CN116396301B - Polymerizable metal phthalocyanine and preparation method thereof, solar cell and preparation method thereof - Google Patents

Polymerizable metal phthalocyanine and preparation method thereof, solar cell and preparation method thereof Download PDF

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CN116396301B
CN116396301B CN202310388796.1A CN202310388796A CN116396301B CN 116396301 B CN116396301 B CN 116396301B CN 202310388796 A CN202310388796 A CN 202310388796A CN 116396301 B CN116396301 B CN 116396301B
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metal phthalocyanine
transport layer
layer
polymerizable metal
polymerizable
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CN116396301A (en
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吴炳辉
申宇玺
冯奇凡
黄晓锋
尹君
李静
郑南峰
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Tan Kah Kee Innovation Laboratory
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/549—Organic PV cells

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Abstract

The embodiment of the application discloses polymerizable metal phthalocyanine and a preparation method thereof, a solar cell and a preparation method thereof, wherein the structural formula of the polymerizable metal phthalocyanine is as followsModification group-OR at beta position thereof 1 、‑OR 2 、‑OR 3 、‑OR 4 Comprising an alkoxyl ether group structure and an unsaturated alkenyl or alkynyl group, on the one hand, can improve the conductivity of the material, and on the other hand, when the polymerizable metal phthalocyanine is applied to a hole transport material or an interfacial layer material in a solar cell, the lone pair electrons existing in oxygen atoms can react with metal cations such as Pb on the perovskite surface 2+ Coordination bonding to form Pb-O bond, which plays a role in fixing metal cations, improves the stability of solar cells, and can effectively inhibit halogen anions such as I on perovskite surface after alkenyl or alkynyl is polymerized in situ to form molecular polymer ‑ Upward migration further enhances the stability and cell efficiency of the solar cell.

Description

Polymerizable metal phthalocyanine and preparation method thereof, solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to polymerizable metal phthalocyanine and a preparation method thereof, a solar cell and a preparation method thereof.
Background
In recent years, organic-inorganic hybrid perovskite solar cells have been rapidly developed, and have been receiving attention because of their advantages such as excellent absorption coefficient, tunable band gap, suitable forbidden band width, higher charge mobility and longer charge diffusion length. A general perovskite solar cell includes an anode, an electron transport layer, a perovskite light absorption layer, a hole transport layer, and a cathode, wherein the hole transport layer serves as a transport channel for carriers, and functions to extract and transport holes. Currently, a relatively widely used hole transport material is 2,2 ', 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), but the hole mobility is improved by doping the material. The introduction of doping materials (such as lithium salts) tends to result in reduced device stability of perovskite solar cells.
Disclosure of Invention
The embodiment of the application provides polymerizable metal phthalocyanine and a preparation method thereof, a solar cell and a preparation method thereof, and aims to solve the technical problem that the stability of devices of the existing solar cell is poor.
In order to solve the problems, the technical scheme provided by the invention is as follows:
the embodiment of the application provides a polymerizable metal phthalocyanine, and the structural formula of the polymerizable metal phthalocyanine is shown as the following formula (I):
Wherein M is selected from zinc, nickel, copper, palladium, aluminum, iron, cobalt, magnesium, platinum, indium, ruthenium, titanium, lead, gallium or manganese;
R 1 、R 2 、R 3 、R 4 independently of one another selected fromWherein R is 5 Bonded to O in formula (I), R 5 Selected from single bond, alkyl with 1-2 carbon atoms with at least one H substituted or unsubstituted by alkoxy, or alkoxy ether with 2-4 carbon atoms, L is selected from O or single bond, and L is selected from O, R 5 Selected from single bonds not occurring simultaneously, R 6 Including groups terminated with a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group.
In some embodiments of the present application, the R 5 Selected from alkyl groups having 1 to 2 carbon atoms, R 6 Selected from alkenyl, alkynyl or phenylalkenyl.
In some embodiments of the present application, the polymerizable metal phthalocyanine comprises at least one of the following structural formulas:
wherein R is 6 Each occurrence is independently selected from alkenyl, alkynyl or alkenyl containing one benzene ring.
In some embodiments of the present application, the polymerizable metal phthalocyanine comprises at least one of the following structural formulas:
the embodiment of the application also provides a preparation method of the polymerizable metal phthalocyanine in the embodiment, which comprises the following steps:
carrying out a first reaction and impurity removal on 4-nitrophthalonitrile and a first reactant at a first temperature to obtain a first intermediate, wherein the structural formula of the first reactant is as follows: The structural formula of the first intermediate is as follows:
carrying out a second reaction and impurity removal on the first intermediate and 1, 8-diazabicyclo [5.4.0] undec-7-ene at a second temperature to obtain a second intermediate, wherein the structural formula of the second intermediate is as follows:
performing third reaction and impurity removal on the second intermediate and metal salt of M metal at a third temperature to obtain the polymerizable metal phthalocyanine, wherein the structural formula of the polymerizable metal phthalocyanine is as follows:
in some embodiments of the present application, the molar ratio of 4-nitrophthalonitrile to the first reactant is 1 (1-2); and/or the molar ratio of the second intermediate to M metal ions in the metal salt is 1 (1-3).
In some embodiments of the present application, the first temperature is 55 to 65 ℃ and the first reaction time is 3 to 5 hours; and/or the second temperature is 135-145 ℃, and the second reaction time is 13-17 h; and/or the third temperature is 155-165 ℃, and the time of the third reaction is 4-8 h.
The embodiment of the application also provides a solar cell, which comprises a first electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second electrode which are sequentially laminated, wherein the hole transport layer comprises a metal phthalocyanine polymer; alternatively, the solar cell comprises a first electrode, an electron transport layer, a perovskite light absorption layer, an interface layer, a hole transport layer and a second electrode which are sequentially laminated, wherein the interface layer comprises a metal phthalocyanine polymer; wherein the metal phthalocyanine polymer comprises a polymer polymerized from the polymerizable metal phthalocyanine of the above embodiment or comprises a polymer polymerized from the polymerizable metal phthalocyanine produced by the production method of the above embodiment.
The embodiment of the application also provides a preparation method of the solar cell, which comprises the following steps:
providing a substrate comprising a first electrode and an electron transport layer laminated in sequence;
forming a perovskite light absorbing layer on the electron transport layer;
forming a hole transport layer on the perovskite light absorption layer, wherein the material of the hole transport layer comprises a polymer formed by polymerizing the polymerizable metal phthalocyanine in the embodiment or comprises a polymer formed by polymerizing the polymerizable metal phthalocyanine prepared by the preparation method in the embodiment;
forming a second electrode on the hole transport layer;
or, the preparation method comprises the following steps:
providing a substrate comprising a first electrode and an electron transport layer laminated in sequence;
forming a perovskite light absorbing layer on the electron transport layer;
forming an interface layer on the perovskite light absorption layer, wherein the material of the interface layer comprises a polymer formed by polymerizing the polymerizable metal phthalocyanine in the embodiment or comprises a polymer formed by polymerizing the polymerizable metal phthalocyanine prepared by the preparation method in the embodiment;
forming a hole transport layer on the interfacial layer;
a second electrode is formed on the hole transport layer.
In some embodiments of the present application, when the material of the hole transport layer includes the polymer described above, the forming of the hole transport layer includes the steps of:
mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine;
coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer;
and carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction.
In some embodiments of the present application, when the material of the interface layer includes the polymer described above, the forming of the interface layer includes the steps of:
mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine;
coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer;
and carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction.
The beneficial effects of this application are: the structural formula of the polymerizable metal phthalocyanine is as followsModification group-OR at beta position thereof 1 、-OR 2 、-OR 3 、-OR 4 Comprising an alkoxyl ether group structure and an unsaturated alkenyl or alkynyl group, on the one hand, can improve the conductivity of the material, and on the other hand, when the polymerizable metal phthalocyanine is applied to a hole transport material or an interfacial layer material in a solar cell, the lone pair electrons existing in oxygen atoms can react with metal cations such as Pb on the perovskite surface 2+ Coordination bonding to formPb-O bond, which has the function of fixing metal cation, improves the stability of solar cell, and can effectively inhibit halogen anion such as I on perovskite surface after alkenyl or alkynyl forms molecular polymer after in-situ polymerization - Upward migration further enhances the stability and cell efficiency of the solar cell.
Drawings
In order to more clearly illustrate the embodiments or the technical solutions in the prior art, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of steps of a preparation method of polymerizable metal phthalocyanine according to an embodiment of the present application.
Fig. 2 is a schematic structural diagram of a solar cell according to an embodiment of the present application.
Fig. 3 is a step flowchart of a method for manufacturing a solar cell according to an embodiment of the present application.
FIG. 4 is an ultraviolet fluorescence absorbance spectrum of beta-tetraethyleneoxy ethoxy zinc phthalocyanine.
FIG. 5 is an infrared absorption spectrum of a tetra-ethyleneoxy ethoxy zinc phthalocyanine at the beta position.
FIG. 6 is a mass spectrum of tetra-ethyleneoxy ethoxy zinc phthalocyanine at the beta position.
FIG. 7 is a mass spectrum of beta-position tetra-vinyl phenoxy zinc phthalocyanine.
Fig. 8 is a graph comparing the stability of solar cells prepared in device examples 1 and 2 and device comparative examples 1 and 2.
Fig. 9 is a graph of current versus voltage for the performance of solar cells prepared for device examples 1, 2 and device comparative examples 1, 2.
Fig. 10 is a graph of current versus voltage for the performance of solar cells prepared in device example 3 and device comparative example 2.
Fig. 11 is a graph of current versus voltage for the performance of the solar cell prepared in device comparative example 3.
Fig. 12 is a time resolved photoluminescence spectrum of a solar cell prepared in device example 1, device comparative example 1, and a perovskite light absorbing layer alone.
Fig. 13 is a steady state fluorescence spectrum of the solar cell and the perovskite light absorbing layer alone prepared by device example 1, device comparative example 1.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower directions of the device in actual use or operation, and in particular, the directions of the drawings in the drawings. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction.
In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.
In this application, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c" or "at least one (individual) of a, b, and c" may each denote: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The application provides a polymerizable metal phthalocyanine, the structural formula of which is shown as a formula (I):
wherein M comprises a transition metal, M is selected from zinc, nickel, copper, palladium, aluminum, iron, cobalt, magnesium, platinum, indium, ruthenium, titanium, lead, gallium or manganese. R is R 1 、R 2 、R 3 、R 4 Independently of one another selected fromI.e. R 1 、R 2 、R 3 、R 4 The same groups may be selected from different groups, wherein R 5 Bonded to O in formula (I), L is selected from O or a single bond, R 5 Selected from single bond, alkyl group with 1-2 carbon atoms, or alkoxy ether group with 2-4 carbon atoms, wherein at least one H is substituted or unsubstituted by alkoxy, R 6 Including groups having terminal groups that are substituted or unsubstituted alkenyl groups, or substituted unsubstituted alkynyl groups. In the present application, unless otherwise indicated, "substituted or unsubstituted" means that the carbon-linked hydrogen atom is taken by a halogen atomSubstituted or unsubstituted.
Specifically, R 5 When at least one H is an alkyl group having 1 to 2 carbon atoms which is substituted or unsubstituted by an alkoxy group, the carbon atom number of the substituent alkoxy group is 1 to 3, and the alkoxy group may be a methylalkoxy group, an ethylalkoxy group, a propylalkoxy group or the like.
R 5 Selected from alkoxy ether groups with 2-4 carbon atoms, and has a structural general formula of R 7 OR 8 ，R 7 、R 8 Independently of one another selected from-CH 2 -or-CH 2 CH 2 -。
It is understood that when L is selected from single bonds, R 5 And R is R 6 Directly bonded to R 5 When selected from single bonds, L is directly bonded to O in formula (I). Specifically, L is O, R 5 The case of selecting from single bonds does not occur simultaneously.
The application provides polymerizable metal phthalocyanine, its beta-position modification group-OR 1 、-OR 2 、-OR 3 、-OR 4 Comprising an alkoxyl ether group structure and an unsaturated alkenyl or alkynyl group, on the one hand, can improve the conductivity of the material, and on the other hand, when the polymerizable metal phthalocyanine is applied to a hole transport material or an interfacial layer material in a solar cell, the lone pair electrons existing in oxygen atoms can react with metal cations such as Pb on the perovskite surface 2+ Coordination bonding to form Pb-O bond, which plays a role in fixing metal cations, improves the stability of solar cells, and can effectively inhibit halogen anions such as I on perovskite surface after alkenyl or alkynyl is polymerized in situ to form molecular polymer - Upward migration further enhances the stability and cell efficiency of the solar cell.
In some examples, alkyl groups such as propyl are directly used for modifying the alpha position of the metal phthalocyanine, and although the hydrophobic performance of the perovskite light absorption layer can be improved, water vapor is prevented from entering, the conductivity of the alkyl groups is poor, the electronegativity is weak, the hole mobility is influenced, and the efficiency of the solar cell is low; and the steric hindrance of the alkyl is small, pi-pi interaction among the metal phthalocyanines is difficult to overcome, so that the metal phthalocyanines are easy to gather, hole migration resistance is increased, surface morphology flatness is reduced, a leakage channel is generated, and long-term stability of the solar cell is weakened. Compared with metal phthalocyanine with alpha-alkyl modification groups, the beta-modification groups of the polymerizable metal phthalocyanine comprise an alkoxy ether group structure and unsaturated alkenyl or alkynyl groups, and the polymer formed by the polymerizable metal phthalocyanine has good solubility, lower aggregation degree in solvents such as chloroform and chlorobenzene, better dispersibility and more stable property.
In some embodiments, the R 5 Selected from alkyl groups having 1 to 2 carbon atoms, e.g. -CH 2 -、-CH 2 -CH 2 -or-CH (CH) 3 ) And the water blocking capability of the perovskite light absorbing layer can be improved.
R 6 Selected from alkenyl-hc=ch 2 Alkynyl-c=ch or alkenylThe metal phthalocyanine can be polymerized to form a polymer, so that the stability of the hole transport material is improved. The number n of benzene rings in the phenyl group is not limited, and may be specifically 1, 2 or 3, etc., and H atoms on the benzene rings may be substituted with halogen atoms or carbon chains, such as F, cl, methyl, ethyl, etc.
In some embodiments, the polymerizable metal phthalocyanine is selected from at least one of the following structural formulas:
wherein, in some embodiments, R in the above formula 6 Each occurrence is independently selected from alkenyl, alkynyl or alkenyl containing one benzene ring.
Further, R in the above structural formula 6 Each occurrence of which is independently selected from at least one of alkenyl and alkynyl.
In some embodiments, in particular, the polymerizable metal phthalocyanine includes, but is not limited to, at least one of the following structural formulas:
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the polymerizable metal phthalocyanine provided by the embodiment of the application can be subjected to ultraviolet exposure through the photoinitiator to generate photopolymerization reaction, or subjected to thermal polymerization reaction at a certain temperature through the thermal initiator to generate the metal phthalocyanine polymer, and the metal phthalocyanine polymer can be used as a hole transport material and applied to a hole transport film of a solar cell.
Referring to fig. 1, for the polymerizable metal phthalocyanine in the above embodiment, the present application further provides a preparation method of the polymerizable metal phthalocyanine, including:
s10, carrying out a first reaction and impurity removal on 4-nitrophthalonitrile and a first reactant at a first temperature to obtain a first intermediate, wherein the structural formula of the first reactant is as follows:the structural formula of the first intermediate is as follows:
s20, carrying out a second reaction and impurity removal on the first intermediate and 1, 8-diazabicyclo [5.4.0] undec-7-ene at a second temperature to obtain a second intermediate, wherein the structural formula of the second intermediate is as follows:
s30, carrying out a third reaction and impurity removal on the second intermediate and metal salt of M metal at a third temperature to obtain the polymerizable metal phthalocyanine, wherein the structural formula of the polymerizable metal phthalocyanine is as follows:
specifically, in S10, the structural formula of 4-nitrophthalonitrile is:
in some embodiments, the first reactant includes, but is not limited to, at least one of the following structural formulas:(ethylene glycol monovinyl ether), - (Y-O) and (B) and (C) and (B) and (C) and (>(3-buten-1-ol), -j>(2-propen-1-ol), -j>(ethylene glycol monoallyl ether), - (Y-O) and (B) in the form of a gel>(diethylene glycol monoallyl ether) >(diethylene glycol monovinyl ether)>(4-vinylphenol).
In S10, the molar ratio of the 4-nitrophthalonitrile to the first reactant is 1 (1-2), wherein the molar ratio can be 1:1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:2, the first temperature is 55-65 ℃, and the time of the first reaction is 3-5 hours.
The first intermediate may be prepared using a solution process, and specifically, the step of preparing the first intermediate includes:
s11, respectively weighing 4-nitrophthalonitrile and a first reactant according to the mol ratio of the 4-nitrophthalonitrile to the first reactant of 1 (1-2), and mixing the 4-nitrophthalonitrile, the first reactant, a first catalyst and a first solvent to form a first reaction system;
s12, placing the first reaction system at 55-65 ℃ for 3-5 h;
and S13, sequentially performing cooling, extraction, evaporation and column chromatography on the first reaction system to obtain the first intermediate.
Wherein the first catalyst includes, but is not limited to, potassium carbonate, potassium iodide and tetrabutylammonium iodide, and may also include other catalysts. The first solvent includes, but is not limited to, DMF (dimethylformamide), DMSO (dimethyl sulfoxide).
In S20, 1, 8-diazabicyclo [5.4.0]The structural formula of undec-7-ene (DBU) is:the second temperature is 135-145 ℃, and the second reaction time is 13-17 h.
In some embodiments, the second intermediate may be prepared using a solution process, the preparation of the second intermediate comprising:
s21, mixing DBU, the first intermediate and the second solvent to form a second reaction system;
s22, reacting the second reaction system for 13-17 hours at the temperature of 135-145 ℃;
s23, cooling, centrifuging and carrying out column chromatography on the second reaction system in sequence to obtain the second intermediate.
Wherein the second solvent may be an alcoholic solvent, preferably a high boiling point (greater than 100 ℃) solvent, including but not limited to n-butanol, n-pentanol, and the like.
In S30, the metal salt of M metal includes, but is not limited to, zn 2+ 、Ni 2+ 、Cu 2+ 、Pd 2+ 、Al 3+ 、Fe 2+ 、Co 2+ 、Mg 2+ 、Pt 2+ 、In 3+ 、Ru 2+ 、Ti 4+ 、Pb 2+ 、Ga 2+ Or Mn of 2+ Is a metal salt of (a) a metal salt of (b). The molar ratio of the second intermediate to the M metal ions in the metal salt is 1 (1-3), the molar ratio can be specifically 1:1,1:1.2,1:1.5,1:1.7,1:1.8,1:2,1:2.2,1:2.5,1:2.7,1:2.9 or 1:3, the third temperature can be 155-165 ℃, and the time of the third reaction can be 4-8 h.
Specifically, the polymerizable metal phthalocyanine may be prepared by a solution method in S30, and the step of S30 includes:
S31, mixing a third solvent with a second catalyst to form a reaction system A;
s32, respectively weighing the second intermediate and the metal salt of the M metal according to the molar ratio of the second intermediate to the metal salt of the M metal of 1 (1-3), and mixing to form a reaction system B;
s33, mixing the reaction system A and the reaction system B to form a third reaction system, and reacting the third reaction system for 4-8 hours at 155-165 ℃;
and S34, sequentially cooling, centrifuging and carrying out column chromatography on the third reaction system to obtain the polymerizable metal phthalocyanine.
Referring to fig. 2, the embodiment of the present application further provides a solar cell, which includes a stacked first electrode 10, an electron transport layer 20, a perovskite light absorbing layer 30, a hole transport layer 40, and a second electrode 50.
The first electrode 10 may be a transparent conductive electrode including, but not limited to, FTO (fluorine doped tin oxide) electrode, ITO (indium tin oxide) electrode. The thickness of the first electrode 10 is 5 to 20nm, and specifically may be 5nm, 10nm, 15nm, 20nm, or the like.
The material of the electron transport layer 20 includes, but is not limited to, PCBM, tiO 2 、SnO 2 ZnO, znO-ZnS. The thickness of the electron transport layer 20 is 10 to 120nm, specifically 10nm, 20nm, 50nm, 70nm, 80nm, 100nm, 120nm, or the like.
The perovskite light absorbing layer 30 material includes, but is not limited to, a a B b X c Wherein A is an organic cation or an inorganic cation, B is a metal cation, and X is a halogen or halogen-like group. a. And b and c satisfy the law of conservation of charge. A includes but is not limited to CH 3 NH 3 + (abbreviated as MA) + )、HC(NH 2 ) 2 + (abbreviated as FA + )、Cs + Or Rb + At least one of them. B includes but is not limited to Pb 2 + 、Sn 2+ 、Ti 4+ 、Zn 2+ At least one of them. C includes but is not limited to Cl - 、Br - At least one of them.
The thickness of the perovskite light absorbing layer 30 is 200 to 900nm, specifically 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or the like.
The material of the hole transport layer 40 includes a metal phthalocyanine polymer including at least one of the polymers polymerized from the polymerizable metal phthalocyanines of the above embodiments. The thickness of the hole transport layer 40 is 30 to 300nm, specifically 30nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, or the like.
The second electrode 50 includes, but is not limited to, a gold electrode or a carbon-based electrode. The thickness of the second electrode 50 is 30 to 200nm, and may be 30nm, 50nm, 60nm, 80nm, 100nm, 120nm, 150nm, 180nm or 200nm.
In other embodiments, the metal phthalocyanine may be used as a material for the interface layer. Specifically, the solar cell includes a first electrode, an electron transport layer, a perovskite light absorption layer, an interface layer, a hole transport layer, and a second electrode, which are sequentially stacked.
The solar cell in this embodiment is different from the solar cell structure shown in fig. 2 in that the solar cell further includes an interfacial layer between the perovskite light absorbing layer and the hole transporting layer, the interfacial layer including the metal phthalocyanine polymer of the above embodiment, and the hole transporting layer may be made of an existing material. Other structures are the same as those of the solar cell shown in fig. 2, and will not be described here again.
Referring to fig. 3, based on the structure of the solar cell shown in fig. 2, the present application further provides a method for manufacturing a solar cell, which includes the following steps:
s100, providing a substrate including a first electrode 10 and an electron transport layer 20 laminated in this order;
s200, forming a perovskite light absorption layer 30 on the electron transport layer 20;
s300, forming a hole transport layer 40 on the perovskite light absorption layer 30, wherein the material of the hole transport layer 40 comprises a metal phthalocyanine polymer, and the metal phthalocyanine polymer is polymerized by the polymerizable metal phthalocyanine in the embodiment;
s400, forming a second electrode 50 on the hole transport layer 40.
In S300, the preparation of the hole transport layer 40 includes:
s310, mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine;
S320, coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer;
s330, carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction.
Wherein, the polymerizable metal phthalocyanine is cured to form a hole transport layer while undergoing polymerization reaction.
The coating method includes, but is not limited to, at least one of spin coating and knife coating.
In the mixed solution, the mass fraction of the polymerizable metal phthalocyanine is 0.1% -3%, and specifically can be 0.5%, 1% or 3%.
The initiator includes a photoinitiator, which may be DMAP (4-dimethylaminopyridine), or a thermal initiator, which may be AIBN (azobisisobutyronitrile). When the photoinitiator is selected, the pre-prepared film layer can be subjected to ultraviolet irradiation to initiate photopolymerization, wherein the ultraviolet irradiation time is 2-4 min, and can be specifically 2min, 3min or 4min; when the thermal initiator is selected, the preformed film layer may be heated to initiate the thermal polymerization reaction at a temperature of 45-65deg.C, specifically 45 deg.C, 50 deg.C, 60 deg.C, 65 deg.C.
In the examples of the present application, each of the above preparation steps is performed in an atmosphere having a humidity of 10% to 15%.
The embodiment of the application also provides another preparation method of the solar cell, which comprises the following steps: providing a substrate comprising a first electrode and an electron transport layer laminated in sequence; forming a perovskite light absorbing layer on the electron transport layer; forming an interface layer on the perovskite light absorption layer, wherein the material of the interface layer comprises a polymer polymerized by the polymerizable metal phthalocyanine in the embodiment; forming a hole transport layer on the interfacial layer; a second electrode is formed on the hole transport layer.
In this embodiment, the hole transport layer material includes, but is not limited to, 2", 7" -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene. The difference between this embodiment and the embodiment shown in fig. 3 is that the preparation method further includes preparation of an interface layer, and the material of the hole transport layer is different from that of the embodiment shown in fig. 3, and other film structures and preparation processes are the same as or similar to those of the embodiment shown in fig. 3, which is described above.
The forming of the interface layer comprises the following steps: mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine; coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer; and carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction.
The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.
Example 1
S10, synthesizing 4- (ethyleneoxy ethoxy) -1, 2-phthalonitrile by adopting a liquid-phase potassium carbonate catalytic method: the reactants are respectively measured according to the mol ratio of the 4-nitrophthalonitrile to the ethylene glycol monovinyl ether of 1:2: 4g of 4-nitrophthalonitrile and 4g of ethylene glycol monovinyl ether, then the reactants and a first catalyst (12 g of potassium carbonate, 5g of potassium iodide and 5g of tetrabutylammonium iodide) are dissolved in 40mL of DMF solvent and mixed to form a first reaction system, the first reaction system is added into a 150mL flask, and then the flask is placed in a water bath at 60 ℃ and stirred and mixed for 4h, so that the reactants in the flask react. After cooling, 100mL of ethyl acetate and 400mL of ultrapure water are used for extraction, an upper ethyl acetate organic phase is taken, ethyl acetate solvent is removed by rotary evaporation, a product is obtained, the product is subjected to column chromatography purification by taking neutral alumina with 200-300 meshes as a stationary phase and a mixture of dichloromethane and petroleum ether with the volume ratio of dichloromethane to petroleum ether being 2:1 as a mobile phase, and a needle-like white crystal product 4- (ethyleneoxyethoxy) -1, 2-phthalonitrile is obtained. Wherein the petroleum ether is C n H 2n+2 (n＝5～8)。
The chemical reaction formula involved in the above reaction is shown as follows:
s20, adopting liquid-phase DBU to catalyze and synthesize beta-tetraethyleneoxy ethoxy phthalocyanine: 15mL of N-pentanol and 0.5mL of DBU were measured respectively according to a volume ratio of N-pentanol to DBU of 30:1, and then mixed with 2g of the obtained 4- (ethyleneoxyethoxy) -1, 2-phthalonitrile to form a second reaction system, the second reaction system was added into a 250mL flask, the flask was connected to a condensing reflux device, an oil bath at 140℃was performed (the flask was heated in simethicone), and the mixture was stirred under N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 15 h. After cooling, centrifuging the materials in the flask, taking the precipitate as a product, and taking 200-300 mesh neutral alumina as a stationary phaseDichloromethane: ethyl acetate: and (3) performing column chromatography purification by taking a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:1 as a mobile phase to obtain the product beta-tetraethyleneoxy ethoxy phthalocyanine, wherein the color is dark green.
The chemical reaction formula involved in the above reaction is shown as follows:
s30, catalyzing and synthesizing beta-tetraethyleneoxy ethoxy zinc phthalocyanine by adopting liquid-phase tri-n-propylamine: according to the volume ratio of n-amyl alcohol to tri-n-propylamine of 30:1, respectively measuring 15mL of n-amyl alcohol and 0.5mL of tri-n-propylamine, and mixing to form a reaction system A; according to the mol ratio of the beta-tetraethyleneoxy ethoxy phthalocyanine to the zinc acetate dihydrate of 1:3, respectively measuring 3.56g of the beta-tetraethyleneoxy ethoxy phthalocyanine and 2.63g of the zinc acetate dihydrate, and mixing to form a reaction system B; the reaction system A, B was put into a 250mL flask, the flask was connected to a condensing reflux apparatus, the flask was subjected to an oil bath at 160℃and N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 6 h. And cooling, centrifuging, taking a precipitate to obtain a product, and carrying out column chromatography purification on the product by taking neutral alumina with 200-300 meshes as a stationary phase and taking a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:3 as a mobile phase to obtain the product, namely beta-tetraethyleneoxy ethoxy zinc phthalocyanine with deep blue color.
Wherein the tri-n-propylamine has the structural formulaThe structural formula of the beta-tetraethyleneoxy ethoxy zinc phthalocyanine is +.>
The chemical reaction formula related to the above is shown as follows:
referring to fig. 4, 5 and 6, fig. 4 is an ultraviolet fluorescence absorption spectrum of beta-tetraethyleneoxy ethoxy zinc phthalocyanine, fig. 5 is an infrared absorption spectrum of beta-tetraethyleneoxy ethoxy zinc phthalocyanine, and fig. 6 is a mass spectrum of beta-tetraethyleneoxy ethoxy zinc phthalocyanine.
When the metal element in the phthalocyanine is other metal element, zinc acetate dihydrate in the embodiment 1 can be replaced by corresponding metal salt, such as copper chloride and nickel acetate, and other preparation methods are the same, and reference can be made to the embodiment 1.
When the substituent at the β -position in the phthalocyanine is other types of alcohol compounds, the ethylene glycol monovinyl ether in example 1 may be replaced with an alcohol compound corresponding to the substituent at the β -position, such as 3-buten-1-ol, diethylene glycol monovinyl ether, etc., and other preparation methods are the same, and reference is made to example 1.
Example 2
S10, synthesizing 4- (4-ethyleneoxyphenoxy) -1, 2-phthalonitrile by adopting a liquid-phase potassium carbonate catalytic method: the reactants are respectively measured according to the mol ratio of the 4-nitrophthalonitrile to the 4-vinyl phenol of 1:2: 4g of 4-nitrophthalonitrile and 5.5g of 4-vinylphenol, then the reactants and a first catalyst (12 g of potassium carbonate, 5g of potassium iodide and 5g of tetrabutylammonium iodide) are dissolved in 40mL of DMF solvent and mixed to form a first reaction system, the first reaction system is added into a 150mL flask, and then the flask is placed in a water bath at 60 ℃ and stirred and mixed for 4 hours to allow the reactants in the flask to react. After cooling, 100mL of ethyl acetate and 400mL of ultrapure water are used for extraction, an upper ethyl acetate organic phase is taken, ethyl acetate solvent is removed by rotary evaporation, a product is obtained, neutral alumina with 200-300 meshes is taken as a stationary phase, a mixture of dichloromethane and petroleum ether with the volume ratio of dichloromethane to petroleum ether being 1:4 is taken as a mobile phase for column chromatography purification, and a powdery white crystal product 4- (4-vinyl phenoxy) -1, 2-benzene dinitrile is obtained. Wherein the petroleum ether is C n H 2n+2 (n＝5～8)。
Wherein, the structural formula of the 4-vinyl phenol is as follows:the structural formula of the 4- (4-vinyl phenoxy) -1, 2-phthalonitrile is as follows: / >
The chemical reaction formula involved in the above reaction is shown as follows:
s20, adopting liquid-phase DBU to catalyze and synthesize beta-tetravinyl phenoxy phthalocyanine: 15mL of N-pentanol and 0.5mL of DBU were measured respectively according to a volume ratio of N-pentanol to DBU of 30:1, and then mixed with 1.5g of the obtained 4- (4-vinylphenoxy) -1, 2-phthalonitrile to form a second reaction system, the second reaction system was added into a 250mL flask, the flask was connected to a condensing reflux device, an oil bath at 140℃was performed (the flask was heated in simethicone), and the mixture was stirred under N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 15 h. After cooling, centrifuging the materials in the flask, taking a precipitate as a product, taking 200-300 mesh neutral alumina as a stationary phase, and taking methylene dichloride as a stationary phase: ethyl acetate: and (3) performing column chromatography purification on a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:1 serving as a mobile phase to obtain the product beta-tetravinyl phenoxy phthalocyanine, wherein the color of the product beta-tetravinyl phenoxy phthalocyanine is dark green.
The chemical reaction formula involved in the above reaction is shown as follows:
s30, catalyzing and synthesizing beta-tetra-vinyl phenoxy zinc phthalocyanine by adopting liquid-phase tri-n-propylamine: according to the volume ratio of n-amyl alcohol to tri-n-propylamine of 30:1, respectively measuring 15mL of n-amyl alcohol and 0.5mL of tri-n-propylamine, and mixing to form a reaction system A; According to the mol ratio of the beta-site tetra-vinyl phenoxy phthalocyanine to the zinc acetate dihydrate of 1:3, respectively measuring 1.5g of beta-site tetra-vinyl phenoxy phthalocyanine and 0.9g of zinc acetate dihydrate, and mixing to form a reaction system B; the reaction system A, B was put into a 250mL flask, the flask was connected to a condensing reflux apparatus, the flask was subjected to an oil bath at 160℃and N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 6 h. And (3) cooling, centrifuging, taking a precipitate to obtain a product, and carrying out column chromatography purification on the product by taking neutral alumina with 200-300 meshes as a stationary phase and taking a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:3 as a mobile phase to obtain the product, namely beta-tetravinyl phenoxy zinc phthalocyanine with a dark blue color.
Wherein, the structural formula of the beta-tetravinyl phenoxy zinc phthalocyanine is as follows:
the chemical reaction formula related to the above is shown as follows:
referring to fig. 7, fig. 7 is a mass spectrum of β -tetra-vinyl phenoxy zinc phthalocyanine.
Comparative example 1
S10, synthesizing 4- (methoxyethoxy) -1, 2-phthalonitrile by adopting a liquid-phase potassium carbonate catalytic method: the reactants are respectively measured according to the mol ratio of the 4-nitrophthalonitrile to the ethylene glycol monomethyl ether of 1:2: 4g of 4-nitrophthalonitrile and 3.52g of ethylene glycol monomethyl ether, then the reactants and a first catalyst (12 g of potassium carbonate, 5g of potassium iodide and 5g of tetrabutylammonium iodide) are dissolved in 40mL of DMF solvent and mixed to form a first reaction system, the first reaction system is added into a 150mL flask, and then the flask is placed in a water bath at 60 ℃ and stirred and mixed for 4 hours to react the reactants in the flask. After cooling, 100mL ethyl acetate, 400mL super was used Extracting with pure water, taking an upper ethyl acetate organic phase, removing an ethyl acetate solvent by rotary evaporation to obtain a product, and carrying out column chromatography purification on the product by taking neutral alumina with 200-300 meshes as a stationary phase and taking a mixture of dichloromethane and petroleum ether with the volume ratio of dichloromethane to petroleum ether of 1:1 as a mobile phase to obtain an acicular white crystal product 4- (methoxyethoxy) -1, 2-phthalonitrile. Wherein the petroleum ether is C n H 2n+2 (n＝5～8)。
Wherein, the structural formula of the ethylene glycol monomethyl ether is:the structural formula of the 4- (methoxyethoxy) -1, 2-phthalonitrile is as follows: />
The chemical reaction formula involved in the above reaction is shown as follows:
/>
s20, adopting liquid-phase DBU to catalyze and synthesize beta-tetramethoxyethoxy phthalocyanine: 15mL of N-pentanol and 0.5mL of DBU were measured respectively according to a volume ratio of N-pentanol to DBU of 30:1, and then mixed with 2g of the obtained 4- (ethoxymethoxy) -1, 2-phthalonitrile to form a second reaction system, the second reaction system was added into a 250mL flask, the flask was connected to a condensing reflux device, an oil bath at 140℃was performed (the flask was heated in simethicone), and the mixture was stirred under N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 15 h. After cooling, centrifuging the materials in the flask, taking a precipitate as a product, taking 200-300 mesh neutral alumina as a stationary phase, and taking methylene dichloride as a stationary phase: ethyl acetate: and (3) performing column chromatography purification by taking a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:1 as a mobile phase to obtain the product beta-tetramethoxyethoxy phthalocyanine, wherein the color is dark green.
Wherein, the structural formula of the beta-tetramethoxyethoxy phthalocyanine is as follows:
the chemical reaction formula involved in the above reaction is shown as follows:
s30, catalyzing and synthesizing beta-tetramethoxyethoxy zinc phthalocyanine by adopting liquid-phase tri-n-propylamine: according to the volume ratio of n-amyl alcohol to tri-n-propylamine of 30:1, respectively measuring 15mL of n-amyl alcohol and 0.5mL of tri-n-propylamine, and mixing to form a reaction system A; according to the mol ratio of the beta-tetramethoxyethoxy phthalocyanine to the zinc acetate dihydrate of 1:3, respectively measuring 2g of the beta-tetramethoxyethoxy phthalocyanine and 1.53g of the zinc acetate dihydrate, and mixing to form a reaction system B; the reaction system A, B was put into a 250mL flask, the flask was connected to a condensing reflux apparatus, the flask was subjected to an oil bath at 160℃and N 2 The reaction was allowed to react completely in the flask by stirring under an atmosphere for 6 h. And (3) cooling, centrifuging, taking a precipitate to obtain a product, and carrying out column chromatography purification on the product by taking neutral alumina with 200-300 meshes as a stationary phase and taking a mixture of dichloromethane, ethyl acetate and ethanol with the volume ratio of 200:100:1 as a mobile phase to obtain the product, namely the beta-tetramethoxyethoxyzinc phthalocyanine with deep blue color.
Wherein the tri-n-propylamine has the structural formula The structural formula of the beta-tetramethoxyethoxy zinc phthalocyanine is +.>
The chemical reaction formula related to the above is shown as follows:
device example 1
Configuration of perovskite precursor solution: pbI is prepared 2 The CsI, FAI and NMP (N-methylpyrrolidone) were dissolved in DMF (N, N-dimethylformamide) at a molar ratio of 1:0.1:0.9:1, and stirred continuously for 1 hour to dissolve completely to prepare FA 0.9 Cs 0.1 PbI 3 Perovskite precursor solution, the concentration is 1.4mol/L;
cleaning a substrate: will be made of conductive glass/dense ZnO-ZnS layer/mesoporous SnO 2 The substrate formed by the layers is annealed for 60min under the air atmosphere and the temperature condition of 150 ℃, and after the temperature is reduced to room temperature, the substrate is transferred to a glove box. Wherein the conductive glass is FTO glass, znO-ZnS layer/mesoporous SnO 2 The layer is an electron transport layer.
Preparation of perovskite light absorbing layer: FA is set up 0.9 Cs 0.1 PbI 3 Spin-coating the perovskite precursor solution on the substrate, wherein the rotating speed is 6000r/min, and the spin-coating time is 30s, and 1mL of diethyl ether is dropwise added at 27 s; annealing at 110 ℃ for 30min; and then annealing at 130 ℃ for 30min to form the perovskite light absorption layer. The thickness of the perovskite light absorbing layer is 400nm.
Preparation of hole transport layer: mixing the polymerizable metal phthalocyanine in the example 1, namely beta-tetraethyleneoxy ethoxy zinc phthalocyanine, with DMAP and chloroform to form a polymerizable metal phthalocyanine mixed solution, wherein the concentration of the beta-tetraethyleneoxy ethoxy zinc phthalocyanine is 15mg/mL, and the concentration of the DMAP is 0.15mg/L; spin-coating the polymerizable metal phthalocyanine mixed solution on the perovskite light absorption layer, wherein the rotating speed is 4000r/min, the spin-coating time is 20s, and at the 5 th s, 15 mu L of trichloromethane solution (with the concentration of 15 mg/mL) of beta-tetraethyleneoxy ethoxy zinc phthalocyanine is dropwise added to form a prefabricated film layer; and irradiating for 3min under ultraviolet light to enable beta-tetraethyl oxyethoxy zinc phthalocyanine to form poly beta-tetraethyl oxyethoxy zinc phthalocyanine on the perovskite surface in situ, and curing the prefabricated film layer to obtain the hole transport layer. The thickness of the hole transport layer was 30nm.
Preparation of a second electrode: and forming a gold electrode on the hole transport layer by using a thermal evaporation method. The thickness of the gold electrode was 60nm.
The preparation process is carried out in an environment with the humidity of 10-15%.
Device example 2
The difference from device example 1 is that the polymerizable metal phthalocyanine in device example 2 employs the beta-tetra-vinyl phenoxy zinc phthalocyanine in example 2, and the other preparation process is the same as device example 1.
Device example 3
The difference from device example 1 is that the material of the hole transport layer is different, and the preparation of device example 3 further includes preparing an interface layer between the perovskite light absorbing layer and the hole transport layer, other preparation processes being the same as device example 1.
Preparation of an interface layer: mixing the polymerizable metal phthalocyanine in the example 1, namely beta-tetraethyleneoxy ethoxy zinc phthalocyanine, with DMAP and chloroform to form a polymerizable metal phthalocyanine mixed solution, wherein the concentration of the beta-tetraethyleneoxy ethoxy zinc phthalocyanine is 1mg/mL, and the concentration of the DMAP is 0.1mg/L; spin-coating the polymerizable metal phthalocyanine mixed solution on the perovskite light absorption layer, wherein the rotating speed is 4000r/min, the spin-coating time is 20s, and at the 5 th s, 15 mu L of trichloromethane solution (with the concentration of 1 mg/mL) of beta-tetraethyleneoxy ethoxy zinc phthalocyanine is dropwise added to form a prefabricated film layer; and irradiating for 3min under ultraviolet light to enable beta-tetraethyleneoxy ethoxy zinc phthalocyanine to form poly beta-tetraethyleneoxy ethoxy zinc phthalocyanine on the perovskite surface in situ, and curing the prefabricated film layer to obtain the interface transmission layer.
The hole transport layer is made of a main material of spiro-OMeTAD, a doping material of tetra-tert-butylpyridine (tBP) and lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI).
Preparation of hole transport layer: after mixing a solution of spiro-OMeTAD in chlorobenzene (30 mg/mL concentration) with tetra-tert-butylpyridine (tBP) and 9.1mg of lithium bistrifluoromethane-sulfonyl-imide (Li-TFSI) uniformly, spin-coating on FA 0.9 Cs 0.1 PbI 3 The perovskite film is coated with the coating material, wherein the rotating speed is 4000r/min, and the spin coating time is 20s; then atAnd irradiating for 3min under ultraviolet light to obtain the hole transport layer. Wherein, in the mixed solution, tBP is 28.8 mu L and Li-TFSI is 9.1mg in each milliliter of chlorobenzene.
Device comparative example 1
The difference from device example 1 is that the polymerizable metal phthalocyanine in device comparative example 1 employs the β -tetramethoxyethoxy zinc phthalocyanine in comparative example 1. Other preparation processes were the same as in device example 1.
Device comparative example 2
The difference from device example 1 is that the hole transport layer of device comparative example 2 is made of a host material of spiro-ome tad and a doping material of tetra-t-butylpyridine (tBP) and lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI), unlike the hole transport layer of device comparative example 2. Other preparation processes were the same as in device example 1.
Specifically, preparation of a hole transport layer: after mixing a solution of spiro-OMeTAD in chlorobenzene (30 mg/mL concentration) with tetra-tert-butylpyridine (tBP) and 9.1mg of lithium bistrifluoromethane-sulfonyl-imide (Li-TFSI) uniformly, spin-coating on FA 0.9 Cs 0.1 PbI 3 The perovskite film is coated with the coating material, wherein the rotating speed is 4000r/min, and the spin coating time is 20s; and irradiating for 3min under ultraviolet light to obtain the hole transport layer. Wherein, in the mixed solution, tBP is 28.8 mu L and Li-TFSI is 9.1mg in each milliliter of chlorobenzene.
Device comparative example 3
The difference from device example 1 is that the hole transport layer was prepared in device comparative example 3 by a process different from that of device comparative example 3 in that the hole transport layer was prepared without ultraviolet irradiation, i.e., beta-tetraethyleneoxy ethoxy zinc phthalocyanine was not polymerized, and other preparation processes were the same as those of device example 1.
Referring to fig. 8, fig. 8 is a graph comparing the stability of solar cells prepared in device examples 1 to 2 and device comparative examples 1 to 2. Wherein the abscissa is the solar cell placement Time (Time) and the ordinate is the photoelectric conversion efficiency (Normalized PCE), and the test is measured under the conditions of humidity of 85RH% and temperature of 85 ℃. As can be seen from fig. 8, the solar energy in device example 1 and device example 2 After the solar cell is placed for 800 hours, the photoelectric conversion efficiency of the solar cell is maintained to be about 95% of the original efficiency, the solar cell taking the Spiro-OMeTAD as a hole transport layer in the device comparative example 2 is rapidly reduced after being placed for 200 hours, and after the solar cell is placed for 800 hours, the photoelectric conversion efficiency of the solar cell is less than 20% of the original efficiency, and obviously, the stability of the solar cell can be greatly improved by the polymerizable metal phthalocyanine provided by the application. The possible reason is that in the beta-substituent of the polymerizable metal phthalocyanine of the present application, the lone pair electrons present in the oxygen atom can be bonded to the metal cation such as Pb of the perovskite surface 2+ Coordination combination is carried out to form Pb-O bond, the effect of fixing metal cations is achieved, the stability of the solar cell can be improved, and after alkenyl or alkynyl is polymerized in situ to form a molecular polymer, halogen anions such as I-upward migration on the surface of perovskite can be effectively inhibited, so that the stability of the solar cell is further enhanced.
The solar cells prepared in device examples 1 to 3 and device comparative examples 1 to 3 were tested for performance, and the test results are shown in table 1, fig. 9, fig. 10 and fig. 11. Wherein V is oc Is open circuit voltage, J sc For short-circuit current, FF is the fill factor and PCE is the photoelectric conversion efficiency. Fig. 9 is a graph of current versus voltage for the solar cell performance prepared in device examples 1 and 2 and device comparative examples 1 and 2, fig. 10 is a graph of current versus voltage for the solar cell performance prepared in device example 3 and device comparative example 2, and fig. 11 is a graph of current versus voltage for the solar cell performance prepared in device comparative example 3.
TABLE 1
Device and method for manufacturing the same V oc (V) J sc (mA/cm 2 ) FF(％) PCE(％)
Device example 1 1.04 23.26 73.51 17.87
Device example 2 1.03 22.33 72.87 16.75
Device example 3 1.06 23.97 76.00 19.29
Device comparative example 1 1.04 22.23 72.83 16.81
Device comparative example 2 1.09 27.76 73.99 20.48
Device comparative example 3 0.82 22.42 29.93 5.49
From Table 1, and FIGS. 9 and 11, it is understood that the photoelectric conversion efficiency of the solar cell of device example 1 is superior to that of the solar cell of device comparative example 1, probably because, among the β -substituent groups of the polymerizable metal phthalocyanine, the terminal group containing a carbon-carbon double bond or a carbon-carbon triple bond is effective in inhibiting halogen anions such as I on the perovskite surface after the alkenyl or alkynyl group is polymerized in situ to form a molecular polymer as compared with the alkoxy terminal group - Migrate upward to improve battery efficiency.
From Table 1 and FIG. 10, it is understood that the photoelectric conversion efficiency of the solar cell of device example 3 is superior to that of the solar cell of device comparative example 2, probably because the lone pair electrons present in the oxygen atom can be combined with the metal cation such as Pb on the perovskite surface when the polymerizable metal phthalocyanine is applied to the interfacial layer in the solar cell 2+ Coordination bonding to form Pb-O bond, which plays a role in fixing metal cations, improves the stability of solar cells, and can effectively inhibit halogen anions such as I on perovskite surface after alkenyl or alkynyl is polymerized in situ to form molecular polymer - Upward migration further enhances the stability and cell efficiency of the solar cell.
In addition, the inventors performed fluorescence lifetime tests on device example 1, device comparative example 2, and perovskite film layers alone. Referring to fig. 12 and 13, fig. 12 is a time resolved photoluminescence spectrum of device example 1, device comparative example 1, and the perovskite light absorbing layer alone, and fig. 13 is a steady state fluorescence spectrum of device example 1, device comparative example 2, and the perovskite light absorbing layer. In fig. 12, the faster the ordinate of the photoluminescence spectrum curve (corresponding to the fluorescence lifetime curve) decreases over time, indicating the faster the hole extraction. As can be seen from fig. 12 and 13, when the polymerizable metal phthalocyanine provided in device example 1 is used as a hole transport material, it has excellent hole extraction ability and can effectively conduct out holes in the perovskite light absorbing layer.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and for parts of one embodiment that are not described in detail, reference may be made to related descriptions of other embodiments.
The polymerizable metal phthalocyanine, the preparation method thereof, the solar cell and the preparation method thereof provided by the embodiment of the invention are described in detail, and specific examples are applied to the description of the principle and the implementation mode of the invention, and the description of the above examples is only used for helping to understand the technical scheme and the core idea of the invention; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. A polymerizable metal phthalocyanine, which is characterized by having a structural formula (I) as follows:
wherein M is selected from zinc, nickel, copper, palladium, aluminum, iron, cobalt, magnesium, platinum, indium, ruthenium, titanium, lead, gallium or manganese;
R 1 、R 2 、R 3 、R 4 independently of one another selected fromWherein R is 5 Bonded to O in formula (I), R 5 Selected from single bond, alkyl group with 1-2 carbon atoms with 1-3 carbon atoms substituted or unsubstituted alkoxy group with 1-3 carbon atoms, or alkoxy ether group with 2-4 carbon atoms, L is selected from O or single bond, and L is selected from O, R 5 Selected from single bonds not occurring simultaneously, R 6 Selected from vinyl, ethynyl or vinyl phenyl;
wherein when R is 6 Is selected from vinyl or ethynyl, R when L is selected from single bond 5 Selected from the group consisting of an alkyl group having 1 to 2 carbon atoms in which the at least one H is substituted with an alkoxy group having 1 to 3 carbon atoms, and an alkoxy ether group having 2 to 4 carbon atoms.
2. The polymerizable metal phthalocyanine according to claim 1, wherein R 5 Selected from alkyl groups having 1 to 2 carbon atoms.
3. The polymerizable metal phthalocyanine of claim 1, wherein said polymerizable metal phthalocyanine comprises at least one of the following structural formulas:
4. A process for the preparation of a polymerizable metal phthalocyanine according to any one of claims 1 to 3, comprising the steps of:
carrying out a first reaction and impurity removal on 4-nitrophthalonitrile and a first reactant at a first temperature to obtain a first intermediate, wherein the structural formula of the first reactant is as follows:the structural formula of the first intermediate is as follows:
combining said first intermediate with 1, 8-diazabicyclo [5.4.0]Performing a second reaction and impurity removal on undec-7-ene at a second temperature to obtain a second intermediate, wherein the structural formula of the second intermediate is as follows:
performing third reaction and impurity removal on the second intermediate and metal salt of M metal at a third temperature to obtain the polymerizable metal phthalocyanine, wherein the structural formula of the polymerizable metal phthalocyanine is as follows:
5. the process for producing a polymerizable metal phthalocyanine according to claim 4, wherein the molar ratio of 4-nitrophthalonitrile to said first reactant is 1 (1-2); and/or the molar ratio of the second intermediate to M metal ions in the metal salt is 1 (1-3).
6. The method for preparing a polymerizable metal phthalocyanine according to claim 4, wherein the first temperature is 55 to 65 ℃ and the first reaction time is 3 to 5 hours; and/or the second temperature is 135-145 ℃, and the second reaction time is 13-17 h; and/or the third temperature is 155-165 ℃, and the time of the third reaction is 4-8 h.
7. A solar cell comprising a first electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second electrode, which are laminated in sequence, wherein the hole transport layer comprises a metal phthalocyanine polymer;
alternatively, the solar cell comprises a first electrode, an electron transport layer, a perovskite light absorption layer, an interface layer, a hole transport layer and a second electrode which are sequentially laminated, wherein the interface layer comprises a metal phthalocyanine polymer;
wherein the metal phthalocyanine polymer is a polymer polymerized from the polymerizable metal phthalocyanine according to any one of claims 1 to 3 or a polymer polymerized from the polymerizable metal phthalocyanine produced by the production method according to any one of claims 4 to 6.
8. A method of manufacturing a solar cell, the method comprising the steps of:
providing a substrate comprising a first electrode and an electron transport layer laminated in sequence;
forming a perovskite light absorbing layer on the electron transport layer;
forming a hole transport layer on the perovskite light absorbing layer, wherein the material of the hole transport layer comprises a polymer polymerized by the polymerizable metal phthalocyanine according to any one of claims 1 to 3 or a polymer polymerized by the polymerizable metal phthalocyanine prepared by the preparation method according to any one of claims 4 to 6;
Forming a second electrode on the hole transport layer;
or, the preparation method comprises the following steps:
providing a substrate comprising a first electrode and an electron transport layer laminated in sequence;
forming a perovskite light absorbing layer on the electron transport layer;
forming an interface layer on the perovskite light absorbing layer, wherein the material of the interface layer comprises a polymer polymerized by the polymerizable metal phthalocyanine according to any one of claims 1 to 3 or a polymer polymerized by the polymerizable metal phthalocyanine prepared by the preparation method according to any one of claims 4 to 6;
forming a hole transport layer on the interfacial layer;
a second electrode is formed on the hole transport layer.
9. The method for manufacturing a solar cell according to claim 8, wherein when the material of the hole transport layer includes the polymer, the forming of the hole transport layer includes the steps of:
mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine;
coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer;
carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction;
Or, when the interfacial layer comprises the polymer, the preparation of the interfacial layer comprises the following steps:
mixing the polymerizable metal phthalocyanine, an initiator and a solvent to form a mixed solution of the polymerizable metal phthalocyanine;
coating the mixed solution of the polymerizable metal phthalocyanine on the perovskite light absorption layer to form a prefabricated film layer;
and carrying out ultraviolet light treatment or heating treatment on the prefabricated film layer so as to enable the polymerizable metal phthalocyanine to carry out polymerization reaction.
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