiance of standard cell determination light source whether compound AM1.5G.Standard silicon photovoltaic cell is through calibration: under AM1.5G standard spectrum, i.e. when the illumination of 100 milliwatts/square centimeter radiant illumination is penetrated, the short circuit current obtained is 125 milliamperes.After determining irradiance, can test device.
Strengthening the effect in photovoltaic cell performance for showing device architecture and the method for the present invention relates to of the present invention, adopting conventional device as a comparison.
Embodiment 1
, as electron transfer layer, PFO-DBT35 is as electron donor material, and PCBM is electron acceptor material to adopt poly-[3,4,5-trimethoxy-1-[(3-amino-4-nitrobenzophenone) sulfo-] benzene].Compared with the conventional device not having electron transfer layer, open circuit voltage, by 0.60-0.65 volt, increases substantially 0.90-0.95 volt.
Embodiment 2
, as electron transfer layer, PFO-DBT15 is as electron donor material, and PCBM is electron acceptor material to adopt poly-[3,4,5-trimethoxy-1-[(3-acetamido-4-nitrobenzophenone) sulfo-] benzene].Compared with the conventional device not having electron transfer layer, its open circuit voltage, by 0.60-0.65 volt, increases substantially 0.85 volt.
Embodiment 3
, as electron transfer layer, PFO-DBT15 is as electron donor material, and PCBM is electron acceptor material to adopt poly-[3-[(3,4,5-trimethoxyphenyl) sulfo-] benzothiophene-2-methyl formate].Compared with the conventional device not having electron transfer layer, its open circuit voltage, by 0.60-0.65 volt, increases substantially 0.85 volt.
Embodiment 4
, as electron transfer layer, PFO-DBT15 is as electron donor material, and PCBM is electron acceptor material to adopt poly-[2-amino-3-hydroxy-n-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide].Compared with the conventional device not having electron transfer layer, its open circuit voltage, by 0.70-0.75 volt, significantly brings up to 1.00-1.05 volt.
Embodiment 5
, as electron transfer layer, PFO-DBT15 is as electron donor material, and PCBM is electron acceptor material to adopt poly-[2-fluorenes methoxy amide groups-3-acetoxyl group-N-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide].Compared with the conventional device not having electron transfer layer, its open circuit voltage, by 0.70-0.75 volt, significantly brings up to 1.00-1.05 volt.
Compared with prior art, tool of the present invention has the following advantages:
(1) device architecture that the present invention relates to, method significantly can improve the performance of photovoltaic cell device, especially this important indicator of open circuit voltage.
(2) device architecture that the present invention relates to adopts solution processing technology, and preparation technology is simple, and cost of manufacture is low.
(3) the material soluble solution of electron transfer layer of the present invention is in water or methyl alcohol polar solvent.And active layer material and electron acceptor material are generally insoluble to this kind solvent, therefore when forming this laminated device, between electron transfer layer and active layer, mixing phenomena can not be there is.
Certainly; the present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection range that all should belong to the claim appended by the present invention.

Claims (9)

1. the manufacture method of a photovoltaic cell, comprise and prepare substrate, anode, active layer and negative electrode successively, this manufacture method is also included between active layer and negative electrode prepares electron transfer layer, electron transfer layer is for having the polymer of general formula (I) structure, its polymerization degree n is the arbitrary integer of 1 ~ 300, and the manufacture method of this polymer comprises the steps:
The first, obtain compound 2 by compound 1 decarboxylative nitration, restore into compound 3, and then diazotising, with ehtyl potassium xanthate reacting generating compound 4;
The second, by aromatic amine 5 diazotising, then iodo product 6 fragrant with sodium iodide Reactive Synthesis;
Three, first compound 4 is reduced into benzenethiol 7, under being then dissolved in base catalyst effect with fragrant chlorinated compound 8 or fragrant iodo compound 6, obtains compound of Formula I;
Wherein, A is selected from substituted-phenyl that 4-nitro shown in formula II replaces, the 4-alkoxyl shown in formula II I replaces substituted-phenyl, the substituted heterocycle shown in structural formula IV or the substituted heterocycle shown in structural formula V;
Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18independently be selected from hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl, nitro, amide groups, haloalkyl, acyl group, aldehyde radical, carboxyl, alkoxy carbonyl group or acyloxy, and R 5, R 6, R 7, R 8be asynchronously hydrogen;
R 9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y are independently selected from nitrogen, oxygen or sulphur;
Wherein said alkyl is 1-6 carbon atom alkyl; Described alkoxyl is alkyl oxy or the oxygen base alkyl of 1-6 carbon atom; Described haloalkyl is by the alkyl of 1-6 carbon atom of F, Cl or Br replacement; Alkoxy carbonyl group is the alkoxy carbonyl group of 1-6 carbon atom.
2. manufacture method as claimed in claim 1, is characterized in that, when described A is substituted-phenyl II, and wherein R 1, R 2, R 3, R 4separately refer to hydrogen, halogen, hydroxyl, amido, methyl, ethyl; Described R 1, R 2, R 3and R 4in have one at least for hydroxyl or amido, described hydroxyl or amido are replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative further.
3. manufacture method as claimed in claim 1, is characterized in that, when described A is substituted-phenyl III, and wherein R 5, R 6, R 7, R 8separately refer to hydrogen, halogen, hydroxyl, amido, methyl, ethyl, benzyl, alkoxyl, nitro, acyloxy or amide groups, and R 5, R 6, R 7, R 8be asynchronously hydrogen; Described R 5, R 6, R 7and R 8in have one at least for hydroxyl or amido, described hydroxyl or amido are replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative further.
4. manufacture method as claimed in claim 1, is characterized in that, when described A is substituted heterocycle IV or substituted heterocycle V, and R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18independently be selected from hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl.
5. manufacture method as claimed in claim 1, it is characterized in that, the compound of described general formula I is:
3,4,5-trimethoxy-1-[(3-amino-4-nitrobenzophenone) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-acetamido-4-nitrobenzophenone) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-nitro-4-methoxyphenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-amino-4-methoxyl phenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(the fluoro-4-methoxyphenyl of 3-) sulfo-] benzene,
3,4,5-trimethoxy-1-[(4-ethoxyl phenenyl) sulfo-] benzene,
3,4,5-trimethoxy-1-[(3-benzyloxy-4-methoxyphenyl) sulfo-] benzene,
5-trifluoromethyl-2-[(3,4,5-trimethoxyphenyl) sulfo-] pyridine,
3-[(3,4,5-trimethoxyphenyl) sulfo-] benzothiophene-2-methyl formate,
2-fluorenes methoxy amide groups-3-acetoxyl group-N-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide,
2-amino-3-hydroxy-n-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide, or
3,4,5-trimethoxy-1-[(3-hydroxyl-4-methoxyphenyl) sulfo-] benzene.
6. the manufacture method according to any one of Claims 1 to 5, is characterized in that, in step one,
The reaction temperature of decarboxylative nitration is 0-100 DEG C; Reduction reaction reducing agent used is zinc powder, iron powder, magnesium powder, palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, iron powder/hydrazine hydrate or palladium carbon/hydrogen, and acid is acetic acid or hydrochloric acid, and reaction temperature is 0-100 DEG C; In diazotation step, reagent is natrium nitrosum, potassium nitrite or nitrobutane, and acid is hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, and reaction temperature is-20-10 DEG C; Dithiocarbonic acids salinization reagent is alkyl xanthate, and reaction temperature is 0-120 DEG C;
7. the manufacture method according to any one of Claims 1 to 5, is characterized in that, in step 2,
Diazotation step tetrahydrochysene lithium aluminium/oxolane reduces or is hydrolyzed with sodium hydrate aqueous solution, and reaction temperature is 0-100 DEG C; And the reaction dissolvent of iodide reaction is ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, benzene, toluene, acetone, oxolane, dioxane, DMF, pyridine, methyl-sulfoxide, carrene, chloroform or dichloroethanes.
8. the manufacture method according to any one of Claims 1 to 5, is characterized in that, in step 3,
Base catalyst is potash, sodium carbonate, NaOH, potassium hydroxide or sodium hydride, and reaction temperature is 0-200 DEG C.
9. the manufacture method according to any one of Claims 1 to 5, it is characterized in that, active layer comprises the electron donor material and electron acceptor material that are laminated, wherein electron donor material is conjugated polymer or Organic micromolecular semiconductor material, electron acceptor material is carbon 60 and derivative thereof or carbon 70 and derivative thereof or inorganic semiconductor nano particle, is coated in hole transmission layer surface forms by the solution formed by above-mentioned material.
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