CN103022360B - A kind of manufacture method of photovoltaic cell of high open circuit voltage - Google Patents

A kind of manufacture method of photovoltaic cell of high open circuit voltage Download PDF

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CN103022360B
CN103022360B CN201210472367.4A CN201210472367A CN103022360B CN 103022360 B CN103022360 B CN 103022360B CN 201210472367 A CN201210472367 A CN 201210472367A CN 103022360 B CN103022360 B CN 103022360B
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张俊
丛国芳
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LIYANG PRODUCTIVITY PROMOTION CENTER
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Abstract

The invention discloses a kind of photovoltaic cell manufacture method with high open circuit voltage, comprise and prepare substrate, anode, active layer, electron transfer layer and negative electrode successively; Electron transfer layer is for having the polymer of general formula (I) structure, its polymerization degree n is the arbitrary integer of 1 ~ 300, the manufacture method of this polymer comprises: compound 1 decarboxylative nitration under red fuming nitric acid (RFNA) and acetic acid effect obtains compound 2, compound 3 is become again with zinc powder/acetic acid or palladium carbon/hydrazine hydrate reduction, then make diazonium salt solution with natrium nitrosum and hydrochloric acid, then with ehtyl potassium xanthate reacting generating compound 4; (2), by aromatic amine 5 natrium nitrosum and hydrochloric acid diazonium salt solution is made, then iodo product 6 fragrant with sodium iodide Reactive Synthesis; (3), by compound 4 be dissolved in oxolane, become benzenethiol 7 with tetrahydrochysene lithium aluminium reducing; (4), by fragrant iodo compound 6 and benzenethiol 7 be dissolved in ethylene glycol and isopropyl alcohol or toluene equal solvent, under potash and cuprous iodide effect, composite structure is the material of general formula I.This material is adopted to have higher open circuit voltage and good device performance as the photovoltaic cell of electron transfer layer manufacture.<!--1-->

Description

A kind of manufacture method of photovoltaic cell of high open circuit voltage
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 with the photovoltaic cell of high open circuit voltage, this photovoltaic cell has higher open circuit voltage and device performance.
The photovoltaic cell manufacture method with high open circuit voltage 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:
(1), compound 1 decarboxylative nitration under red fuming nitric acid (RFNA) and acetic acid effect obtains compound 2, compound 3 is become again with zinc powder/acetic acid or palladium carbon/hydrazine hydrate reduction, then make diazonium salt solution with natrium nitrosum and hydrochloric acid, then with ehtyl potassium xanthate reacting generating compound 4;
(2), by aromatic amine 5 natrium nitrosum and hydrochloric acid diazonium salt solution is made, then iodo product 6 fragrant with sodium iodide Reactive Synthesis;
(3), by compound 4 be dissolved in oxolane, become benzenethiol 7 with tetrahydrochysene lithium aluminium reducing;
(4), by fragrant iodo compound 6 and benzenethiol 7 be dissolved in ethylene glycol and isopropyl alcohol or toluene equal solvent, under potash and cuprous iodide effect, composite structure is the material of general 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.
Actual conditions in each step is as follows:
Decarboxylative nitration step reaction temperature in step (1) is 0-100 DEG C, reduction reaction reducing agent used can be zinc powder, iron powder, magnesium powder, acid can be acetic acid, hydrochloric acid, reducing agent also can be palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, iron powder/hydrazine hydrate, palladium carbon/hydrogen etc., reaction temperature is 0-100 DEG C, diazo reagent can be natrium nitrosum, potassium nitrite, nitrobutane, acid used can be hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, reaction temperature is-20-10 DEG C, dithiocarbonic acids salinization reagent can be various alkyl xanthate, reaction temperature is 0-120 DEG C,
Diazotising diazo reagent used in step (2) can be natrium nitrosum, potassium nitrite, nitrobutane, and acid used can be hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, and reaction temperature is-20-10 DEG C; Iodide reaction is so iodo reagent can be sodium iodide, KI, elemental iodine, lodine chloride, and reaction temperature is 0-100 DEG C;
Reduction step in step (3) can use tetrahydrochysene lithium aluminium/oxolane reduction, and also can be hydrolyzed with sodium hydrate aqueous solution, reaction temperature is 0-100 DEG C;
In step (4), the reaction dissolvent of iodide reaction can be the alcohol such as ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, benzene, toluene, acetone, oxolane, dioxane, N, dinethylformamide, pyridine, methyl-sulfoxide, carrene, chloroform, dichloroethanes or mixed solvent etc., base catalyst used is potash, sodium carbonate, NaOH, potassium hydroxide, sodium hydride, various potassium alcoholate or sodium alkoxide etc., and catalyst is cuprous iodide, cupric iodide, and 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 of the photovoltaic cell of high open circuit voltage 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 3,4,5-trimethoxy-1-[(3-nitro-4-methoxyphenyl) sulfo-] benzene (ZLM-6)
Be dissolved in THF (32mL) by O-ethyl-S-(3,4,5-trimethoxyphenyl) dithiocarbonate ZLM-1 (2.42g), slow gradation adds LiAlH 4(1.3g), backflow 1h, is chilled to room temperature, is adjusted to pH=5 with 10%HCl, then extract 20mL × 4 with EA, merges organic phase, adds anhydrous sodium sulfate drying 1h, then suction filtration, obtain filtrate, revolve desolventizing, obtain yellow oil.Under nitrogen protection; first by potash (1.16g, 8.40mmol, 2.0eq), CuI (400mg; 2.10mmol; 0.5eq) and ethylene glycol (0.49mL, 8.40mmol, 2.0eq) add in 25mL bis-neck bottle; again upper step gained yellow oil is dissolved in isopropyl alcohol (4.0mL); then added in reaction bulb, in 80 DEG C of backflow 20h, be chilled to room temperature; suction filtration; filter residue EA washing several, obtains filtrate, revolves desolventizing; silicagel column is separated; obtain 597mg yellow solid, productive rate 40%, mp168.1-170.2 DEG C. 1hNMR (400MHz, CDCl 3): δ 3.81 (s, 6H), 3.85 (s, 3H), 3.95 (s, 3H), 6.61 (s, 2H), 7.03 (d, J=8.8Hz, 1H), 7.48 (dd, J=6.4,2.2Hz, 1H), 7.81 (d, J=6.4Hz, 1H). 13cNMR (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:351 (M +).
Embodiment 2
Preparation 3,4,5-trimethoxy-1-[(3-amino-4-methoxyl phenyl) sulfo-] benzene (ZLM-7)
By embodiment 1, with 3,4,5-trimethoxy-1-[(3-nitro-4-methoxyphenyl) sulfo-] benzene ZLM-6 (300mg) replaces 1-(3 '-nitro-4 '-methoxyphenyl)-2-methyl-5-(3 ', 4 ', 5 '-trimethoxyphenyl) pyrroles ZLM-12, obtain 181mg white solid, productive rate 66%, mp168.1-170.2 DEG C. 1hNMR (400MHz, CDCl 3): δ 3.77 (s, 6H), 3.81 (s, 3H), 3.86 (s, 3H), 6.50 (s, 2H), 6.75 (d, J=8.4Hz, 1H), 6.78 (d, J=2.4Hz, 1H), 6.83 (dd, J=6.4,2.0Hz, 1H). 13cNMR (400MHz, CDCl3): δ 55.5,56.0,60.9,106.4,110.7,118.6,122.9,125.3,132.6,136.4,136.8,147.2,153.3.MS (EI) m/z:321 (M +).
Embodiment 3
Preparation 3,4,5-trimethoxy-1-[(4-nitrobenzophenone) sulfo-] benzene (ZLM-8)
By embodiment 1, with replacing 3-nitro-4-methoxyl group iodobenzene to nitro iodobenzene (200mg), obtain 194mg faint yellow solid, productive rate 76%, mp168.1-170.2 DEG C. 1hNMR (400MHz, CDCl 3): δ 3.85 (s, 6H), 3.91 (s, 3H), 6.79 (s, 2H), 7.17 (d, J=8.8Hz, 2H), 8.09 (d, J=8.8Hz, 2H). 13cNMR (400MHz, CDCl3): δ 56.3,61.0,112.0,124.1,124.2,125.9,138.4,145.1,149.1,154.1.MS (EI) m/z:321 (M +).
Embodiment 4
Preparation 3,4,5-trimethoxy-1-[(the fluoro-4-methoxyphenyl of 3-) sulfo-] benzene (ZLM-9)
By embodiment 1, replace 3-nitro-4-methoxyl group iodobenzene with 3-fluoro-4-methoxyl group iodobenzene (282mg), obtain 222mg white solid, productive rate 69%, mp168.1-170.2 DEG C. 1hNMR (400MHz, CDCl 3): δ 3.80 (s, 6H), 3.84 (s, 3H), 3.90 (s, 3H), 6.55 (s, 2H), 6.91-6.95 (m, 1H), 7.10-7.14 (m, 2H). 13cNMR (400MHz, CDCl3): δ 56.1,56.2,60.9,107.8,113.6,119.1,119.2,126.9,127.0,127.6,130.6,137.2,147.2,147.3,151.0,153.5.MS (EI) m/z:324 (M +).
Embodiment 5
Preparation 3,4,5-trimethoxy-1-[(4-ethoxyl phenenyl) sulfo-] benzene (ZLM-11)
By embodiment 1, replace methoxyl group iodobenzene with 4-ethyoxyl iodobenzene (248mg), obtain 89mg yellowish-white solid, productive rate 27.8%, mp91.4-93.3 DEG C. 1hNMR (400MHz, CDCl 3): δ 1.43 (t, J=7.0Hz, 3H), 3.76 (s, 6H), 3.81 (s, 3H), 4.04 (q, J=7.2Hz, 3H), 6.45 (s, 2H), 6.88 (d, J=8.8Hz, 2H), 7.38 (d, J=8.8Hz, 2H). 13cNMR (400MHz, CDCl 3): δ 14.7,56.0,60.9,63.5,106.1,115.3,124.7,132.8,134.5,136.5,153.4,159.0.MS (EI) m/z:320 (M +).
Embodiment 6
Preparation 3,4,5-trimethoxy-1-[(3-benzyloxy-4-methoxyphenyl) sulfo-] benzene (ZLM-12)
By embodiment 1, replace methoxyl group iodobenzene with 3-benzyloxy-4-methoxyl group iodobenzene (1.02g), obtain 728mg white solid, productive rate 58.9%, mp100.6-101.1 DEG C. 1hNMR (400MHz, CDCl 3): δ 3.73 (s, 6H), 3.83 (s, 3H), 3.90 (s, 3H), 5.10 (s, 2H), 6.43 (s, 2H), 6.86 (d, J=8.8Hz, 1H), 6.95 (d, J=2.0Hz, 1H), 7.02 (dd, J=6.8,2.0Hz, 1H), 7.28-7.38 (m, 5H). 13cNMR (400MHz, CDCl 3): δ 56.0,56.1,60.9,70.9,106.7,112.1,117.8,125.5,125.6,127.2,127.9,128.5,132.0,136.5,136.7,148.4,149.6,153.4.MS (EI) m/z:412 (M +).
Embodiment 7
Preparation 2-amino-3-hydroxy-n-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide (ZLM-16)
By 2-fluorenes methoxy amide groups-3-acetoxyl group-N-[2-methoxyl group-5-(3,4,5-trimethoxyphenyl) sulfo-] propionamide ZLM-15 (232mg) is dissolved in appropriate carrene: methyl alcohol=1: in the mixed solvent of 1, add 0.36mL2N sodium hydrate aqueous solution again, stirring at room temperature 2h, revolve desolventizing, obtain 256mg yellowish-brown grease.(carrene: methyl alcohol=10: 1), obtains 56mg white solid, productive rate 41.6% in silicagel column separation. 1HNMR(400MHz，CDCl 3)：δ2.16(br，3H)，3.62(t，J＝2.6Hz，1H)，3.78(s，6H)，3.81(s，3H)，3.90(s，3H)，3.99(dd，J＝4.8，6.0Hz，1H)，6.55(s，2H)，6.84(d，J＝8.4Hz，1H)，7.11(dd，J＝6.4，2.2Hz，1H)，8.55(d，J＝2.0Hz，1H)，9.91(s，1H). 13CNMR(400MHz，CDCl 3)：δ55.9，56.2，56.5，60.9，65.1，107.4，110.7，123.6，126.5，127.6，128.2，132.0，137.0，148.3，153.4，171.5.MS(EI)m/z：408(M +)。
Embodiment 8
Preparation 3,4,5-trimethoxy-1-[(3-hydroxyl-4-methoxyphenyl) sulfo-] benzene (ZLM-17)
By 3,4,5-trimethoxy-1-[(3-benzyloxy-4-methoxyphenyl) sulfo-] benzene ZLM-12 (200mg) is dissolved in carrene: trifluoroacetic acid=1: in the mixed solvent 4.8mL of 1, stirring at room temperature 15h, except desolventizing, obtain brown-red oil, silicagel column is separated (benzinum: ethyl acetate=4: 1), obtain 32mg pale yellow oil, productive rate 20.7%. 1HNMR(400MHz，CDCl 3)：δ3.78(s，6H)，3.82(s，3H)，3.88(s，3H)，5.70(br，1H)，6.55(s，2H)，6.82(d，J＝8.4Hz，2H)，6.93(dd，J＝1.8，6.8Hz，1H)，6.98(d，J＝2.0Hz，1H).MS(EI)m/z：322(M +)。
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.
Hole transmission layer 3 is preferably PEDOT:PSS, also can be the polymer of other EDOT (3,4-ethylene dioxythiophene).The formation method of hole transmission layer 3 is rotary coating, spraying, silk screen printing, ink jet printing 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, electron acceptor material is carbon 60 and derivative thereof or carbon 70 and derivative thereof or inorganic semiconductor nano particle, and its formation method is rotary coating, spraying, silk screen printing, ink jet printing etc.
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.
The 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 JobinYvonSpexFluorolog-3double-grating fluorescence spectrophotometer can test photoluminescence spectra.In addition, also available discrete light sources excites, and spectra collection INSTASPECIV 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 (10)

1. there is a photovoltaic cell manufacture method for high open circuit voltage, comprise and prepare substrate, anode, active layer and negative electrode successively, it is characterized in that,
This manufacture method is also included between active layer and negative electrode prepares electron transfer layer, the polymer of electron transfer layer to be structure be general formula (I), and its polymerization degree n is the arbitrary integer of 1 ~ 300,
The manufacture method of this polymer comprises the steps:
(1), compound 1 decarboxylative nitration under red fuming nitric acid (RFNA) and acetic acid effect obtains compound 2, compound 3 is become again with zinc powder/acetic acid or palladium carbon/hydrazine hydrate reduction, then make diazonium salt solution with natrium nitrosum and hydrochloric acid, then with ehtyl potassium xanthate reacting generating compound 4;
(2), by aromatic amine 5 natrium nitrosum and hydrochloric acid diazonium salt solution is made, then iodo product 6 fragrant with sodium iodide Reactive Synthesis;
(3), by compound 4 be dissolved in oxolane, become benzenethiol 7 with tetrahydrochysene lithium aluminium reducing;
(4), by fragrant iodo compound 6 and benzenethiol 7 be dissolved in ethylene glycol and isopropyl alcohol or toluene solvant, under potash and cuprous iodide effect, composite structure is the polymer of general 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, is characterized in that, to be the polymer of general formula (I) be described structure:
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, it is characterized in that, decarboxylative nitration step reaction temperature in step (1) 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, acid is acetic acid or hydrochloric acid, reaction temperature is 0-100 DEG C, diazo reagent is natrium nitrosum, potassium nitrite or nitrobutane, acid used is hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, reaction temperature is-20-10 DEG C, dithiocarbonic acids salinization reagent is various alkyl xanthates, reaction temperature is 0-120 DEG C.
7. the manufacture method according to any one of Claims 1 to 5, it is characterized in that, diazotising diazo reagent used in step (2) is natrium nitrosum, potassium nitrite or nitrobutane, and acid used is hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, and reaction temperature is-20-10 DEG C; Iodide reaction is so iodo reagent is sodium iodide, KI, elemental iodine or lodine chloride, and reaction temperature is 0-100 DEG C.
8. the manufacture method according to any one of Claims 1 to 5, is characterized in that, the tetrahydrochysene lithium aluminium of the reduction step in step (3)/oxolane reduces or is hydrolyzed with sodium hydrate aqueous solution, and reaction temperature is 0-100 DEG C.
9. the manufacture method according to any one of Claims 1 to 5, it is characterized in that, in step (4), the reaction dissolvent of iodide reaction can be ethanol, methyl alcohol, isopropyl alcohol, the alcohol such as ethylene glycol, benzene, toluene, acetone, oxolane, dioxane, N, dinethylformamide, pyridine, methyl-sulfoxide, carrene, chloroform, dichloroethanes or mixed solvent, base catalyst used is potash, sodium carbonate, NaOH, potassium hydroxide, sodium hydride, various potassium alcoholate or sodium alkoxide, catalyst is cuprous iodide, cupric iodide, reaction temperature is 0-200 DEG C.
10. the manufacture method according to any one of Claims 1 to 5, is characterized in that, the method preparing active layer is rotary coating, spraying, silk screen printing or ink jet printing.
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CN1906777A (en) * 2004-05-11 2007-01-31 Lg化学株式会社 Organic electronic device
CN1583947A (en) * 2004-06-07 2005-02-23 中国科学院广州化学研究所 Luminescent polymer materials containing 8-hydroxy quinoline metal complex and their preparation and use
CN101540371A (en) * 2009-04-15 2009-09-23 河北大学 Flexible polymer solar battery of anode layer of metal grid and preparation method

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