CN110858626A - Blend, blend film containing blend, photovoltaic active layer and device and preparation method of blend - Google Patents

Blend, blend film containing blend, photovoltaic active layer and device and preparation method of blend Download PDF

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CN110858626A
CN110858626A CN201810973429.7A CN201810973429A CN110858626A CN 110858626 A CN110858626 A CN 110858626A CN 201810973429 A CN201810973429 A CN 201810973429A CN 110858626 A CN110858626 A CN 110858626A
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blend
active layer
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CN110858626B (en
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朱晓张
周子春
许胜杰
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Institute of Chemistry CAS
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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Abstract

The invention belongs to the technical field of organic solar cells, and particularly relates to a blend suitable for a photovoltaic active layer, a blend film containing the blend, the photovoltaic active layer, a device and a preparation method of the photovoltaic active layer and the device. The blend film can be used as a photovoltaic active layer of an organic solar cell, and a solar device comprising the photovoltaic active layer has excellent photoelectric conversion efficiency which can reach 13.20 +/-0.25% at most, and is beneficial to industrial large-scale preparation. In addition, the invention clearly represents and infers the morphology details influencing the photoelectric performance parameters in the ternary blend film for the first time, and provides a strategy for finely controlling the morphology of the ternary blend film. Compared with a binary device, under the action of the hierarchical structure morphology, the performance of the ternary device is improved by over 50 percent, which is far superior to the reported result of the current ternary device.

Description

Blend, blend film containing blend, photovoltaic active layer and device and preparation method of blend
Technical Field
The invention belongs to the technical field of organic solar cells, and particularly relates to a blend, a blend film containing the blend, a photovoltaic active layer, a photovoltaic active device and a preparation method of the blend.
Background
The core of the organic solar cell for realizing photoelectric conversion is a binary organic blend film composed of a donor and a receptor, but the organic material is limited by the characteristic that the absorption bandwidth is too narrow, and the film composed of binary components cannot fully absorb the energy of the full wavelength of the solar spectrum. The ternary organic solar cell can fully absorb sunlight by introducing a third component material with more complementary spectrum, and simultaneously constructs a more favorable electronic structure and a more favorable molecular accumulation morphology structure, so that the ternary organic solar cell is an important way for improving the energy conversion efficiency of the organic solar cell. In the ternary organic solar cell, how to effectively utilize the interaction among three components to form the most favorable morphology structure is a necessary way to obtain a high-performance solar cell, thereby ensuring that sufficient current is generated, effective charge transmission is ensured, and open-circuit voltage loss is inhibited. However, in the ternary organic solar cell reported in the literature at present, research focuses mainly on a large number of blind choices of materials, the material selection principle is only limited to electronic structure matching, and the performance improvement of the ternary device relative to the binary device is also weak. In addition, the appearance details in the ternary blend film cannot be accurately characterized and inferred at present, so that the influence of the appearance details on the final photovoltaic performance parameters cannot be systematically researched, and a clear ternary blend film appearance control strategy cannot be provided for promoting the development of the ternary organic solar cell.
Disclosure of Invention
To ameliorate the above technical problem, the present invention provides a blend suitable for use in a photovoltaic active layer, the blend comprising a strong crystalline donor, a non-fullerene acceptor and a fullerene derivative.
According to the invention, the strong crystalline donor is selected from strong crystalline, wide band gap donors; the non-fullerene receptor is selected from the group consisting of weakly crystalline, narrow bandgap non-fullerene receptors.
According to the present invention, the miscibility between the non-fullerene acceptor and the strong crystalline donor is good.
According to the invention, the mass ratio of the strong crystal donor, the non-fullerene acceptor and the fullerene derivative is 1 (0.1-0.9):1, preferably 1 (0.2-0.8):1, such as 1:0.2:1, 1:0.4:1, 1:0.6:1, 1:0.8: 1.
According to the invention, the non-fullerene receptor is selected from compounds of formula (I):
Figure BDA0001776817710000021
in formula (I), Q, Q' are identical or different and are independently selected from
Figure BDA0001776817710000022
R、R’、R”、R”’、R1、R2Identical or different, independently of one another, from hydrogen, halogen, hydroxyl, mercapto, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio, -NRaRbRc、-C(＝O)Rd、-OC(＝O)Rd、-S(＝O)Rd、-S(＝O)2Rd(ii) a A. A', equal to or different from each other, are independently selected from the following groups:
Figure BDA0001776817710000024
Figure BDA0001776817710000031
R3、R4、R5、R6、R7、R8、R9、R10identical or different, independently of one another, from hydrogen, halogen, hydroxyl, mercapto, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycleAlkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio, -NRaRbRc、-C(＝O)Rd、-OC(＝O)Rd、-S(＝O)Rd、-S(＝O)2Rd；
X1、X2Identical or different, independently from each other selected from O, S, Se;
Y1、Y2identical or different, independently of one another, from N, unsubstituted or substituted by RsSubstituted CH;
each Y3Identical or different, independently of one another, from O, S, Se, unsubstituted or substituted by RsSubstituted of the following groups: CH (CH)2、NH；
Z1、Z2Identical or different, independently from each other selected from O, S;
Ra、Rb、Rc、Rdidentical or different, independently of one another, from hydrogen, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl;
each RsIdentical or different, independently of one another, from: halogen, hydroxy, mercapto, cyano, nitro, carbonyl, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio.
According to the present invention, the compound of formula (I) is a weakly crystalline, narrow bandgap non-fullerene acceptor.
According to the invention, the strong crystalline donor is selected from compounds of formula (II):
Figure BDA0001776817710000041
in formula (II), E, E ', E ', G, G ' are the same or different and are each otherIndependently selected from hydrogen, halogen, hydroxy, mercapto, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio, heterocycloalkylthio, heterocycloalkyloxy, arylthio, and the like,
Figure BDA0001776817710000042
RnSelected from hydrogen, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl;
Rshaving the definitions as described above.
According to the invention, the compound of formula (II) is a strongly crystalline, wide band gap donor.
According to the invention, the miscibility of the compound of formula (I) with the compound of formula (II) is good.
According to the invention, the fullerene derivative is selected from a C60 derivative or a C70 derivative, including but not limited to: PC (personal computer)61BM([6,6]-phenyl C61 butyric acid methyl ester), PC71BM([6,6]-phenyl C71 methyl butyrate), indene-containing fullerenes, and the like.
According to the invention, the mass ratio of the compound shown in the formula (II), the compound shown in the formula (I) and the fullerene derivative is 1 (0.1-0.9):1, preferably 1 (0.2-0.8):1, such as 1:0.2:1, 1:0.4:1, 1:0.6:1 and 1:0.8: 1.
The invention also provides a blended film suitable for a photovoltaic active layer, which comprises the blend, wherein the blended film has graded morphology.
According to the invention, the grading morphology is specifically: the non-fullerene acceptor and the strong crystal donor in the blended film are taken as a whole and are separated from the fullerene derivative, and the fullerene derivative forms a large-scale network structure and is taken as an expressway for electron transmission. The non-fullerene acceptor creates a phase separation of a small scale from the strong crystalline donor and isolates the contact between the strong crystalline donor and the fullerene derivative, dominating the photoelectric process of charge generation and charge separation. The separated holes migrate in the strongly crystalline donor. The separated electrons are transferred to the electrode at a high speed through the fullerene derivative and then extracted by an external circuit, and the open voltage loss generated by the contact of the fullerene derivative and the strong crystal donor is completely suppressed in the process.
According to the invention, the thickness of the blend film can be 100-500nm, preferably 200-500nm, such as 200nm, 300nm, 400nm, 500 nm.
The invention also provides a preparation method of the blend film, which comprises a step of spin coating film formation and a step of solvent steam treatment.
According to the invention, the preparation method specifically comprises the following steps:
(1) preparing a blend solution;
(2) spin-coating the blend solution to form a film;
(3) and (3) treating the blended film obtained in the step (2) by using solvent steam, and inducing crystallization to obtain the blended film.
According to the invention, the step (1) is specifically as follows: dissolving the blend in a solvent; the solvent may be one, two or more selected from halogenated hydrocarbon solvents, ether solvents, alcohol solvents, etc., preferably halogenated hydrocarbon solvents such as chloroform.
According to the invention, the mass ratio of the strong crystal donor, the non-fullerene acceptor and the fullerene derivative in the blend is 1 (0.1-0.9):1, preferably 1 (0.2-0.8):1, such as 1:0.2:1, 1:0.4:1, 1:0.6:1, 1:0.8: 1.
According to the present invention, in the step (3), the solvent vapor treatment is preferably a Solvent Vapor Annealing (SVA) treatment;
the solvent used in the solvent vapor treatment may be one, two or more kinds of ether solvents, halogenated hydrocarbon solvents, ketone solvents, etc., preferably an ether solvent such as tetrahydrofuran.
The invention also provides a photovoltaic active layer, which comprises the blend film.
According to the present invention, the photovoltaic active layer may be a photovoltaic active layer of an organic solar cell.
According to the invention, the non-fullerene acceptor and fullerene derivatives in the photovoltaic active layer can be used as photovoltaic acceptor materials, and the strong crystal donor can be used as photovoltaic donor materials.
According to the invention, the thickness of the photovoltaic active layer can be 100-500nm, preferably 200-500nm, such as 200nm, 300nm, 400nm, 500 nm.
The invention also provides a device comprising the photovoltaic active layer.
According to the invention, the device is a solar cell device, for example an organic solar cell device.
According to the invention, the device comprises the following structure stacked in sequence: the photovoltaic device comprises a conductive substrate layer, a hole buffer layer, the photovoltaic active layer, an electron transport layer and a conductive cathode;
according to the invention, the conductive substrate layer is an ITO electrode;
the hole buffer layer is made of PEDOT: PSS;
the electron transport layer is PNDIT-F3N;
the conductive cathode is aluminum;
according to the invention, when the thickness of the photovoltaic active layer is 300nm, the energy conversion rate (PCE) of the device can be as high as 13.20 +/-0.25%; the energy conversion (PCE) of the device can reach 10.56 +/-0.23% when the thickness of the photovoltaic active layer is 500 nm.
The invention also provides a preparation method of the device, which comprises the following steps:
(1) performing surface pretreatment on the conductive substrate layer;
(2) spin coating a hole buffer layer material on the base layer;
(3) preparing a photovoltaic active layer substance solution;
(4) spin coating a photovoltaic active layer material solution on the surface of the hole buffer layer;
(5) spin-coating an electron transport layer material solution on the surface of the photovoltaic active layer;
(6) and thermally evaporating a cathode material onto the electron transport layer to obtain the device.
According to the invention, in step (1), the conductive substrate layer is preferably an ITO glass substrate.
According to the invention, in step (1), the pretreatment may be specifically: and ultrasonically cleaning the conductive substrate layer by using soap water, deionized water, acetone and isopropanol in sequence. The washed substrate is subjected to oxygen plasma treatment to remove organic components from the surface of the substrate.
According to the invention, in step (2), the reaction further comprises a step of removing water from the hole buffer layer, for example, a step of heating and curing at a temperature of 120 ℃ to 180 ℃, for example, 150 ℃ to remove water.
According to the invention, step (3) may be specifically: dissolving a photovoltaic active layer material in a solvent; the solvent is selected from one, two or more of halogenated hydrocarbon solvents, ether solvents, alcohol solvents and the like, and preferably halogenated hydrocarbon solvents such as chloroform.
Advantageous effects
The invention provides a blend suitable for a photovoltaic active layer, a blend film containing the blend, the photovoltaic active layer, a device and a preparation method thereof, wherein the blend film can be used as the photovoltaic active layer of an organic solar cell, the photoelectric conversion efficiency of the solar device containing the photovoltaic active layer is excellent and can reach 13.20 +/-0.25% at most, the blend film is one of the highest performances of a ternary organic solar cell, and the blend film is a high-performance organic photovoltaic device which can be constructed under the condition of a film thickness of more than 200nm and is beneficial to industrial large-scale preparation. In addition, the invention clearly represents and infers the morphology details influencing the photoelectric performance parameters in the ternary blend film for the first time, and provides a strategy for finely controlling the morphology of the ternary blend film. Compared with a binary device, under the action of the hierarchical structure morphology, the performance of the ternary device is improved by over 50 percent, which is far superior to the reported result of the current ternary device. The hierarchical morphology structure solves the fundamental contradiction of phase separation and phase purity in the binary blend film, and is a great breakthrough in morphology control of the active layer of the organic solar cell.
Drawings
FIG. 1 is a schematic representation of a graded profile. Wherein, the gray line is a strong crystal donor, the black line is a non-fullerene receptor, and the gray globule is a fullerene derivative. Electron (e)-) And a cavity (h)+) Electrons are generated between the strong crystalline donor and the non-fullerene acceptor, transferred from the non-fullerene acceptor to the fullerene derivative, and finally transferred to the electrode.
Figure 2 is a statistical analysis of reported ternary device performance. The ternary device in the invention has low energy loss close to ideal under the action of hierarchical morphology, and has obvious effect of improving the performance of the binary device. The performance of the ternary device is improved by over 50 percent.
Detailed Description
Definition and description of terms
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and definitions of groups and structures of compounds after combination are intended to fall within the scope of the present disclosure.
"halogen" as used herein refers to fluorine, chlorine, bromine and iodine.
The numerical ranges used herein at least indicate the number of each integer recited in the range. For example, a numerical range of 1 to 30 indicates values in which 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 are recited.
"alkyl" as used herein alone or as a suffix or prefix, is intended to mean branched and straight chain saturated aliphatic hydrocarbon groups, preferably including branched and straight chain saturated aliphatic hydrocarbon groups having from 1 to 30 carbon atoms (or a specific number of carbon atoms if provided). For exampleThe alkyl group may be C1-10Alkyl radical, said "C1-10Alkyl "denotes alkyl groups having 1,2, 3, 4, 5, 6, 7, 8, 9 and 10 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 2-dimethylbutyl, 2-ethylhexyl, 3-ethylhexyl, 2-hexyldecyl, and the like, and all isomeric forms of the foregoing.
"alkenyl" as used herein alone or as a suffix or prefix, means branched and straight chain aliphatic hydrocarbon radicals containing one or more double bonds, and preferably includes branched and straight chain aliphatic hydrocarbon radicals containing one or more double bonds having from 2 to 30 carbon atoms (or a particular number of carbon atoms if provided). For example, the alkenyl group may be C2-6An alkenyl group. Said "C2-6Alkenyl "denotes alkenyl having 2,3, 4, 5 or 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3-methylbut-1-enyl, 1-pentenyl, 3-pentenyl, and 4-hexenyl.
"alkynyl" as used herein alone or as a suffix or prefix, means branched and straight chain aliphatic hydrocarbon radicals containing one or more triple bonds, and preferably includes branched and straight chain aliphatic hydrocarbon radicals containing one or more triple bonds having from 2 to 30 carbon atoms (or a particular number of carbon atoms if provided). For example ethynyl, propynyl (e.g., l-propynyl, 2-propynyl), 3-butynyl, pentynyl, hexynyl and 1-methylpent-2-ynyl.
The term "aryl" as used herein means an aromatic ring structure composed of carbon atoms, preferably an aromatic ring structure composed of 5 to 20 carbon atoms. For example: the ring structure containing 5, 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as phenyl; the ring structure containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms may be polycyclic, e.g. naphthyl, anthracenyl. The aryl group may be substituted with the above-mentioned substituents at one or more ring positions. For example, one or more of the 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-positions of the aryl group may have the above-mentioned substituents, if appropriate.
The term "aryl" also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are "fused rings"), wherein at least one of the rings is aromatic and the other cyclic rings can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl. Examples of polycyclic rings include, but are not limited to, 2, 3-dihydro-1, 4-benzodioxine and 2, 3-dihydro-1-benzofuran.
The term "cycloalkyl" as used herein means a saturated hydrocarbon ring, which may include fused or bridged polycyclic ring systems. The cycloalkyl group preferably has 3 to 40 carbon atoms in its ring structure. Preferably, the cycloalkyl group has 3, 4, 5 or 6 carbon atoms in its ring structure. For example, "C3-6Cycloalkyl "denotes a group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
As used herein, "heteroaryl" refers to a heteroaromatic heterocycle having at least 1 (e.g., 1,2, or 3 or more) ring heteroatoms (e.g., sulfur, oxygen, or nitrogen). Heteroaryl groups include monocyclic ring systems and polycyclic ring systems (e.g., having 2,3, or 4 fused rings). Examples of heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolinyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, indolyl, pyrrolyl, oxazolyl, benzofuryl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2, 4-thiadiazolyl, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo [1,4] dioxanyl, benzo [1,3] dioxolyl, and the like. In some embodiments, heteroaryl groups have from 3 to 40 carbon atoms and in other embodiments from 3 to 20 carbon atoms. In some embodiments, heteroaryl groups contain 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, heteroaryl has 1 to 4, 1 to 3, or 1 to 2 heteroatoms. In some embodiments, the heteroaryl group has 1 heteroatom.
The heteroaryl group may be substituted with the above substituents at one or more ring positions. For example, one or more of the 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-positions of the heteroaryl group may have the above-mentioned substituents, if appropriate. As an example, when the heteroaryl group is a thienyl or furyl group, one or more of the 2-position, 3-position, 4-position, 5-position thereof may have the above-mentioned substituent. For example, the substituents which form them may be 3-substituted thiophen 2-yl, 4-substituted thiophen 2-yl, 5-substituted thiophen 2-yl, more particularly 3-alkylthiophen 2-yl, 4-alkylthiophen 2-yl, 5-alkylthiophen 2-yl, wherein alkyl has the above-mentioned definition.
The term "heterocyclyl" as used herein, refers to a saturated, unsaturated or partially saturated monocyclic, bicyclic or tricyclic ring (unless otherwise specified) containing 3 to 20 atoms, wherein 1,2, 3, 4 or 5 ring atoms are selected from nitrogen, sulfur or oxygen, which may be attached through carbon or nitrogen, unless otherwise specified, wherein-CH is2-the group is optionally replaced by-c (o) -; and wherein unless otherwise stated to the contrary, the ring nitrogen atom or the ring sulfur atom is optionally oxidized to form an N-oxide or S-oxide or the ring nitrogen atom is optionally quaternized; wherein-NH in the ring is optionally substituted with acetyl, formyl, methyl or methanesulfonyl; and the ring is optionally substituted with one or more halogens. It is understood that when the total number of S and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other. If the heterocyclyl is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is monocyclic, it is not necessarily aromatic. Examples of heterocyclyl groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, N-formylpiperazinyl, N-methanesulfonylpiperazinylHomopiperazinyl, piperazinyl, azetidinyl, oxetanyl, morpholinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, indolinyl, tetrahydropyranyl, dihydro-2H-pyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl-1-oxide, tetrahydrothiopyranyl-1, 1-dioxide, 1H-pyridin-2-one, and 2, 5-dioxoimidazolidinyl.
According to the present invention, the alkylthio group means an alkyl-substituted thio group, the alkyl group having the definition of alkyl group as described above.
According to the present invention, the trialkylsilylethynyl group means an alkyl-substituted silylethynyl group, the alkyl group having the alkyl definition as described above. The trialkylsilylethynyl group may be, for example, trimethylsilylethynyl group, triethylsilylethynyl group, triisopropylsilylethynyl group, tri-tert-butylsilylethynyl group or the like.
A compound of formula (I)
According to an embodiment of the present invention, the compound of formula (I) is selected, for example, from the compounds represented by the following formula (I-1) or the compounds represented by the following formula (I-2).
Figure BDA0001776817710000111
Preparation of Compounds of formula (I)
In the present invention, the preparation method of the compound represented by the formula (I) includes, but is not limited to, the following steps:
1) a compound of the formula:
Figure BDA0001776817710000121
and one or more compounds of formula III selected from:
Figure BDA0001776817710000122
reacting to obtain, for example, one or more compounds of formula IV selected from the group consisting of;
Figure BDA0001776817710000123
2) a compound of formula IV and one or more compounds of formula V selected from:
Figure BDA0001776817710000131
Figure BDA0001776817710000132
reacting to obtain a compound shown as a formula (I);
wherein L is a leaving group, e.g. selected from halogen, such as Br, I; the other groups independently have the definitions described above.
Blends
According to an embodiment of the present invention, preferably, alkyl is C1-30Alkyl, alkenyl being C2-30Alkenyl, alkynyl being C2-30Alkynyl, cycloalkyl being C3-30Cycloalkyl, heterocycloalkyl, being C3-30Heterocycloalkyl, aryl being C6-30Aryl, heteroaryl being C3-30Heteroaryl, trialkylsilylethynyl as tri (C)1-30Alkyl) silylethynyl.
According to an embodiment of the present invention, the blend may include a compound of formula (I-1), a compound of formula (II-1), and PC71BM; wherein, the compound of formula (I-1), the compound of formula (II-1), PC71The BM structure is:
Figure BDA0001776817710000133
among the above compounds, "-C6H13"represents" n-hexyl "," -C8H17"represents" n-octyl "," EH "represents" 2-ethylhexyl ", and" HD "represents" 2-hexyloctyl ".
EXAMPLE 1 preparation of Compound (I-2)
Figure BDA0001776817710000142
1) Preparation of compound 3: n is a radical of2Under the environment, dissolving the compound 1(0.1mmol) and the compound 2(0.3mmol) in a mixed solvent of 3mL of sodium carbonate solution (2M) and 6mL of dioxane, adding tetrakis (triphenylphosphine) palladium (0.026mmol), reacting for 16h at 95 ℃ in the dark, decompressing, removing the solvent, and carrying out column chromatography separation on a residue to obtain an orange compound 3 with the yield of 65%. MS (MALDI-TOF) 1065.2[ M ]]+。
2) Preparation of Compound (I-2): n is a radical of2Under the environment, dissolving the compounds 3(0.065mmol) and 4(0.390mmol) in 6mL of trichloromethane solution, dropwise adding 3 drops of pyridine solution, reacting at 75 ℃ for 16h, removing the solvent by decompression and rotary separation, and carrying out column chromatography separation and purification on residues to obtain a black product, namely the compound (I-2), wherein the yield is 86%. MS (MALDI-TOF) 1417.3[ M ]]+。
Example 2
With reference to the procedure of example 1, other compounds within the scope of formula (I) are prepared, including but not limited to: compound (I-1).
Example 3 preparation of organic solar cell device
The structure of the device is as follows: ITO/PEDOT PSS/photovoltaic active layer/PNDIT-F3N/Al. And ultrasonically cleaning the ITO glass substrate by using soap water, deionized water, acetone and isopropanol in sequence. The washed substrate was subjected to UV irradiation treatment for 10 minutes to remove organic components from the surface of the substrate. Firstly, the method comprises the following steps of: PSS (Clevios P VP 4083) was spin-coated on an ITO substrate at 3000rpm (about 30nm) and heated at 150 ℃ for 5 minutes. The substrate was then transferred to a glove box filled with nitrogen. Subsequently, the compound of the formula (II-1), the compound of the formula (I-1) and PC71Blended chloroform solution of BM spin-coated PEDOT: and (3) the PSS layer. The concrete proportion is as follows: 25mg of the compound of the formula (II-1), 10mg of the compound of the formula (I-1) and 25mg of PC71BM (1:0.4:1) in 1mL of chloroform. Under the condition of representing simulated sunlight irradiation, the photoelectric conversion performance of the device is as high as 13.20 +/-0.25%. The surface profilometer (Dektak XT, Bruker) test shows that the best performance corresponds to the film of the photovoltaic active layerThe thickness is about 300 nm. After the active layer was spin coated, a Solvent Vapor Anneal (SVA) was performed using THF to optimize the mixture morphology and to promote device performance. The procedure was specifically to place the photovoltaically active layer on a 60mm glass petri dish containing 200 μ L THF for various periods of time. The optimum solvent vapor anneal duration was 60 seconds by screening. A methanol solution of PNDIT-F3N as an electron transport layer was then spin coated on the photovoltaic active layer. In the final stage, aluminum (100nm) was thermally evaporated onto the photovoltaic active layer as the top electrode.
Example 4
Referring to the method of example 3, except that the thickness of the photovoltaic active layer was 500nm, the energy conversion rate (PCE) of the organic solar cell device could reach 10.56 ± 0.23%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A blend suitable for use in a photovoltaic active layer, wherein the blend comprises a strong crystalline donor, a non-fullerene acceptor and a fullerene derivative.
2. The blend according to claim 1, characterized in that the strong crystalline donor is selected from strong crystalline, wide bandgap donors; the non-fullerene receptor is selected from the group consisting of weakly crystalline, narrow bandgap non-fullerene receptors;
preferably, the mass ratio of the strong crystal donor, the non-fullerene acceptor and the fullerene derivative is 1 (0.1-0.9):1, preferably 1 (0.2-0.8):1, such as 1:0.2:1, 1:0.4:1, 1:0.6:1, 1:0.8: 1.
3. The blend according to claim 1 or 2, characterized in that said non-fullerene acceptor is selected from the compounds of formula (I):
Figure FDA0001776817700000011
in formula (I), Q, Q' are identical or different and are independently selected from
Figure FDA0001776817700000012
Figure FDA0001776817700000013
R、R’、R”、R”’、R1、R2Identical or different, independently of one another, from hydrogen, halogen, hydroxyl, mercapto, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio, -NRaRbRc、-C(＝O)Rd、-OC(＝O)Rd、-S(＝O)Rd、-S(＝O)2Rd(ii) a A. A', equal to or different from each other, are independently selected from the following groups:
Figure FDA0001776817700000021
R3、R4、R5、R6、R7、R8、R9、R10identical or different, independently of one another, from hydrogen, halogen, hydroxyl, mercapto, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio, -NRaRbRc、-C(＝O)Rd、-OC(＝O)Rd、-S(＝O)Rd、-S(＝O)2Rd；
X1、X2Identical or different, independently from each other selected from O, S, Se;
Y1、Y2identical or different, independently of one another, from N, unsubstituted or substituted by RsSubstituted CH;
each Y3Identical or different, independently of one another, from O, S, Se, unsubstituted or substituted by RsSubstituted of the following groups: CH (CH)2、NH；
Z1、Z2Identical or different, independently from each other selected from O, S;
Ra、Rb、Rc、Rdidentical or different, independently of one another, from hydrogen, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl;
each RsIdentical or different, independently of one another, from: halogen, hydroxy, mercapto, cyano, nitro, carbonyl, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio;
preferably, the compound of formula (I) is a weakly crystalline, narrow bandgap non-fullerene acceptor.
4. The blend according to any of claims 1 to 3, characterized in that said strong crystallization donor is selected from compounds of formula (II):
Figure FDA0001776817700000031
in formula (II), E, E ', E ', G, G ' are the same or different and are independently selected from hydrogen, halogen, hydroxyl, sulfhydryl, cyano, nitro, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, alkenyl, alkynyl,Cycloalkyl, heterocycloalkyl, aryl, heteroaryl, trialkylsilylethynyl, alkyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkylthio, arylthio, heteroarylthio,
Figure FDA0001776817700000032
RnSelected from hydrogen, unsubstituted or optionally substituted by one or more RsSubstituted of the following groups: alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl;
preferably, the compound of formula (II) is a strong crystalline, wide band gap donor.
5. The blend according to any of claims 1-4, characterized in that the fullerene derivative is selected from C60 derivatives or C70 derivatives, such as selected from: PC (personal computer)61BM([6,6]-phenyl C61 butyric acid methyl ester), PC71BM([6,6]-methyl phenyl C71 butyrate), one, two or more indene-containing fullerenes;
preferably, the mass ratio of the compound represented by the formula (II), the compound represented by the formula (I) and the fullerene derivative is 1 (0.1-0.9):1, preferably 1 (0.2-0.8):1, such as 1:0.2:1, 1:0.4:1, 1:0.6:1 and 1:0.8: 1.
6. A blended film suitable for use in a photovoltaic active layer, comprising the blend of any of claims 1-5, wherein the blended film has a graded morphology;
preferably, the thickness of the blend film is 100-500nm, preferably 200-500nm, such as 200nm, 300nm, 400nm, 500 nm.
7. The method for preparing a blend film suitable for a photovoltaic active layer according to claim 6, comprising a step of spin coating to form a film and a step of solvent vapor treatment;
preferably, the preparation method comprises the following steps:
(1) preparing a blend solution;
(2) spin-coating the blend solution to form a film;
(3) and (3) treating the blended film obtained in the step (2) by using solvent steam, and inducing crystallization to obtain the blended film.
8. A photovoltaic active layer comprising the blend film of claim 6;
preferably, the photovoltaic active layer is a photovoltaic active layer of an organic solar cell;
preferably, the non-fullerene acceptor and fullerene derivative in the photovoltaic active layer are used as photovoltaic acceptor materials, and the strong crystal donor is used as a photovoltaic donor material;
preferably, the thickness of the photovoltaic active layer is 100-500nm, preferably 200-500nm, such as 200nm, 300nm, 400nm, 500 nm.
9. A device comprising the photovoltaic active layer of claim 8;
preferably, the device is a solar cell device, such as an organic solar cell device;
preferably, the device comprises the following structures stacked in sequence: the photovoltaic device comprises a conductive substrate layer, a hole buffer layer, the photovoltaic active layer, an electron transport layer and a conductive cathode.
10. A method for making a device according to claim 9, comprising the steps of:
(1) performing surface pretreatment on the conductive substrate layer;
(2) spin coating a hole buffer layer material on the base layer;
(3) preparing a photovoltaic active layer substance solution;
(4) spin coating a photovoltaic active layer material solution on the surface of the hole buffer layer;
(5) spin-coating an electron transport layer material solution on the surface of the photovoltaic active layer;
(6) and thermally evaporating a cathode material onto the electron transport layer to obtain the device.
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