CN103811658A - Efficient organic photovoltaic cell provided with electronic transmission layer and hole transmission layer - Google Patents
Efficient organic photovoltaic cell provided with electronic transmission layer and hole transmission layer Download PDFInfo
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- CN103811658A CN103811658A CN201310545486.2A CN201310545486A CN103811658A CN 103811658 A CN103811658 A CN 103811658A CN 201310545486 A CN201310545486 A CN 201310545486A CN 103811658 A CN103811658 A CN 103811658A
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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Abstract
The invention discloses an efficient organic photovoltaic cell provided with an electronic transmission layer and a hole transmission layer. The efficient organic photovoltaic cell comprises a substrate, a positive electrode, the hole transmission layer, an active layer, the electronic transmission layer and a negative electrode which are stacked in sequence, wherein the hole transmission layer is PEDOT: PSS. The active layer comprises an electron donor material and an electron acceptor material which are stacked, wherein the electron donor material is an organic compound represented by a general formula (VI), and the electron acceptor material is C60 or other derivates or C70 and other derivates. The electronic transmission layer is a monomer polymer represented by a structural formula (I). The efficient organic photovoltaic cell has high energy conversion efficiency and open-circuit voltage.
Description
Technical field
The present invention relates to field of photoelectric devices, relate in particular to a kind of photovoltaic cell.
Background technology
Along with the increase year by year of global energy demand, the day by day exhaustion of the disposable energy such as oil, coal, people have dropped into more concern and research to the renewable resource such as wind energy, solar energy, and wherein the photovoltaic cell based on photovoltaic effect is one of focus wherein.
At present, solar 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 battery are occupied an leading position on civilian photovoltaic cell market.Through the development of more than 50 years, the photoelectric conversion efficiency of inorganic single crystal silicon solar cell is by 6% at the beginning of invention, bringing up to current peak efficiency can reach more than 30%, but because inorganic semiconductor solar cell is very high to the requirement of material purity, and expensive, therefore its application is very limited.
1986, Kodak introduced to body and acceptor material first in same device, formed hetero-junction solar cell conversion efficiency and reached 1%, indicated that photovoltaic device prepared by organic semiconductor makes a breakthrough.Sariciftci in 1992 etc. are to MEH-PPV/C
60in the research of compound system, find that the two does not interact in ground state, but C
60the fluorescence of MEH-PPV is but had to very strong quenching effect, and propose to exist Photoinduced Electron to shift in system.People further investigate different compound systems, have proved the existence that Photoinduced Electron shifts.This process completes in several psecs, and electronics and the hole that can effectively stop optical excitation to produce occur compound again.The discovery of Photoinduced Charge fast energy transfer phenomena is the important breakthrough of polymer solar cells theoretical side, for the raising of polymer solar cells efficiency provides theoretical support.
The people such as nineteen ninety-five Yu Gang, by by electron donor material and acceptor material blend, make the solar cell of conjugated polymer MEH-PPV and carbon 60 inierpeneirating network structures, and its energy conversion efficiency reaches 2.9%.In this system, electron donor material and acceptor material form the interpenetrating networks shape structure of co-continuous, this structure has increased the two interfacial area greatly, heterojunction is disperseed more, this structure that heterojunction structure is distributed to whole active layer, in fact whole active layer is become to a large body heterojunction, thereby any position in active layer all can produce electric charge.As long as each phase material forms the continuous passage from the two interface to each self-electrode, so, can be greatly improved to the conversion efficiency of electronics by photon.The photovoltaic cell that Here it is it has often been said.
Bulk heterojunction concept produces the fault of construction that has overcome individual layer, bilayer/multilayer device.Due to electron donor and the network-like continuous phase of the each self-forming of electron acceptor, the electronics that photoinduction produces and hole respectively separately mutually in transport and be collected on corresponding electrode, photo-generated carrier is greatly reduced by again compound probability before the corresponding electrode of arrival, thereby has improved 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 solar cell based on polymer, and energy conversion efficiency can reach more than 5%, and it has tempting developing direction.In addition, the open circuit voltage of organic photovoltaic cell generally can only reach 0.60～0.80eV left and right at present, still can not reach the requirement of large-scale production.Therefore, people have carried out a large amount of experiments and have found active layer material and the higher electric transmission layer material of open circuit voltage that energy conversion efficiency is higher, expect to obtain the organic photovoltaic battery that device performance is higher.
Summary of the invention
The invention discloses the high efficiency organic photovoltaic cells with electron transfer layer and hole transmission layer, it has higher energy conversion efficiency and open circuit voltage simultaneously, thereby has good device performance.
The organic photovoltaic battery with electron transfer layer and hole transmission layer of the present invention comprises the substrate, anode, hole transmission layer, active layer, electron transfer layer and the negative electrode that stack gradually, wherein,
Hole transmission layer is PEDOT:PSS;
Active layer comprises the electron donor material and the electron acceptor material that are laminated, and wherein electron donor material is the organic compound that general formula (VI) represents, electron acceptor material is carbon 60 and derivative or carbon 70 and derivative thereof,
Wherein ,-A-B-represents phenylene;
P and Q represent independently: chemical bond or there is no substituting group or have one or more substituent (C
6-C
30) arlydene, described substituting group is selected from straight or branched and the saturated or undersaturated (C that there is no halogenic substituent or have halogenic substituent
1-C
30) alkyl, (C
6-C
30) aryl and halogen;
R
1represent hydrogen, (C
6-C
30) aryl;
R
2, R
3and R
4represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
11to R
18represent independently hydrogen, straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
21, R
22and R
23represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl; With
M is 1 or 2 integer;
The material of electron transfer layer is the polymer that monomer has structural formula (I), and its polymer n is the arbitrary integer between 1～300,
A is selected from the substituted heterocycle shown in substituted-phenyl, the structural formula IV that the 4-alkoxyl shown in substituted-phenyl, the formula II I that 4-nitro shown in formula II replaces replaces 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 respectively 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
8when different, be hydrogen;
R
9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y is independently selected from respectively 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
4refer to independently respectively 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 further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
When described A is substituted-phenyl III, wherein R
5, R
6, R
7, R
8refer to independently respectively hydrogen, halogen, hydroxyl, amido, methyl, ethyl, benzyl, alkoxyl, nitro, acyloxy or amide groups, and R
5, R
6, R
7, R
8when different, be hydrogen.Described R
5, R
6, R
7and R
8in preferably have one at least for hydroxyl or amido, described hydroxyl or amido are further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
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 respectively hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl.
Preferably, the material of substrate is glass, flexible macromolecule or metal base.
Preferably, the material of anode is metal oxide or the metal oxide that contains alloy.
Preferably, the material of negative electrode is light tight metal.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic photovoltaic battery with electron transfer layer and hole transmission layer of the present invention.
Embodiment
As shown in Figure 1, photovoltaic cell of the present invention comprises the substrate 1, anode 2, hole transmission layer 3, active layer 4, electron transfer layer 6 and the negative electrode 5 that stack gradually.
Wherein, active layer comprises the electron donor material and the electron acceptor material that are laminated, and wherein electron donor material is the organic compound that general formula (VI) represents, electron acceptor material is carbon 60 and derivative or carbon 70 and derivative thereof,
Wherein ,-A-B-represents phenylene;
P and Q represent independently: chemical bond or there is no substituting group or have one or more substituent (C
6-C
30) arlydene, described substituting group is selected from straight or branched and the saturated or undersaturated (C that there is no halogenic substituent or have halogenic substituent
1-C
30) alkyl, (C
6-C
30) aryl and halogen;
R
1represent hydrogen, (C
6-C
30) aryl;
R
2, R
3and R
4represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
11to R
18represent independently hydrogen, straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
21, R
22and R
23represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl; With
M is 1 or 2 integer;
Prerequisite is that A, B, P and Q can not be chemical bond simultaneously; If-A-B-and-P-Q-is phenylene, R
1must represent hydrogen; Do not comprise-A-B-and-P-Q-is spiral shell two fluorenylidenes, described arlydene and aryl can be further by straight or branched and saturated or undersaturated (C
1-C
30) alkyl, (C
1-C
30) alkoxyl, halogen, (C
3-C
12) cycloalkyl, phenyl, naphthyl or anthryl further replace.
In general formula (VI), R
1represent hydrogen, phenyl, naphthyl, anthryl, xenyl, phenanthryl, aphthacene base, fluorenyl, 9,9-dimethyl-fluorenes-2-base, pyrenyl, benzene anthryl (phenylenyl), fluoranthene base, trimethyl silyl, triethylsilyl, tripropyl silicyl, tri-tert silicyl, t-butyldimethylsilyl, triphenyl silicyl or phenyl dimetylsilyl; R
2, R
3and R
4represent independently methyl, ethyl, n-pro-pyl, isopropyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, cetyl, phenyl, naphthyl, anthryl or fluorenyl; R
11to R
18independently selected from: hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, cetyl, phenyl, naphthyl, anthryl and fluorenyl.
In chemical formula of the present invention, if A or B do not comprise any element be and R
1or anthracene connects, or P or Q do not comprise any element and be just connected with Si or anthracene, is referred to as chemical bond; But A, B, P and Q can not be chemical bond simultaneously.If-A-B-and-P-Q-is phenylene, R
1must represent hydrogen; Do not comprise-A-B-and-P-Q-is spiral shell two fluorenylidenes.
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,
A is selected from the substituted heterocycle shown in substituted-phenyl, the structural formula IV that the 4-alkoxyl shown in substituted-phenyl, the formula II I that 4-nitro shown in formula II replaces replaces 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 respectively 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
8when different, be hydrogen;
R
9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y is independently selected from respectively 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
4refer to independently respectively 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 further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
When described A is substituted-phenyl III, wherein R
5, R
6, R
7, R
8refer to independently respectively hydrogen, halogen, hydroxyl, amido, methyl, ethyl, benzyl, alkoxyl, nitro, acyloxy or amide groups, and R
5, R
6, R
7, R
8when different, be hydrogen.Described R
5, R
6, R
7and R
8in preferably have one at least for hydroxyl or amido, described hydroxyl or amido are further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
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 respectively 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,
The fluoro-4-methoxyphenyl of 3,4,5-trimethoxy-1-[(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 material of other of photovoltaic cell layer is 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 that contains alloy (doped), preferential oxidation indium tin (ITO), tin oxide, fluorine doped tin oxide etc.Anode can form by any traditional method, such as vapour deposition, sputter 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 of manufacturing negative electrode 5 can be vapour deposition method deposition etc.
The manufacture method of photovoltaic cell of the present invention comprises each layer for preparing active layer material, preparation electric transmission layer material and stack gradually photovoltaic cell.
The embodiment that wherein prepares active layer material is exemplified below:
Example 1: the preparation of active layer material 102 comprises the steps:
1, the preparation of compound (201)
In flask, add 1,2-dibromobenzene (100.0 grams, 423.9 mMs), 2-naphthalene boronic acids (80.2 grams, 466.3 mMs), toluene (1000 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (24.5 grams, 21.2 mMs), under argon gas atmosphere, stir this mixture.Then in mixture, drip wet chemical (300 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.By adding distilled water (2000 milliliters) will react quencher, extract this reactant mixture with ethyl acetate (1000 milliliters).Organic extract anhydrous magnesium sulfate drying, filters and reduces pressure down concentrated.By silica gel chromatography (ethyl acetate: hexane=1:50), and the acquisition bromo-2-of 1-(2-naphthyl) benzene (63.59 grams, 224.7 mMs, productive rate: 53.0%).
In the round-bottomed flask of 1 liter, add (42.0 grams of the bromo-2-of 1-(2-naphthyl) benzene, 148.5 mMs) and oxolane (1000 milliliters), drip positive BuLi (1.6M hexane solution) (89.0 milliliters, 222.5 mMs) in-78 ℃ to this flask.At same temperature, stir this mixture after 1 hour, in reactant mixture, drip trimethylborate (24.8 milliliters, 222.5 mMs), temperature is increased to room temperature.Stir this reactant mixture 12 hours, in the time that reaction completes, add 1M hydrochloric acid solution (500 milliliters), the mixture that stirring forms 5 hours.The organic extract anhydrous magnesium sulfate drying obtaining with distilled water (500 milliliters) and ethyl acetate (600 milliliters) extraction, filters and reduces pressure down concentrated.From ethyl acetate (80 milliliters) and methyl alcohol (600 milliliters) recrystallization, and acquisition compound (201) (27.28 grams, 110.0 mMs, productive rate: 74.1%).
2, the preparation of compound (202)
In 500 milliliters of round-bottomed flasks, add (27.28 grams of compounds (201), 110.0 mMs), 9-bromine anthracene (28.16 grams, 88.0 mMs), toluene (500 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (2.45 grams, 2.05 mMs), under argon gas atmosphere, stir this mixture.Then in this mixture, drip wet chemical (100 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.In the time completing reaction, in reactant mixture, add distilled water (600 milliliters), then use ethyl acetate (400 milliliters) extraction.Organic extract anhydrous magnesium sulfate drying, filters and reduces pressure down concentrated.By silica gel chromatography (carrene: hexane=1:15), and acquisition compound (202) (25.20 grams, 66.32 mMs, productive rate: 75.4%).
3, the preparation of compound (203)
In 500 milliliters of round-bottomed flasks, add (35.20 grams of compounds (202), 92.62 mMs), (18.13 grams of N-bromine succinimides, 101.9 mMs) and carrene (500 milliliters), this mixture under room temperature, stirred 12 hours.In the time completing reaction, decompression is lower to desolventizing.From carrene (100 milliliters) and hexane (500 milliliters) recrystallization, and acquisition compound (203) (34.51 grams, 75.33 mMs, productive rate: 81.3%).
4, the preparation of compound (204)
In 500 milliliters of round-bottomed flasks, add (42.56 grams of compounds (203), 92.62 mMs) and oxolane (1000 milliliters), drip positive BuLi (1.6M hexane solution) (55.57 milliliters, 138.9 mMs) in-78 ℃ to this flask.At same temperature, stir this mixture 1 hour, in reactant mixture, drip trimethylborate (15.49 milliliters, 138.9 mMs), temperature is increased to room temperature.Stir this reactant mixture 12 hours, in the time that reaction completes, add 1M hydrochloric acid solution (500 milliliters), the mixture that stirring forms 5 hours.The organic extract anhydrous magnesium sulfate drying obtaining with distilled water (500 milliliters) and ethyl acetate (400 milliliters) extraction, filters and reduces pressure down concentrated.From ethyl acetate (50 milliliters) and methyl alcohol (600 milliliters) recrystallization, and acquisition compound (204) (30.43 grams, 71.78 mMs, productive rate: 77.5%).
5, the preparation of compound (102)
In 500 milliliters of round-bottomed flasks, add (30.43 grams of compounds (204), 71.78 mMs), compound (205) (30.43 grams, 57.42 mMs), toluene (500 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (4.15 grams, 3.59 mMs), under argon gas atmosphere, stir this mixture.Then drip therein wet chemical (200 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.In the time completing reaction, in reactant mixture, add distilled water (600 milliliters), then use ethyl acetate (500 milliliters) extraction.The organic extract anhydrous magnesium sulfate drying obtaining, filters and reduces pressure down concentrated.By silica gel chromatography (carrene: hexane=1:10) with from hexane recrystallization, and acquisition compound (102) (35.78 grams, 43.11 mMs, productive rate: 75.1%), be light yellow product.
1H?NMR(400MHz,CDCl
3):=7.94(d,1H),7.92(d,1H),7.89(s,1H),7.84(s,1H),7.79(s,1H),7.75(d,1H),7.68-7.65(m,7H),7.61(d,1H),7.56-7.53(m,9H),7.38-7.35(m,9H),7.33-7.27(m,8H),1.65(s,6H)
MS/FAB C
63h
46si 830.34 (measured value).(831.12 calculated value)
Example 2: the preparation of active layer material (103) comprises the steps
1, the preparation of compound (206)
In 1 liter of round-bottomed flask, add 1, (100 grams of 2-dibromobenzenes, 423.9 mMs), 2-(9,9 '-dimethyl) fluorenes boric acid (111.0 grams, 466.3 mMs), toluene (1000 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (24.5 grams, 21.2 mMs), under argon gas atmosphere, stir this mixture.Then in mixture, drip wet chemical (300 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.In the time completing reaction, in reactant mixture, add distilled water (1500 milliliters), then use ethyl acetate (800 milliliters) extraction.The organic extract anhydrous magnesium sulfate drying obtaining, filters and reduces pressure down concentrated.By silica gel chromatography (ethyl acetate: hexane=1:30), obtain product, the bromo-2-of 1-(9,9 '-dimethyl) fluorenyl benzene (75.52 grams, 217.0 mMs, productive rate: 51.2%).
In 1 liter of round-bottomed flask, add the bromo-2-(9 of 1-, 9 '-dimethyl) (51.68 grams of fluorenyl benzene, 148.5 mMs) and oxolane (1000 milliliters), drip positive BuLi (1.6M hexane solution) (89.0 milliliters, 222.5 mMs) in-78 ℃ to this flask.At same temperature, stir this mixture 1 hour, in reactant mixture, drip trimethylborate (24.8 milliliters, 222.5 mMs), temperature is increased to room temperature.Stir this reactant mixture 12 hours, in the time that reaction completes, add therein 1M hydrochloric acid solution (500 milliliters, stir the mixture 5 hours forming.The organic extract anhydrous magnesium sulfate drying obtaining with distilled water (500 milliliters) and ethyl acetate (400 milliliters) extraction, filters and reduces pressure down concentrated.From ethyl acetate (50 milliliters) and methyl alcohol (600 milliliters) recrystallization, and acquisition compound (206) (29.31 grams, 93.34 mMs, productive rate: 62.9%).
2, the preparation of compound (207)
In 500 milliliters of round-bottomed flasks, add (34.54 grams of compounds (206), 110.0 mMs), (28.16 grams of 9-bromine anthracenes, 88.0 mMs), toluene (500 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (2.45 grams, 2.05 mMs), under argon gas atmosphere, stir this mixture.Then drip therein wet chemical (100 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.In the time completing reaction, in reactant mixture, add distilled water (500 milliliters), then use ethyl acetate (500 milliliters) extraction.The organic extract anhydrous magnesium sulfate drying obtaining, filters and reduces pressure down concentrated.By silica gel chromatography (carrene: hexane=1:15), and acquisition compound (207) (32.34 grams, 72.51 mMs, productive rate: 82.4%).
3, the preparation of compound (208)
In 500 milliliters of round-bottomed flasks, add (41.44 grams of compounds (207), 92.62 mMs), (18.13 grams of N-bromine succinimides, 101.9 mMs) and carrene (250 milliliters), this mixture under room temperature, stirred 12 hours.In the time completing reaction, decompression is lower to desolventizing.From carrene (150 milliliters) and hexane (800 milliliters) recrystallization, and acquisition compound (208) (30.52 grams, 58.24 mMs, productive rate: 62.9%).
4, the preparation of compound (209)
In the round-bottomed flask of 500 milliliters, add (48.53 grams of compounds (208), 92.62 mMs) and oxolane (800 milliliters), drip positive BuLi (1.6M hexane solution) (55.57 milliliters, 138.9 mMs) in-78 ℃ to this flask.At same temperature, stir this mixture 1 hour, in reactant mixture, drip trimethylborate (15.49 milliliters, 138.9 mMs), temperature is increased to room temperature.Stir this reactant mixture 12 hours, in the time that reaction completes, add therein 1M hydrochloric acid solution (400 milliliters), the mixture that stirring forms 5 hours.The organic extract anhydrous magnesium sulfate drying obtaining with distilled water (500 milliliters) and ethyl acetate (500 milliliters) extraction, filters and reduces pressure down concentrated.From ethyl acetate (100 milliliters) and methyl alcohol (800 milliliters) recrystallization, and acquisition compound (209) (32.33 grams, 65.98 mMs, productive rate: 71.2%).
5, the preparation of compound (103)
In 500 milliliters of round-bottomed flasks, add (35.17 grams of compounds (209), 71.78 mMs), compound (205) (30.43 grams, 57.42 mMs), toluene (600 milliliters) and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) (4.15 grams, 3.59 mMs), under argon gas atmosphere, stir this mixture.Then drip therein wet chemical (100 milliliters), the mixture of formation heats 4 hours under stirring and counterflow condition.When completing when reaction, in reactant mixture, add distilled water (500 milliliters, then use ethyl acetate (500 milliliters) extraction.The organic extract anhydrous magnesium sulfate drying obtaining, filters and reduces pressure down concentrated.By silica gel chromatography (carrene: hexane=1:10) with from hexane recrystallization, and acquisition compound (103) (31.76 grams, 35.45 mMs, productive rate: 61.7%), be faint yellow product.
1H?NMR(400MHz，CDCl
3):δ=7.94(d，1H)，7.90(d，2H)，7.84-7.82(m，2H)，7.78(s，2H)，7.68-7.65(m，5H)，7.62(d，2H)，7.57-7.54(m，9H)，7.38-7.34(m，10H)，7.33-7.27(m，7H)，1.67(s，6H)，1.66(s，6H)
MS/FAB C
69h
52si 896.38 (measured value).(897.23 calculated value)
The method of preparing electron transfer layer comprises two kinds, as described below respectively.
One of 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, react synthesizing fragrant iodo product 6 by aromatic amine 5 diazotising, then with sodium iodide;
Three, first compound 4 is reduced into benzenethiol 7, is then dissolved under base catalyst effect and obtains compound of Formula I with fragrant chlorinated compound 8 or fragrant iodo compound 6;
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 1 is 0-100 ℃; Reduction reaction reducing agent used can be zinc powder, iron powder, magnesium powder, and acid can be acetic acid, hydrochloric acid, and reducing agent can be also palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, and iron powder/hydrazine hydrate, palladium carbon/hydrogen etc., reaction temperature is 0-100 ℃; 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 ℃; Dithiocarbonic acids salinization reagent can be various alkyl xanthates, and reaction temperature is 0-120 ℃;
Diazotation step in step 2 can be used the reduction of tetrahydrochysene lithium aluminium/oxolane, also can be hydrolyzed with sodium hydrate aqueous solution, and reaction temperature is 0-100 ℃; 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 ℃.
The another kind of manufacture method of electric transmission layer material of the present invention comprises following steps:
(1), compound 1 decarboxylative nitration under red fuming nitric acid (RFNA) and acetic acid effect obtains compound 2, become compound 3 with zinc powder/acetic acid or palladium carbon/hydrazine hydrate reduction again, then make diazonium salt solution with natrium nitrosum and hydrochloric acid, then with ehtyl potassium xanthate reacting generating compound 4;
(2), aromatic amine 5 use natrium nitrosums and hydrochloric acid are made to diazonium salt solution, then react synthesizing fragrant iodo product 6 with sodium iodide;
(3), compound 4 is dissolved in to oxolane, become benzenethiol 7 with tetrahydrochysene lithium aluminium reducing;
(4), fragrant iodo compound 6 is dissolved in ethylene glycol and isopropyl alcohol or toluene equal solvent to the material that composite structure is general formula I under potash and cuprous iodide effect with benzenethiol 7;
Particularly, in each step, actual conditions is as follows:
Decarboxylative nitration step reaction temperature in step (1) is 0-100 ℃, reduction reaction reducing agent used can be zinc powder, iron powder, magnesium powder, acid can be acetic acid, hydrochloric acid, reducing agent can be also palladium carbon/hydrazine hydrate, magnesium powder/hydrazine hydrate, iron powder/hydrazine hydrate, palladium carbon/hydrogen etc., reaction temperature is 0-100 ℃, 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 ℃, dithiocarbonic acids salinization reagent can be various alkyl xanthates, reaction temperature is 0-120 ℃,
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 ℃; So iodide reaction iodo reagent can be sodium iodide, KI, elemental iodine, lodine chloride, reaction temperature is 0-100 ℃;
Reduction step in step (3) can be used the reduction of tetrahydrochysene lithium aluminium/oxolane, also can be hydrolyzed with sodium hydrate aqueous solution, and reaction temperature is 0-100 ℃;
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 ℃.
The embodiment that stacks gradually each layer of photovoltaic cell 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 successively acetone, micron order semiconductor special purpose detergent, deionized water, 10 minutes clean ITO substrate surfaces of the ultrasonic processing of isopropyl alcohol, put into subsequently and at 80 ℃ of constant temperature ovens, leave standstill 4 hours and dry.
ITO substrate after oven dry is used oxygen plasma treatment 4 minutes, remove organic attachment film and the organic pollution of ITO surface attachment, be placed on sol evenning machine (KW-4A type), with the rotating speed rotations of 2000 revs/min 60 seconds, (BAYTRON P 4083, purchased from Bayer AG company for the hole transmission layer PEDOT:PSS suspension of spin coating one deck approximately 40 nanometer thickness.Before spin coating, the spin coating of PEDOT:PSS suspension is first through 0.45 micron of Kynoar (PVDF) membrane filtration, the insoluble particles that elimination is larger.
In preparation process, the thickness of gained film is by surface profiler (Alpha-Tencor500 of Teriek company type) actual observation record.After film forming, proceed in constant-temperature vacuum baking oven and dry at 80 ℃ as the ITO Conducting Glass of hole transmission layer being coated with PEDOT:PSS, or be on 100-200 ℃ of heating station in temperature, under atmospheric environment, dry, to remove residual solvent, firm obtained film.
Subsequently the substrate being made by said method proceeded to anhydrous and oxygen-free, be full of the special gloves case (manufacture of VAC company of the U.S.) of high pure nitrogen.Under this glove box inert atmosphere, electron donor material and electron acceptor material are placed in respectively to clean sample bottle, with conventional organic solvent (as chlorobenzene, toluene etc.) dissolve and be mixed with solution, be placed on heating and stir on mixing platform, obtain clear filtrate with 0.45 micron of polytetrafluoroethylene (PTFE) membrane filtration.Then according to a certain percentage electron donor material and electron acceptor material are mixed, be placed on heating mixing platform and stir.
Electric transmission layer material 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; in the methyl alcohol that is added with a small amount of acetic acid, dissolve the solution that is made into 0.01-1.5%; be placed on mixing platform and stir, obtain settled solution with 0.45 micron of membrane filtration.The preparation of active layer makes by the solution that applies electron donor material and electron acceptor material mixing on substrate.For this reason, first the negative-pressure adsorption that just ITO substrate produces by mechanical pump is on sol evenning machine, after instillation electron donor material and electron acceptor material mixing are molten, make through high speed spin coating (600-6000 rev/min), generally speaking, the active layer thickness that requirement makes is in 20-500 nanometer, and preferred film thickness is 70-200 nanometer.Thickness is by regulating the rotating speed of sol evenning machine and the concentration of control electron donor material and electron acceptor material mixed solution to control.
Above-mentioned electron donor material and electron acceptor material mixed solution are after ITO/PEDOT:PSS substrate film forming, after drying, the above-mentioned electric transmission layer material that instils in the above again, 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 to the pattern designing.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual region covering of ITO.
Except the preparation of PEDOT:PSS film, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided or in vacuum.In order to make above-mentioned vacuum thermal evaporation metallic film process, the growth rate of settling of film and total deposit thickness be by the thermal power control applying, and by quartz crystal oscillator film thickness monitor (STM-100 type, Sycon company manufactures) monitoring in real time.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 nanometers of test.
The measuring process of the photoluminescence spectra of above-mentioned electron donor material is as follows: according to the test result of its absorption spectrum, choose suitable excitaton source.The light path that above-mentioned film substrate is placed in to Jobin Yvon Spex Fluorolog-3 double-grating fluorescence spectrophotometer can be tested photoluminescence spectra.In addition, also available discrete light sources excites, and spectra collection completes with INSTASPEC IV type grating beam splitting CCD (charge coupled device) spectrometer.The excitation source that can Gong 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.
Solar cell is energy conversion device, solar energy is converted to electric energy, thus the mensuration of any solar cell device performance parameter, finally all will be take sunlight as testing standard.In laboratory, the radiant illumination of conventional AM1.5G measurement standard is 100 milliwatt/square centimeters.In the time carrying out polymer solar cells performance test with solar simulation light, first determine the whether irradiance of compound AM1.5G of light source with standard cell.Standard silicon solar cell is through calibration: under AM1.5G standard spectrum, when the irradiation of 100 milliwatt/square centimeter radiant illuminations, the short circuit current obtaining is 125 milliamperes.Determine after irradiance, can test device.
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention adopts active layer material and electric transmission layer material can improve performance, especially energy conversion efficiency and the open circuit voltage of photovoltaic cell device.(2) device architecture the present invention relates to adopts solution processing technology, and preparation technology is simple, and cost of manufacture is low.(3) material of electron transfer layer of the present invention is dissolvable in water in water or methyl alcohol isopolarity solvent.And electron donor material and electron acceptor material are generally insoluble to this kind solvent in active layer, therefore, in the time forming this laminated device, between electron transfer layer and active layer, can there is not mixing phenomena.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (7)
1. there is the high efficiency organic photovoltaic cells of electron transfer layer and hole transmission layer, comprise the substrate, anode, hole transmission layer, active layer, electron transfer layer and the negative electrode that stack gradually, it is characterized in that,
Hole transmission layer is PEDOT:PSS;
Active layer comprises the electron donor material and the electron acceptor material that are laminated, and wherein electron donor material is the organic compound that general formula (VI) represents, electron acceptor material is carbon 60 and derivative or carbon 70 and derivative thereof,
Wherein ,-A-B-represents phenylene;
P and Q represent independently: chemical bond or there is no substituting group or have one or more substituent (C
6-C
30) arlydene, described substituting group is selected from straight or branched and the saturated or undersaturated (C that there is no halogenic substituent or have halogenic substituent
1-C
30) alkyl, (C
6-C
30) aryl and halogen;
R
1represent hydrogen, (C
6-C
30) aryl;
R
2, R
3and R
4represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
11to R
18represent independently hydrogen, straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl;
R
21, R
22and R
23represent independently straight or branched and saturated or undersaturated (C
1-C
30) alkyl or (C
6-C
30) aryl; With
M is 1 or 2 integer;
The material of electron transfer layer is the polymer that monomer has structural formula (I), and its polymer n is the arbitrary integer between 1～300,
A is selected from the substituted heterocycle shown in substituted-phenyl, the structural formula IV that the 4-alkoxyl shown in substituted-phenyl, the formula II I that 4-nitro shown in formula II replaces replaces 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 respectively 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
8when different, be hydrogen;
R
9be selected from alkyl or the 1-3 carbon atom substituted alkyl of 1-3 carbon atom;
X, Y is independently selected from respectively 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. photovoltaic cell 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
4refer to independently respectively 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 further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
3. photovoltaic cell 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
8refer to independently respectively hydrogen, halogen, hydroxyl, amido, methyl, ethyl, benzyl, alkoxyl, nitro, acyloxy or amide groups, and R
5, R
6, R
7, R
8when different, be hydrogen.Described R
5, R
6, R
7and R
8in preferably have one at least for hydroxyl or amido, described hydroxyl or amido are further replaced to its corresponding phosphate, carboxylate, sulphonic acid ester, acid amides, peptide class and corresponding organic salt or inorganic salts derivative.
4. photovoltaic cell 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 respectively hydrogen, halogen, hydroxyl, amido, substituted amido, cyano group, alkyl, alkoxyl.
5. the photovoltaic cell as described in any one in claim 1～4, is characterized in that, the material of substrate is glass, flexible macromolecule or metal base.
6. the photovoltaic cell as described in any one in claim 1～4, is characterized in that, the material of anode is metal oxide or the metal oxide that contains alloy.
7. the photovoltaic cell as described in any one in claim 1～4, is characterized in that, the material of negative electrode is light tight metal.
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2013
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