CN114409549A - Fullerene derivative material, preparation method thereof and perovskite solar cell - Google Patents

Fullerene derivative material, preparation method thereof and perovskite solar cell Download PDF

Info

Publication number
CN114409549A
CN114409549A CN202210085896.2A CN202210085896A CN114409549A CN 114409549 A CN114409549 A CN 114409549A CN 202210085896 A CN202210085896 A CN 202210085896A CN 114409549 A CN114409549 A CN 114409549A
Authority
CN
China
Prior art keywords
formula
fullerene derivative
derivative material
fullerene
solar cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210085896.2A
Other languages
Chinese (zh)
Inventor
李卫东
张赟
肖平
赵志国
王力军
秦校军
李新连
夏渊
熊继光
刘入维
申建汛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
Original Assignee
Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huaneng Clean Energy Research Institute, Huaneng Renewables Corp Ltd filed Critical Huaneng Clean Energy Research Institute
Priority to CN202210085896.2A priority Critical patent/CN114409549A/en
Publication of CN114409549A publication Critical patent/CN114409549A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/31—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the six-membered aromatic ring being part of a condensed ring system formed by at least three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/11—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a fullerene derivative material, a preparation method thereof, a perovskite solar cell and a fullerene derivativeThe material has a structure of formula I, formula II, formula III or formula IV, each X is independently selected from halogen; each R is independently selected from-H or C1-C6 alkyl. The invention improves the solubility of target molecules in alcohols or other green solutions by replacing ester groups on PCBM and Bis-PCBM molecules with alkyl ammonium salt substituents, thereby realizing the purpose of green processing and reducing the damage to human bodies and the environment.

Description

Fullerene derivative material, preparation method thereof and perovskite solar cell
Technical Field
The invention belongs to the technical field of electron transmission materials, and particularly relates to a fullerene derivative material, a preparation method thereof and a perovskite solar cell.
Background
Solution processability is one of the driving forces for the rapid development of perovskite solar cells, and besides the solution processability of perovskite layers, the solution processability of other functional layers such as carrier transport layers (hole and electron transport layers) and even transparent electrodes and metal electrodes is a hot spot of research.
At present, most of solvents used for various materials, particularly organic semiconductor functional materials, contain benzene rings or other heterocycles or polar solvents such as chloroform, and the solvents are generally high in toxicity and are not suitable for the requirements of industrial production. Therefore, it is imperative to develop functional materials that are soluble in alcohols or other low-toxic green solvents.
The fullerene is a hollow molecule completely composed of carbon, is spherical, ellipsoidal, columnar or tubular, contains five-membered rings, six-membered rings and even seven-membered rings, and is most widely applied to spherical or ellipsoidal, such as C60, C70, C80 and the like. Due to the unique chemical structure of fullerene materials, fullerene materials are generally used as electron transport materials, but pure fullerene materials have poor dissolving capacity in most solvents, are generally not suitable for solution processing, and limit the application range of the fullerene materials. Based on the current situation, a series of fullerene derivative materials, such as PC, are developed60BM、PC70BM、Bis-PC60BM and Bis-PC70BM, and the like. At present, fullerene derivatives can be dissolved and processed into thin films by adopting aromatic solvents (toluene, chlorobenzene, xylene, dichlorobenzene and the like), and the processing method has the defect that the aromatic solvents are mostly strong carcinogenic substances, so that development of fullerene materials soluble in green solvents is necessary.
Disclosure of Invention
In view of the above, the present invention provides a fullerene derivative material, which can be dissolved in a green solvent such as methanol, ethanol or polyol, a method for preparing the same, and a perovskite solar cell.
The invention provides a fullerene derivative material which has a structure shown in a formula I, a formula II, a formula III or a formula IV:
Figure BDA0003487934920000021
each R is independently selected from-H and/or C1-C6 alkyl;
each X is independently selected from halogen.
Preferably, the alkyl of C1-C6 is a linear alkyl of C1-C6;
each X is independently selected from-Cl, -Br or-I.
Preferably, the fullerene derivative material is selected from formula 101, formula 102, formula 103, formula 104 or
Formula 106:
Figure BDA0003487934920000022
Figure BDA0003487934920000031
preferably, the fullerene derivative material is soluble in a green solvent; the green solvent includes one or more of methanol, ethanol, and a polyol.
The invention provides a preparation method of a fullerene derivative material in the technical scheme, which comprises the following steps:
reacting fullerene with a material shown as a formula 201 to obtain an intermediate product;
Figure BDA0003487934920000032
each R is selected from-H and/or C1-C8 alkyl;
the fullerene is selected from C60 or C70;
the intermediate product has a structure of formula 202, formula 203, formula 204, or formula 205:
Figure BDA0003487934920000041
and reducing the intermediate product, and carrying out quaternization reaction to obtain the fullerene derivative material.
The invention provides an electron transport layer, which comprises the fullerene derivative material in the technical scheme or the fullerene derivative material prepared by the preparation method in the technical scheme.
Preferably, the thickness of the electron transport layer is 10-100 nm.
The invention provides a perovskite solar cell which comprises the electron transport layer in the technical scheme.
In the invention, the electron transport layer adopts a solution processing mode;
the solution processing method is selected from a spin coating film forming method, a scraper coating method, a slit extrusion coating method, a wire rod coating method or a roll-to-roll printing method.
The fullerene derivative material with the structure shown in the formula I, the formula II, the formula III or the formula IV comprises alkyl ammonium salt, so that the fullerene derivative material has the dissolving capacity in alcohols or other green solvents, and the purpose of green processing is realized.
Drawings
FIG. 1 is a reaction scheme of fullerene derivative materials of formula I and formula II;
FIG. 2 is a reaction scheme of fullerene derivative materials of formula III and formula IV;
FIG. 3 is a schematic structural diagram of a perovskite solar cell provided by the present invention;
FIG. 4 is a NMR chart of the benzoyl (N, N-) diethyl-1-butanamide product of the first step of example 1;
FIG. 5 is a NMR chart of the second step of example 1 showing the product benzoyl (N, N-) bis-ethyl-1-butanamide p-toluenesulfonylhydrazone.
Detailed Description
The invention provides a fullerene derivative material which has a structure shown in a formula I, a formula II, a formula III or a formula IV:
Figure BDA0003487934920000051
each R is independently selected from-H and/or C1-C6 alkyl;
each X is independently selected from halogen.
In the present invention, the substituent selected for each R in formula I, formula II, formula III or formula IV may be the same or different; each R is independently selected from-H, -CH3、-C2H5、-C3H7、-C4H9、-C5H11or-C6H13(ii) a R is preferably hydrogen or a C1-C6 linear alkyl group, i.e. methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl.
The substituents selected for each X in formula I, formula II, formula III or formula IV may or may not be the same. The X is preferably selected from-Cl, -Br or-I.
In the present invention, the fullerene derivative material is selected from formula 101, formula 102, formula 103, formula 104, or formula 106:
Figure BDA0003487934920000061
the end of a side chain of the fullerene derivative material provided by the invention is ammonium salt, a group R connected with a nitrogen atom in the ammonium salt is hydrogen or alkyl of C1-C6, and X connected with an ammonium salt group is halogen. In the present invention, the fullerene derivative material is soluble in a green solvent; the green solvent includes one or more of methanol, ethanol, and a polyol.
The invention provides a preparation method of a fullerene derivative material in the technical scheme, which comprises the following steps:
reacting fullerene with a material shown as a formula 201 to obtain an intermediate product;
Figure BDA0003487934920000071
each R is selected from-H and/or C1-C8 alkyl;
the fullerene is selected from C60 or C70;
the intermediate product has a structure of formula 202, formula 203, formula 204, or formula 205:
Figure BDA0003487934920000072
and reducing the intermediate product, and carrying out quaternization reaction to obtain the fullerene derivative material.
In the present invention, the fullerene is preferably selected from C60 or C70; the substitution reactions occurring on the fullerene group include both mono-and di-substitution types.
The invention improves the dissolving capacity of the novel molecules in alcohols or other green solvents by replacing ester groups on PCBM and Bis-PCBM molecules with alkyl ammonium salts, thereby realizing the purpose of green processing. Wherein the PCBM and Bis-PCBM comprise PC60BM、PC70BM、Bis-PC60BM and Bis-PC70BM。
In the present invention, the reaction routes of the fullerene derivative materials represented by the formulas I and II are preferably shown in FIG. 1:
the reaction scheme of the fullerene derivative materials shown in the formulas I and II is preferably shown in FIG. 2.
In the present invention, the first step: amide synthesis: under the condition of ice-water bath, adding trichloromethyl chloroformate and triethylamine into a dichloromethane solution of 4-benzoyl butyric acid; adding N, N-dialkyl amine while stirring, and then heating to room temperature to obtain amide;
the second step is that: synthesis of sulfonyl hydrazone: blending the reaction product of the first step and p-toluenesulfonyl hydrazide, dissolving in methanol, carrying out reflux reaction for 5-8 hours under the condition of stirring, standing for 24 hours, and then cooling to-15 ℃; filtering the mixture at low temperature to obtain a product (crystal);
the third step: introduction of fullerene: under the protection of inert gas, dissolving the product of the second step in dry pyridine, then adding sodium methoxide, stirring at room temperature for 14-16 min, and then adding C60Or C70Reacting the o-dichlorobenzene solution at 65-70 ℃ under stirring to obtain a product;
the fourth step: reduction reaction of carbonyl group: under the condition of low-temperature stirring, dissolving sodium borohydride and the product obtained in the third step in 1, 4-dioxane, then slowly adding 1, 4-dioxane of acetic acid, and refluxing while stirring to obtain a reaction product;
the fifth step: synthesis of quaternary ammonium salt: and (3) dissolving the product obtained in the fourth step in tetrahydrofuran, adding excessive alkyl halide and a proper amount of dimethyl sulfoxide, stirring, and reacting to obtain the fullerene derivative material.
From the above synthetic route, it can be seen that: the mono-substituted (formula I, formula II) and di-substituted (formula III, formula IV) products are prepared by five steps of reactions: firstly, introducing secondary amine to 4-butyryl benzoate to prepare amide; secondly, introducing sulfonyl hydrazine groups to carbonyl groups adjacent to benzene rings to prepare sulfonyl hydrazone groups; step three, introducing the product of the step two as a substituent group onto a fullerene group; step four, carbonyl reduction, wherein the carbonyl is reduced into methylene through sodium borohydride; and fifthly, converting the tertiary amine into quaternary ammonium salt, and attacking nitrogen atoms on the tertiary amine by alkyl halide in the presence of tetrahydrofuran and dimethyl sulfoxide to obtain the positively charged quaternary ammonium salt, namely the derivative.
In the synthetic route, fullerene contains C60And C70(ii) a The substitution reaction in the third step reaction comprises mono-substitution and di-substitution; the different halogen atoms and substituent groups R in formulae I, II, III, IV can be achieved by replacing the secondary amine type (R) in the first step and the alkyl halide (X and R) in the fifth step of the synthetic route.
The invention provides an electron transport layer, which comprises the fullerene derivative material in the technical scheme or the fullerene derivative material prepared by the preparation method in the technical scheme.
In the invention, the thickness of the electron transmission layer is 10-100 nm.
The invention provides a perovskite solar cell which comprises the electron transport layer in the technical scheme.
In the invention, the electron transport layer adopts a solution processing mode;
the solution processing method is selected from a spin coating film forming method, a scraper coating method, a slit extrusion coating method, a wire rod coating method or a roll-to-roll printing method.
In the invention, the preparation process parameters of the spin coating film formation are as follows: dissolving fullerene derivative materials of formula I, formula II, formula III and formula IV in methanol, wherein the concentration of the solution is 0.5-5 mg/ml, and the spin-coating speed is 1000 rpm-8000 rmp; the resulting film thickness is 10 to 100nm, preferably 40 to 80 nm.
The preparation process parameters of the wire rod coating film are as follows: the fullerene derivative material with the structure shown in the formula I, the formula II, the formula III and the formula IV is dissolved in methanol, the concentration of the solution is 0.5-5 mg/ml, the coating speed is 5-40 mm/s, the gap between a wire rod and a substrate is 20-300 mu m, and the thickness of the obtained film is 10-100 nm, preferably 40-80 nm.
Fig. 3 is a schematic structural diagram of the perovskite solar cell provided by the invention, wherein 1 is a transparent electrode layer, 2 is a hole transport layer, 3 is a perovskite light absorption layer, 4 is an electron transport layer, and 5 is a metal electrode layer.
The fullerene derivative material with the structure shown in the formula I, the formula II, the formula III or the formula IV comprises alkyl ammonium salt, so that the fullerene derivative material has the dissolving capacity in alcohols or other green solvents, and the purpose of green processing is realized.
In order to further illustrate the present invention, the following will describe the fullerene derivative material and the preparation method thereof and the application thereof in the perovskite solar cell in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Unless otherwise specified, 4-benzoylbutyric acid, trichloromethyl chloroformate, triethylamine, nitrogen bisalkylamine, p-toluenesulfonylhydrazide, C60, C70, alkyl halide, and related catalysts and solvents, which are used as raw materials, are commercially available products and are directly purchased.
Example 1
Synthesis of benzoyl (N, N-) diethyl-1-butanamide: dissolving 4-benzoylbutyric acid (2mmol) in dichloromethane (10mL) at 0 deg.C (ice-water bath), and adding 2mmol of trichloromethyl chloroformate and 6mmol of triethylamine while stirring; 2mmol of diethylamine are added and then the ice water bath is removed; the mixture was stirred at room temperature for 60 minutes; filtering to remove precipitated triethylamine hydrochloride; removing residual solvent by rotary evaporation, and then carrying out silica gel column chromatography purification by using 20% ethyl acetate-n-hexane as a mobile phase to obtain a product; the yield is aboutIs 85 percent; FIG. 4 is a NMR chart of the benzoyl (N, N-) diethyl-1-butanamide product of the first step of example 1;
Figure BDA0003487934920000101
synthesis of benzoyl (nitrogen, nitrogen-) diethyl-1-butanamide p-toluenesulfonylhydrazone: benzoyl butyl (nitrogen, nitrogen-) bisethylamide (0.03mol) and p-toluenesulfonyl hydrazide (0.033mol) were mixed and dissolved in 30ml of methanol; the mixture is refluxed for 5 to 8 hours under the condition of stirring; then the mixture is kept stand for 24 hours and then is cooled to minus 15 ℃; filtering the mixture at low temperature to obtain crystals, washing with cold methanol, and drying in a vacuum oven at 50 deg.C for 24 hr to obtain white solid product with yield of about 81%; FIG. 5 is a NMR chart of a second step of example 1 showing the formation of benzoyl (nitrogen, nitrogen-) bis-ethyl-1-butanamide p-toluenesulfonylhydrazone;
Figure BDA0003487934920000102
61[6,6]synthesis of phenyl C (N, N) diethyl-1-butyryl gastric: 4mmol of benzoyl (N, N) -bis-ethyl-1-butanamide p-toluenesulfonylhydrazone are dissolved in 10ml of dry pyridine in a dry three-neck flask under the protection of nitrogen; then 5mmol of sodium methoxide is added, and the mixture is stirred for 15 minutes at room temperature; 4mmol of C60Dissolved in 100ml of 1, 2-dichlorobenzene and then added to the three-necked flask; the mixture reacts for 24 hours at 65-70 ℃ under stirring (homogeneous reaction); purifying the reactant by silica gel column chromatography, wherein the mobile phase is toluene (note: toluene is the mobile phase when R is short-chain alkyl; and toluene and hexane mixture (volume ratio 9: 1) is the mobile phase when R is long-chain alkyl); the resulting solution was concentrated to 100ml by rotary evaporation and then refluxed for 24 hours; adding methanol into the obtained solution, and drying the filtered precipitate in a vacuum oven at 80 ℃ for 20 hours to obtain a product; yield about 35%;
Figure BDA0003487934920000103
61[6,6]synthesis of phenyl C (N, N) bis-ethyl-1-butylamine: adding 50mmol sodium borohydride and 10mmol [6,6 ] of 1, 4-dioxane into 20ml 1, 4-dioxane under stirring at 10 DEG C]Phenyl radical C61(N, N) -bis-ethyl-1-butyryl-gastric, resulting in a suspension; 50mmol of 1, 4-dioxane (10ml) solution of acetic acid is dripped into the suspension, and the whole dripping process takes 10 minutes; the reaction mixture is refluxed for 2 hours under the condition of stirring; drying the obtained mixture in a vacuum oven at 60 ℃ for 24 hours, washing the residue with water, extracting with chloroform, and repeating the steps twice; the resulting organic layer solution was dried over anhydrous sodium sulfate and then rotary evaporated to remove residual solvent; recrystallizing the residue with methanol and diethyl ether (volume ratio is 4.5:5.5) to obtain the product; the yield was about 74%.
Figure BDA0003487934920000111
61[6,6]Synthesis of phenyl C (N, N) bis-ethyl-1-butylammonium salt：[6,6]Phenyl radical C61(N, N) -bis-ethyl-1-butylamine (40 mmol) was dissolved in 60ml of Tetrahydrofuran (THF) and then excess (molar ratio) of bromoethane and 20ml of dimethyl sulfoxide (DMSO) were added; stirring the mixed solution at 50 ℃ for 3 days; the THF and the remaining bromoalkane were removed by distillation under the reduced pressure, and about 150ml of ethyl acetate was added to the residue; the precipitate was collected by centrifugation (6000-; the washed precipitate was dried under vacuum at 80 ℃ overnight to give the product in about 68.7% yield.
Figure BDA0003487934920000112
Example 2
The fullerene of example 1 is represented by C60Is changed to C70The final product is [6,6 ]]Phenyl radical C71(N, N) -bis-ethyl-1-butylammonium salt (product II), structureThe formula is as follows:
Figure BDA0003487934920000121
example 3
The amount of benzoyl (N, N-) diethyl-1-butanamide p-toluenesulfonylhydrazone added in the third step of the reaction in example 1 was changed to 9mmol (2-fold excess of fullerene), the amount of bromoethane added in the fifth step was doubled, and the reaction time was prolonged to 5 days, to obtain a disubstituted product III, the structural formula of which is shown below:
Figure BDA0003487934920000122
example 4
The disubstituted product IV was prepared by replacing C60 in example 3 with C70 and leaving the same, and the structural formula is shown below:
Figure BDA0003487934920000131
perovskite solar cell example 1
(1) Ultrasonically cleaning the FTO glass with the pattern by deionized water, acetone and isopropanol in sequence, and then carrying out UVO treatment for 15 minutes for later use;
(2) preparing NiO with the thickness of 25nm by the treated FTO glass through a magnetron sputtering processxA hole transport layer;
(3) covering NiOxPlacing the FTO glass of the hole transport layer into a high-temperature oven, annealing for 30 minutes at 300 ℃, and taking out for later use after cooling;
(4) 1290.8mg of PbI are taken2And 445.2mg of MAI dissolved in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO is 4:1), stirring at normal temperature overnight to obtain a perovskite precursor solution, wherein the total concentration of solute in the solution is 1.4 mol/ml;
(5) NiO obtained in step (3)xAnd (3) coating the perovskite precursor solution obtained in the step (4) on a hole transport layer in a spinning mode: machine for finishingThe spin coating process is divided into three steps, firstly spin coating at 4000rpm for 3 seconds; then spin coating at 5000rpm for 30 seconds; finally, 200 mul of chlorobenzene (anti-solvent) is dripped when the high-speed spin coating is carried out at 5000rpm for 11 seconds, all the anti-solvent is dripped within 2 seconds, and the thickness of the perovskite light absorption layer is controlled to be about 500 nm;
(6) annealing the wafer obtained in the step (5) in an oven at 130 ℃ for 20 minutes, cooling and taking out;
(7) [6,6 ] prepared in example 1]Phenyl radical C61Dissolving (N, N) diethyl-1-butylammonium salt in methanol at a concentration of 2mg/ml and a spin-coating speed of 3500rpm to obtain a film with a thickness of 30 nm;
(8) moving the sheet prepared in the step (7) into a vacuum evaporation chamber, and vacuumizing until the vacuum degree is lower than 4 x 10-4Starting to carry out thermal evaporation deposition BCP modification layer after Pa, wherein BCP evaporation rate is less than 0.1 angstrom/second, and film thickness is 6 nm;
(9) preparing the gold electrode by the sheet prepared in the step (8) by adopting a thermal evaporation deposition method, and controlling the vacuum degree to be lower than 4 x 10-4Pa, the initial evaporation rate is 0.2 nm/second, meanwhile, the real-time film thickness is monitored through an online film thickness testing device, after the film thickness is larger than 10nm, the evaporation rate is adjusted to be 1.5 nm/second, after the film thickness is larger than 20nm, the evaporation rate is adjusted to be 4 nm/second, and the final thickness of a gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Perovskite solar cell comparative example
Based on PC61Preparing a perovskite solar cell with BM as an electron transport modification layer:
compared with perovskite solar cell example 1, the difference is that:
(7) taking 12.5mg of PC61BM is dissolved in 1ml of toluene solvent, and stirred overnight at normal temperature to obtain an electron transport layer precursor solution with the concentration of 12.5 mg/ml; spin-coating PC on the sheet obtained in step (6)61BM solution, spin-coated at 4000rpm for 30 seconds, with a film thickness of about 50 nm.
Perovskite solar cell example 2
Compared to perovskite solar cell example 1, the spin coating speed in step (7) was changed to 2500rpm, and the thickness of the film was 50 nm.
Perovskite solar cell example 3
Compared to perovskite solar cell example 1, the spin coating speed in step (7) was changed to 1500rpm and the film thickness was 80 nm.
Perovskite solar cell example 4
Compared with perovskite solar cell embodiment 1, the modified layer film prepared by the spin coating method is prepared by a wire bar coating method, and the preparation process comprises the following steps: [6,6]Phenyl radical C61(N, N) Biethylic-1-butylammonium salt was dissolved in methanol at a concentration of 2mg/ml, a coating speed of 14mm/s, a bar-to-substrate gap of 50 μm, and a film thickness of 50nm was obtained.
Perovskite solar cell example 5
The product obtained based on example 2, namely [6,6 ]]Phenyl radical C71And (N, N) bisethyl-1-butylammonium salt is used for preparing the perovskite solar cell of the electron transport layer. The modified layer film is prepared by a spin coating method, the preparation method is as described in perovskite solar cell example 1, and the thickness of the obtained film is 50 nm.
Perovskite solar cell example 6
C prepared on the basis of example 360And preparing the perovskite solar cell with the electron transport layer by using the double-substituted product. The modified layer film is prepared by a spin coating method, the preparation method is as described in perovskite solar cell example 1, and the thickness of the obtained film is 50 nm.
Perovskite solar cell example 7
C prepared on the basis of example 470And preparing the perovskite solar cell with the electron transport layer by using the double-substituted product. The modified layer film is prepared by a spin coating method, the preparation method is as described in perovskite solar cell example 1, and the thickness of the obtained film is 50 nm.
And (3) performance detection:
and (3) testing the battery performance: the perovskite solar cell prepared in the above example was subjected to a standard solar light intensity (AM1.5G, 100 mW/cm) using a solar simulator (xenon lamp as a light source)2) The test was carried out as described aboveThe solar simulator of (a) was calibrated in the us national renewable energy laboratory using a silicon diode (with KG9 visible filter). The corresponding test results are shown in table 1:
TABLE 1 Performance parameters of perovskite solar cells
Figure BDA0003487934920000151
Figure BDA0003487934920000161
As can be seen from the battery performance test data, the electron transport layer material can be dissolved in green solutions such as methanol, ethanol, glycerol and the like, and can be prepared into a film by various solution processing methods. The electron transport layer thin film can be used for perovskite solar cells. Compared with a perovskite solar cell adopting a green solvent processing method to prepare the novel electron transport layer, the perovskite solar cell adopting the green solvent processing method to prepare the novel electron transport layer has the advantages that the perovskite solar cell adopting the electron transport layer is prepared by adopting PCBM or Bis-PCBM solution film-forming with chlorobenzene, dichlorobenzene and the like as solvents shows equivalent performance parameters.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A fullerene derivative material having the structure of formula i, formula ii, formula iii or formula iv:
Figure FDA0003487934910000011
each R is independently selected from-H and/or C1-C6 alkyl;
each X is independently selected from halogen.
2. A fullerene derivative material according to claim 1, wherein the C1-C6 alkyl group is a C1-C6 straight chain alkyl group;
each X is independently selected from-Cl, -Br or-I.
3. A fullerene derivative material according to claim 1, wherein the fullerene derivative material is selected from formula 101, formula 102, formula 103, formula 104 or formula 106:
Figure FDA0003487934910000012
Figure FDA0003487934910000021
4. a fullerene derivative material according to claim 1, wherein the fullerene derivative material is soluble in a green solvent; the green solvent includes one or more of methanol, ethanol, and a polyol.
5. A method of producing a fullerene derivative material according to claim 1, comprising the steps of:
reacting fullerene with a material shown as a formula 201 to obtain an intermediate product;
Figure FDA0003487934910000022
each R is selected from-H and/or C1-C8 alkyl;
the fullerene is selected from C60 or C70;
the intermediate product has a structure of formula 202, formula 203, formula 204, or formula 205:
Figure FDA0003487934910000031
and reducing the intermediate product, and carrying out quaternization reaction to obtain the fullerene derivative material.
6. An electron transport layer comprising the fullerene derivative material according to any one of claims 1 to 4 or the fullerene derivative material produced by the production method according to claim 5.
7. The electron transport layer of claim 6, wherein the electron transport layer has a thickness of 10 to 100 nm.
8. A perovskite solar cell comprising the electron transport layer of any one of claims 6 to 7.
9. The perovskite solar cell of claim 8, wherein the electron transport layer is solution processed;
the solution processing method is selected from a spin coating film forming method, a scraper coating method, a slit extrusion coating method, a wire rod coating method or a roll-to-roll printing method.
CN202210085896.2A 2022-01-25 2022-01-25 Fullerene derivative material, preparation method thereof and perovskite solar cell Pending CN114409549A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210085896.2A CN114409549A (en) 2022-01-25 2022-01-25 Fullerene derivative material, preparation method thereof and perovskite solar cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210085896.2A CN114409549A (en) 2022-01-25 2022-01-25 Fullerene derivative material, preparation method thereof and perovskite solar cell

Publications (1)

Publication Number Publication Date
CN114409549A true CN114409549A (en) 2022-04-29

Family

ID=81277097

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210085896.2A Pending CN114409549A (en) 2022-01-25 2022-01-25 Fullerene derivative material, preparation method thereof and perovskite solar cell

Country Status (1)

Country Link
CN (1) CN114409549A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090107316A (en) * 2008-04-08 2009-10-13 한국화학연구원 C70 methanofullerene derivatives and organic photovoltaic devices using them
KR20130113210A (en) * 2012-04-05 2013-10-15 타코마테크놀러지 주식회사 Fullerene derivatives and preparation thereof
CN107394047A (en) * 2017-07-31 2017-11-24 苏州大学 Application of the alcohol-soluble fullerene derivate in perovskite solar cell
CN107814724A (en) * 2017-10-12 2018-03-20 苏州协鑫纳米科技有限公司 Electron transport material and preparation method thereof and perovskite solar cell
CN108565339A (en) * 2018-01-11 2018-09-21 华南师范大学 Perovskite solar cell containing fullerene derivate and preparation method thereof
CN109232527A (en) * 2018-08-10 2019-01-18 浙江大学 The organic photovoltaic cell of self-doping type fullerene pyridiniujm electron transport material and its composition
CN109362726A (en) * 2018-09-12 2019-02-22 浙江大学 A kind of purposes of fullerene derivate
CN109950410A (en) * 2019-04-09 2019-06-28 南昌大学 It a kind of preparation method of perovskite thin film and is applied in perovskite solar battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090107316A (en) * 2008-04-08 2009-10-13 한국화학연구원 C70 methanofullerene derivatives and organic photovoltaic devices using them
KR20130113210A (en) * 2012-04-05 2013-10-15 타코마테크놀러지 주식회사 Fullerene derivatives and preparation thereof
CN107394047A (en) * 2017-07-31 2017-11-24 苏州大学 Application of the alcohol-soluble fullerene derivate in perovskite solar cell
CN107814724A (en) * 2017-10-12 2018-03-20 苏州协鑫纳米科技有限公司 Electron transport material and preparation method thereof and perovskite solar cell
CN108565339A (en) * 2018-01-11 2018-09-21 华南师范大学 Perovskite solar cell containing fullerene derivate and preparation method thereof
CN109232527A (en) * 2018-08-10 2019-01-18 浙江大学 The organic photovoltaic cell of self-doping type fullerene pyridiniujm electron transport material and its composition
CN109362726A (en) * 2018-09-12 2019-02-22 浙江大学 A kind of purposes of fullerene derivate
CN109950410A (en) * 2019-04-09 2019-06-28 南昌大学 It a kind of preparation method of perovskite thin film and is applied in perovskite solar battery

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BORIS RUSS ET AL.: "Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors", 《CHEM. SCI.》, vol. 7, pages 1914 - 1919 *
CHAO LIU ET AL.: "Synthesis and Photovoltaic Properties of Novel Monoadducts and Bisadducts Based on Amide Methanofullerene", 《ACS APPL. MATER. INTERFACES》, vol. 4, pages 1065 - 1071 *
HONG DUC PHAM ET AL.: "Organic interfacial materials for perovskite-based optoelectronic devices", 《ENERGY ENVIRON. SCI.》, vol. 12, pages 1177 - 1209 *
YA-PING SUN ET AL.: "Preparation and Characterization of Highly Water-Soluble Pendant Fullerene Polymers", 《MACROMOLECULES》, vol. 32, pages 8747 - 8752, XP002477261, DOI: 10.1021/ma9906736 *
孙璇: "n-型自掺杂富勒烯铵盐及其自组装的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 4, pages 014 - 227 *

Similar Documents

Publication Publication Date Title
CN108546267B (en) Organic conjugated micromolecule material with terminal group containing cycloalkyl chain, preparation method thereof and application thereof in solar cell
JP4612786B2 (en) Manufacturing method of organic field effect transistor
CN111848422B (en) Hole transport material and application thereof in perovskite solar cell
JP2009135237A (en) Soluble fullerene derivative
CN112047958B (en) Organic conjugated micromolecule material containing thianthrene terminal group and preparation method thereof
CN110818725A (en) Conjugated micromolecule based on multi-nitrogen heterocyclic ring and application of conjugated micromolecule in organic photoelectric device
CN107602551B (en) Preparation method and application of wide-band-gap star-shaped non-fullerene small-molecule receptor
WO2012137853A1 (en) PERYLENE TETRACARBOXYLIC ACID BISIMIDE DERIVATIVE, n-TYPE SEMICONDUCTOR, PROCESS FOR PRODUCING n-TYPE SEMICONDUCTOR, AND ELECTRONIC DEVICE
Fan et al. A new small molecule with indolone chromophore as the electron accepting unit for efficient organic solar cells
CN114507337A (en) Conjugated polymer containing quinoxaline structure, and synthetic method and application thereof
Ge et al. Synthesis of highly crystalline copper phthalocyanine needles by solvothermal method
WO2024031993A1 (en) Star-shaped molecule capable of being used for hole transport layer, preparation method therefor, and use thereof
CN112062777A (en) Organic small-molecule photovoltaic material based on dithienylbenzodithiophene donor nucleus and preparation method and application thereof
CN114409549A (en) Fullerene derivative material, preparation method thereof and perovskite solar cell
WO2023142330A1 (en) Fullerene derivative material and preparation method therefor and application thereof in perovskite solar cell
JP4994347B2 (en) Thiazole organic semiconductor compound and organic thin film transistor using the same
CN114133385B (en) Hole transport material with carbazole as core and thiophene or phenoxazine as end group, and synthesis method and application thereof
CN112608333B (en) Micromolecules based on dithiadiazole carbazole derivatives, synthetic method thereof and application of micromolecules in organic photoelectric devices
CN109897055B (en) Organic compound based on bi-carbazole and perylene diimide and preparation method and application thereof
JP7062284B2 (en) A novel porphyrin derivative, a method for producing a porphyrin derivative, a donor material, a photoelectric conversion device, and a method for manufacturing a photoelectric conversion device.
JP2012236777A (en) Indolocarbazole-containing imide compound, and intermediate for synthesizing the same, method for producing them, organic semiconductor composition, and organic solar cell element
CN115073455B (en) Preparation method and application of fluorine substituted perylene imide derivative
CN114349752B (en) Solution-processable electron transport layer modification material and preparation method and application thereof
CN113816974B (en) Porphyrin covalent connection sym-triazacyclonium compound and preparation and application thereof
CN113735876B (en) Benzothienothienobenzene (BTBT) derivative with asymmetric structure and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination