CN115386069A - Copolymer, active layer and organic photovoltaic element - Google Patents
Copolymer, active layer and organic photovoltaic element Download PDFInfo
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- CN115386069A CN115386069A CN202211197788.0A CN202211197788A CN115386069A CN 115386069 A CN115386069 A CN 115386069A CN 202211197788 A CN202211197788 A CN 202211197788A CN 115386069 A CN115386069 A CN 115386069A
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- active layer
- fused ring
- organic photovoltaic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
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- C08G2261/19—Definition of the polymer structure partially conjugated
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- Photovoltaic Devices (AREA)
Abstract
A copolymer as an electron acceptor material, an active layer and an organic photovoltaic element comprising the copolymer. The copolymer has wide absorption wavelength distribution and high absorption in the ultraviolet-visible light region, so that the copolymer can be used as an electron acceptor material for improving the photocurrent density, and the electron acceptor material of the copolymer has excellent photoelectric conversion characteristics.
Description
Technical Field
The present invention relates to a copolymer (biopolymer) capable of being used as an electron acceptor material, an active layer and an organic photovoltaic device including the same, and more particularly, to a random copolymer (random biopolymer), an active layer and an organic photovoltaic device including the same.
Background
With the evolution of the times, the consumption of energy resources such as coal, oil, natural gas and nuclear energy is increasing day by day, and the energy crisis is relatively emerging, so that the solar power generation is developed. Solar power generation is a renewable environment-friendly power generation mode which can reduce environmental pollution. The first generation of solar cells is a bulk of silicon based (silicon based) solar cells, which have high photoelectric conversion efficiency. The second generation solar cell is a thin-film cadmium telluride (CdTe) solar cell, but the toxicity of raw materials and the manufacturing process thereof have great pollution to the environment. Accordingly, third generation organic solar cells have come into development, which include dye-sensitized solar cells (DSSCs), nanocrystalline cells, or organic photovoltaic elements (OPVs). Compared with inorganic materials which need to be manufactured by vacuum process coating, the organic photovoltaic element can be manufactured by using dip coating, rotary coating, slit coating, screen printing, ink jet printing and other modes, so that the economic benefits of low cost and large-scale production are realized more easily. In the fabrication of the organic photovoltaic device of the new generation, an electron acceptor material is used in combination with an electron donor material (polymer) as a material of an active layer (light absorption layer). The new generation of organic photovoltaic elements has several advantages: (1) the weight is light, and the manufacturing cost is low; (2) has flexibility; (3) the designability of the device structure is strong; (4) is suitable for liquid phase process and can be applied in large area wet coating.
Although organic photovoltaic devices have many advantages, most of the current developments on electron acceptor materials are mainly fullerene derivatives (such as PC60BM and PC70 BM), but the fullerene derivatives themselves have the following disadvantages: easy dimerization under illumination, easy crystallization during heating, weak absorption in a visible light region, difficult structural modification and purification, high price and the like. Therefore, non-fullerene electron acceptor materials have been actively developed in recent years to achieve higher performance. As is known, polymer-type electron acceptor materials generally have good mechanical properties, film-forming properties and thermal stability compared to organic small-molecule-type non-fullerene electron acceptor materials, and therefore, the development of polymer-type electron acceptor materials as an active layer of an organic photovoltaic device to improve the energy conversion efficiency (PCE) of the organic photovoltaic device is a focus of research by recent scientists. For example, chinese patent publication nos. CN113174032A (document one) and CN113024780a (document two).
In the fabrication of the active layer of the organic photovoltaic device, the types of solvents capable of dissolving the electron acceptor material in the form of polymer, the solubility, whether or not the precipitate is generated after standing, the film forming property of the formed active layer solution and the influence of the PCE on the formation of the active layer need to be considered. However, the above-mentioned subject is not discussed in the literature, and the kind of solvent used for the active layer is not disclosed. In addition, for environmental protection, the choice of the solvent is preferably a non-chlorine (i.e., chlorine-free) solvent, and even when a non-chlorine solvent is used, the solubility and whether or not the active layer solution precipitates after standing still are considered, and particularly, an active layer solution without precipitates is preferable. Although document two mentions that a non-chlorine solvent such as toluene can be used as the active layer solvent, chloroform containing chlorine is still used as the solvent in the embodiment choice, and the PCE is only up to 12.6%. In fact, when the solvent of the active layer of the second document is changed to a non-chlorine solvent such as xylene, experimental results show that the precipitates of the polymer-type electron acceptor material in the active layer solution are attached to the wall surface of the container (which will be illustrated in the following discussion of comparative examples), and thus when the solvent of the active layer is changed to a non-chlorine solvent such as xylene, the precipitates may cause poor film forming property or defect formation in the formation of the active layer, and the PCE is lower than 12.6%.
One of the factors to consider the problems of the above two documents is that the electron acceptor material in the polymer form of the second document is a homopolymer (homo polymer), and the solubility of the homopolymer is low due to its good crystallinity, which results in that an environmentally-unfriendly solvent containing chlorine, such as chloroform, is required to be used to dissolve the homopolymer for higher solubility, and when a non-chlorine solvent, such as xylene, is used, the above precipitates are liable to occur, thus causing poor film-forming property of the active layer or formation of defects.
Therefore, it is an object of current research to develop a structure of a polymer that can be dissolved using a relatively eco-friendly chlorine-free solvent (e.g., toluene, xylene) as an active layer material so that the active layer solution does not have precipitate generation, and an active layer having both good electron transport properties of fullerene derivatives, and an organic photovoltaic element having a high PCE, for example, more than 16%.
Disclosure of Invention
In view of the problems of the prior organic photovoltaic devices, the present invention provides a copolymer capable of being used as an electron acceptor material, which can be used as an active layer of an organic photovoltaic device in combination with an electron donor material. In particular, the present invention provides a random copolymer comprising at least two repeating units in a random arrangement in a main chain of the random copolymer, the two repeating units being different from each other, thereby reducing crystallinity so that the random copolymer can be dissolved using a relatively environmentally friendly chlorine-free solvent (e.g., toluene, xylene). In addition, the active layer also has good electron transport properties of the fullerene derivative. Surprisingly, the copolymer of the present invention has a wide absorption wavelength distribution and a high absorption degree in the ultraviolet-visible region, so that the absorption in the visible region can be improved, the photocurrent density can be increased, and the organic photovoltaic device can have excellent photoelectric conversion characteristics and good energy conversion efficiency (PCE).
Accordingly, a first object of the present invention is to provide a copolymer. The term copolymer as used in the present invention is understood to mean any random copolymer or block copolymer, except where specifically indicated as random copolymer. Preferably, the copolymers referred to herein are random copolymers.
Thus, the copolymer of the present invention comprises the structure represented by the following formula (I):
[ chemical formula (I)]
Wherein the content of the first and second substances,
the first repeat unit structure is different from the second repeat unit structure;
a and b are both real numbers in mole fraction, and 0 & lt a & lt 1 & gt, 0 & lt b & lt 1 & gt, and the sum of a and b is 1;
π 1 and pi 2 Each independently an aromatic ringRadicals or heteroaromatic ring radicals, pi 1 And pi 2 May be the same or different from each other;
SMA 2 a group of a condensed RING (FUSED RING) structure or a group of a NON-condensed RING (NON FUSED RING) structure;
SMA 1 is composed of
C 1 And C 2 Each independently is
C 1 And C 2 May be the same or different from each other;
x is O, S, se, -NR 5 -or
R 1 And R 2 Each independently is C 1 ～C 30 Alkyl radical, C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl, R 1 And R 2 May be the same or different from each other;
R 3 and R 4 Each independently is unsubstituted or substituted by R 0 Substituted C 1 ～C 30 Alkyl radical, C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl group, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl radicals or C 1 ～C 30 Alkoxyheteroaryl, R 3 And R 4 May be the same or different from each other;
R 0 is C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl group, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl radicals or C 1 ～C 30 An alkoxy heteroaryl group;
R 5 is C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group;
R 6 and R 7 Each independently is H, F, cl, R 8 、-CN、-OR 9 、-SR 10 、-C(＝O)OR 11 Aryl or heteroaryl, R 6 And R 7 May be the same or different from each other;
R 8 to R 11 Are each unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Straight, branched or cyclic alkyl, unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkenyl, or unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkynyl radical, R 12 Is halogen or-CN;
EG is
Z 1 To Z 3 Each independently is H, F, cl, br, R 8 、-CN、-OR 9 、-SR 10 -OR C (= O) OR 11 ，Z 1 To Z 3 May be the same or different from each other.
Specifically, in the present invention, "alkylaryl group", "alkylheteroaryl group", "alkoxyaryl group", and "alkoxyheteroaryl group" refer to "alkyl-substituted aryl group", "alkyl-substituted heteroaryl group", "alkoxy-substituted aryl group", and "alkoxy-substituted heteroaryl group", respectively. In addition, the former carbon number means the carbon number of an alkyl group, e.g. C 1 ～C 30 Alkylaryl is denoted by C 1 ～C 30 Alkyl-substituted aryl, C 1 ～C 30 The alkyl heteroaryl group being denoted by C 1 ～C 30 Alkyl-substituted heteroaromaticsBase, C 1 ～C 30 Alkoxyaryl is designated by the radical C 1 ～C 30 Alkoxy-substituted aryl radicals, C 1 ～C 30 Alkoxy heteroaryl is denoted by C 1 ～C 30 Alkoxy-substituted heteroaryl. The term "small molecule group" refers to a "Residue (Residue) of a compound that is not a polymer or not an Oligomer (Oligomer)". In the present invention, the term "Z" is used 1 To Z 3 Means "Z" as 1 、Z 2 And Z 3 Is the aforementioned "" R "" 8 To R 11 Means "" R " 8 、R 9 、R 10 And R 11 The rest can be analogized and will not be described in detail. From the structure of the EG group, it is known that the EG group is an electron-withdrawing group.
Preferably, SMA 2 Is a group of the fused ring structure.
Preferably, the group of the fused ring structure is a five-membered fused ring derivative group, a seven-membered fused ring derivative group or a nine-membered fused ring derivative group.
Preferably, the five-membered fused ring derivative group is
Preferably, the group of the non-fused ring structure is
R 13 Is 2-ethylhexyl (2-ethylhexyl), R 14 Is 2-hexyldecyl (2-hexyldececyl).
In particular, based on the above examples of the groups of the fused ring structure and the groups of the non-fused ring structure, the groups of the fused ring structure are referred to as SMA 2 In the structure (A) in which plural carbon rings and/or plural hetero rings on the main chain connecting the electron-absorbing groups (EG groups) at the left and right ends thereof are connected in a common ring-edge manner, i.e. SMA 2 The main chains of the two groups are all in a full condensed ring structure connected by condensed rings; in contrast, the non-fused ring structure is referred to as SMA 2 In which at least one single bond appears on the main chain of each other electron-withdrawing group (EG group) connecting the left and right ends thereof to connect a plurality of other carbon rings and/or a plurality of other hetero rings, i.e. SMA 2 The main chain of (A) is a non-fully fused ring structure in which all of them are not linked by fused rings.
Preferably, n 1 And pi 2 Each independently is
V is S, O or Se, R 17 To R 18 Definitions of the above-mentioned R 6 Are as defined and R 17 And R 18 May be the same or different from each other, and n is an integer of 0 to 12.
Accordingly, a second object of the present invention is to provide an active layer comprising the aforementioned copolymer.
Preferably, the active layer comprises an electron donor material and an electron acceptor material, the electron acceptor material comprising the aforementioned copolymer.
Preferably, the electron acceptor material further comprises a fullerene derivative, i.e., the electron acceptor material comprises the copolymer and the fullerene derivative, and the fullerene derivative is PC 60 BM or PC 70 BM。
Therefore, the third objective of the present invention is to provide an organic photovoltaic device comprising the aforementioned copolymer and/or the active layer.
Preferably, the organic photovoltaic device includes a substrate, a first electrode laminated on the substrate, an electron transport layer laminated on the first electrode, an active layer laminated on the electron transport layer, a hole transport layer laminated on the active layer, and a second electrode laminated on the hole transport layer, and the active layer includes the copolymer.
Preferably, the organic photovoltaic device includes a substrate, a first electrode laminated on the substrate, a hole transport layer laminated on the first electrode, an active layer laminated on the hole transport layer, an electron transport layer laminated on the active layer, and a second electrode laminated on the electron transport layer, and the active layer includes the copolymer.
The invention has the following effects: the copolymer used as the electron acceptor material of the invention contains a strong electron-withdrawing group [ SMA ] in the main chain 1 ]And another strongly electron-withdrawing group [ SMA 2 ]The absorption wavelength distribution in the UV-visible region is increased by the different chemical structures and through the conjugated group [ pi ]]To adjust energy level and solubility. Especially when the copolymer is a random copolymer and/or SMA 2 Is a plurality ofWhen the fused cyclic derivative group is present, the copolymer has a reduced crystallinity and/or polarity, and therefore can be dissolved in a relatively environmentally friendly solvent (e.g., toluene or xylene) containing no chlorine. The proper addition of the copolymers of the present invention to the active layer can improve the matching of the energy levels between the electron donor material and the electron acceptor material. Therefore, when the copolymer is used as an electron acceptor material, the photocurrent density is increased by utilizing the absorption wavelength of a wide ultraviolet-visible light region and high absorbance, and the energy conversion efficiency of the organic photovoltaic element is further improved.
Drawings
Other features and effects of the present invention will be apparent from the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a spectrum diagram illustrating UV-visible absorption spectra of copolymers 1-3 and polymers 1-2 in solution;
FIG. 2 is a spectrum diagram showing UV-visible absorption spectra of copolymers 1 to 3 and polymers 1 to 2 formed in a solid state;
FIG. 3 is a photographic image of the solubility of polymers 1-2 and copolymers in xylene;
FIG. 4 is a schematic cross-sectional view illustrating a first structure of the organic photovoltaic device of the present invention;
FIG. 5 is a schematic cross-sectional view illustrating a second structure of the organic photovoltaic device according to the present invention; and
fig. 6 is a graph illustrating voltage-current densities of the organic photovoltaic devices of comparative examples 1 to 3 and application examples 1 to 3, respectively.
[ notation ] to show
70: substrate
80: a first electrode
90: organic semiconductor layer
91: electron transport layer
92: active layer
93: hole transport layer
100: second electrode
Detailed Description
< preparation of copolymers 1 to 3>.
Preparation example 1: copolymer 1 was prepared.
Preparation of compound 3:
dimethylformamide (DMF, 40 mL) was added to the compound 1 (5 g,6.7 mmol), potassium carbonate (5.5 g, 40mmol) and the compound 2 (11g, 27mmol) were added, and the mixture was heated to 80 ℃ to react for 3 hours. Then, heptane and water were added to conduct extraction with decreasing the temperature, and the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by concentration. Finally, after precipitating the solid with heptane and isopropanol, compound 3 was obtained as a brown solid (5.8 g, yield: 67%).
Preparation of compound 4:
compound 3 (5.5g, 4.2 mmol) was dissolved in 1,2-dichloroethane (55 mL) and anhydrous dimethylformamide (19mL, 252mmol) was added and phosphorus oxychloride (12mL, 126mmol) was slowly added dropwise in an ice bath. Then, the mixture was heated to reflux and stirred for 2 hours. After the reaction was completed, dichloromethane was added for extraction, and the organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated in a rotary concentrator and dried. Finally, after purification by silica gel column chromatography (dichloromethane: n-heptane =2:1 as eluent) and drying in vacuo, compound 4 was obtained as an orange liquid (3.8 g, yield: 67%).
Preparation of compound 6:
chloroform (38 mL) was added to compound 4 (3.8g, 0.28mmol) and compound 5 (2.1g, 8.5 mmol), followed by dropwise addition of pyridine (0.3 mL) and reaction under nitrogen atmosphere for 3 hours. After the reaction is finished, cooling, concentrating and draining by a rotary concentrator. Then, a solid was precipitated with methanol, purified by silica gel column chromatography (chloroform as an eluent), and dried under vacuum to obtain a dark purple solid, i.e., compound 6 (4.9 g, yield: 93%).
Preparation of compound 8:
after chloroform (15 mL) was added to compound 7 (1.5g, 1.56mmol) and compound 5 (1.27g, 4.67mmol), pyridine (py, 0.1 mL) was added dropwise slowly and reacted for 3 hours under nitrogen. After the reaction is finished, cooling, concentrating and draining by a rotary concentrator. Then, a solid was precipitated with methanol, purified by silica gel column chromatography (chloroform as an eluent), and dried under vacuum to obtain a dark purple solid, i.e., compound 8 (2.1 g, yield: 90%).
Preparation of copolymer 1:
compound 6 (186 mmol), compound 8 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd 2 (dba) 3 ](10.6 mmol) was charged to a 50mL reaction flask. Then, 12mL of anhydrous chlorobenzene (PhCl) was added, the mixture was stirred at 130 ℃ for 3 hours, the reaction was cooled to room temperature, and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet (Soxhlet) extraction with methanol, acetone and chloroform in this order. Finally, the chloroform residue was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried in vacuum to obtain copolymer 1.
Preparation example 2: copolymer 2 was prepared.
Preparation of compound 10:
compound 9 (2g, 1.85mmol) and compound 5 (1.51g, 5.56mmol) were added to chloroform (20 mL), followed by slow dropwise addition of pyridine (0.2 mL) and reaction under nitrogen for 3 hours. After the reaction is finished, cooling, concentrating and pumping by a rotary concentrator. Then, a solid was precipitated with methanol, purified by silica gel column chromatography (chloroform as an eluent), and dried in vacuo to obtain compound 8 (2.6 g, yield: 88%) as a dark purple solid.
Preparation of copolymer 2:
compound 6 (1.86 mmol), compound 10 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd 2 (dba) 3 ](10.6 mmol) was charged to a 50mL reaction flask. Then, 21mL of anhydrous chlorobenzene (PhCl) was added, the mixture was stirred at 130 ℃ for 3 hours, the reaction was cooled to room temperature, and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet (Soxhlet) extraction with methanol, acetone and chloroform in this order. Finally, the chloroform residue was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried in vacuum to obtain copolymer 2.
Preparation example 3: copolymer 3 was prepared.
Preparation of compound 12:
compound 11 (2g, 1.36mmol) and compound 5 (1.12g, 4.1mmol) were added to chloroform (20 mL), followed by dropwise addition of pyridine (0.2 mL) and reaction under nitrogen atmosphere for 3 hours. After the reaction is finished, cooling, concentrating and draining by a rotary concentrator. Then, a solid was precipitated with methanol, purified by silica gel column chromatography (chloroform as an eluent), and dried under vacuum to obtain a dark purple solid, i.e., compound 12 (2.4 g, yield: 90%).
Preparation of copolymer 3:
compound 6 (1.86 mmol), compound 12 (79.7 mmol), compound 13 (265 mmol), tris (2-furyl) phosphine [ (o-toly) 3 P](42.5 mmol), tris (dibenzylideneacetone) dipalladium [ Pd 2 (dba) 3 ](10.6 mmol) was charged to a 50mL reaction flask. Then, 21mL of anhydrous chlorobenzene (PhCl) was added, the mixture was stirred at 130 ℃ for 3 hours, the reaction was cooled to room temperature, and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration, and the solid was subjected to Soxhlet (Soxhlet) extraction with methanol, acetone and chloroform in this order. Finally, the chloroform residue was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried in vacuum to obtain copolymer 3.
< polymers 1 and 2> used in comparative examples described below were provided.
polymer 2 comprises repeating units as shown below, polymer 2 being a homopolymer:
< ultraviolet-visible (UV-Vis) absorption Spectrum >.
FIG. 1 shows UV-visible absorption spectra of copolymers 1 to 3 and polymers 1 to 2, respectively, dissolved in chloroform and measured with an instrument; FIG. 2 shows the UV-visible absorption spectra of copolymers 1-3 and polymers 1-2, respectively, after they were dissolved in chloroform, coated on a transparent glass slide and dried to form a solid film.
Referring to the spectra of fig. 1 and 2, copolymers 1 to 3 have a broad absorption wavelength distribution in the uv-vis region; further, since the copolymers 1 to 3 have higher absorption in the ultraviolet-visible region than the polymers 1 to 2, the copolymers 1 to 3 can be used as electron acceptor materials having a wide absorption wavelength distribution.
< solubility in chlorine-free solvent >.
FIG. 3 shows the results of charging 10mg of each of polymers 1 to 2 and copolymer 3 in a glass vessel, adding 1ml of a solvent containing no chlorine, i.e., xylene, heating to 100 ℃ and stirring for 3 hours, and then returning to room temperature. Clearly, the left and middle glass containers containing polymers 1 and 2, respectively, had precipitates indicating that polymers 1 and 2 were xylene insoluble or low in solubility; in contrast, the right glass container containing copolymer 3 had no precipitate, indicating that copolymer 3 was xylene soluble and highly soluble.
< organic photoelectric element Structure >
The organic optoelectronic devices of the present invention include, but are not limited to, organic light-emitting diodes (organic light-emitting diodes), organic thin film transistors (organic thin film transistors), organic photovoltaic devices (OPVs), and Organic Photodetectors (OPDs), which are exemplified by the organic photovoltaic devices (OPVs).
FIG. 4 is a cross-sectional view of a first structure of an organic photovoltaic device used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic semiconductor layer 90. The organic semiconductor layer 90 includes an electron transport layer 91 stacked on the first electrode 80, an active layer 92 stacked on the electron transport layer 91, and a hole transport layer 93 stacked on the active layer 92. Therefore, the second electrode 100 is laminated on the hole transport layer 93.
FIG. 5 is a cross-sectional view of a second structure of an organic photovoltaic device used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic semiconductor layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic semiconductor layer 90. The organic semiconductor layer 90 includes a hole transport layer 93 stacked on the first electrode 80, an active layer 92 stacked on the hole transport layer 93, and an electron transport layer 91 stacked on the active layer 92. Therefore, the second electrode 100 is laminated on the electron transport layer 91.
For convenience of illustration and understanding, the structure of the organic photovoltaic device of fig. 4 is used as an example of an application.
< comparative examples 1 to 3 and application examples 1 to 3>.
Organic photovoltaic elements (OPVs) were prepared.
The organic photovoltaic elements of comparative examples 1 to 3 and application examples 1 to 3 were prepared according to the active layer materials (electron donor material and electron acceptor material) of the organic photovoltaic element listed in table 1 below and by the method of preparing an organic photovoltaic element described later.
TABLE 1
The electron donor material used in comparative examples 1-3 and application examples 1-3 was polymer 4, which contained repeating units as shown below, polymer 4 being a homopolymer:
the electron acceptor materials used in comparative examples 1 to 3 and application examples 1 to 3 include compound 14 and compound 15:
the following is a method of making an organic photovoltaic element.
Before the preparation of the organic photovoltaic device, the patterned ITO glass substrate (12 Ω/□) was sequentially cleaned in an ultrasonic oscillation tank for 10 minutes using a cleaning agent, deionized water, acetone and isopropyl alcohol, respectively. The ITO glass substrate was cleaned by ultrasonic oscillation and then surface-treated in an ultraviolet ozone (UV-ozone) cleaner for 30 minutes. Wherein a glass substrate is the substrate 70, ito is the first electrode 80, i.e. the anode in the structure of fig. 3.
Mixing zinc acetate [ Zn (OAc) 2 ]The solution was spin-coated on an ITO glass substrate, and baked at 170 ℃ for 30 minutes to form a ZnO layer (zinc oxide layer), which was the electron transport layer 91 described above.
The polymer 4 listed in comparative example 1 in table 1 was used as an electron donor material, and mixed with a non-fullerene electron acceptor material (compound 14) and a fullerene electron acceptor material (fullerene derivative, compound 15) at a weight ratio of 1.2. In comparative example 1, polymers 1 and 2, polymer 4: compound 14: compound 15: the weight ratio of polymer 1 or polymer 2 is 1:1.2:0.2:0.1.
the copolymer 4 listed in application examples 1 to 3 in table 1 was used as an electron donor material, and was mixed with a non-fullerene electron acceptor material (compound 14), copolymer 1 or 2 or 3, and a fullerene electron acceptor material (compound 15) at a weight ratio of 1.
Next, the active layer solution was spin-coated on the ZnO layer (electron transport layer 91), and baked at 120 ℃ for 10 minutes in nitrogen to form the active layer 92 on the ZnO layer (electron transport layer 91). Then, the mixture is sent into a vacuum chamber and heated to deposit molybdenum trioxide (MoO) 3 ) Metal oxide (about 10 nm) to form the hole transport layer 93 described above on the active layer 92. Next, ag metal (about 100 nm) is deposited by heating as the second electrode 100 described above, i.e., the cathode in the structure of fig. 4.
< Electrical analysis of organic photovoltaic device >
The measurement region of the organic photovoltaic device is defined as 0.04cm by the metal mask 2 . Keithley 2400 as the power supply, controlled by Lab-View program, in the photoDegree of 100mW/cm 2 The electrical properties of the device were measured under simulated sunlight (SAN-EI XES-40S 3) am1.5g of (a), and the voltage-current curves obtained for the organic photovoltaic devices of comparative examples 1 to 3 and application examples 1 to 3 were recorded by a computer program, and are shown in fig. 6.
< analysis of energy conversion efficiency (PCE) of organic photovoltaic element >
TABLE 2
In table 2, voc denotes an open circuit voltage (open voltage), jsc denotes a short-circuit current (short-circuit current), FF denotes a fill factor (fill factor), and PCE denotes an energy conversion efficiency (energy conversion efficiency). The open circuit voltage and the short circuit current are each the intercepts of the voltage-current density curves on the X-axis and the Y-axis, and when these two values are increased, the efficiency of the organic photovoltaic device is preferably improved. Further, the fill factor is a value obtained by dividing an area that can be plotted in a curve by a product of the short-circuit current and the open-circuit voltage. When the three values of the open-circuit voltage, the short-circuit current, and the fill factor are divided by the light to be irradiated, the energy conversion efficiency can be obtained, and the energy conversion efficiency is preferably higher. From the results of table 2, it can be found that the energy conversion efficiency PCE of comparative example 1 =15.7%, the PCEs of comparative examples 2 and 3 are only 10.6% and 10.7%, respectively, and the energy conversion efficiency of the organic photovoltaic cells of application examples 1 to 3 all exceed 16%. Therefore, the addition of the copolymer in the electron acceptor material can amplify the visible light absorption distribution of the active layer and improve the absorbance, thereby increasing the photocurrent density, and simultaneously effectively adjusting the energy level to slightly gain the voltage. In addition, in application examples 1 to 3, the energy conversion efficiency PCE =16.4% of the organic photovoltaic element prepared by adding copolymer 1 and copolymer 3 to the electron acceptor material was also the optimum value.
Therefore, it can be seen from the above results that the copolymer of the present invention has a wide visible light absorption range and a high absorption degree, and thus the addition of the copolymer of the present invention to the active layer formulation can increase the photocurrent density and improve the matching of the energy levels among the donor material of the copolymer, the electron acceptor material other than fullerene, and the electron acceptor material of fullerene. The voltage slightly gains and increases the current density, so that the energy conversion efficiency (PCE) of the organic photovoltaic cell is effectively improved.
However, the above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all simple equivalent changes and modifications made according to the claims and the contents of the patent specification are still included in the scope of the present invention.
Claims (13)
1. A copolymer comprising a repeating unit represented by the following formula (I):
[ chemical formula (I)]
Wherein the content of the first and second substances,
the first repeat unit structure is different from the second repeat unit structure;
a and b are both real numbers in mole fraction, and 0-a-1, 0-b-1, and the sum of a and b is 1;
π 1 and pi 2 Each independently is an aromatic ring group or a heteroaromatic ring group;
SMA 2 being a radical of a condensed or non-condensed ring structure, the radical of the condensed ring structure being defined in SMA 2 In the structure of (1), each of the two electrodes is connected to the left and right endsThe multiple carbocycles and/or multiple heterocycles in the main chain of the subgroup are linked by a common ring-edge, the non-fused ring structure being defined as SMA 2 In the structure of (a), at least one single bond appears on a main chain of each other electron-withdrawing group connected with the left end and the right end of the structure to connect a plurality of other carbon rings and/or a plurality of other heterocyclic rings;
SMA 1 is composed of
C 1 And C 2 Each independently is
X is O, S, se, -NR 5 -or
R 1 And R 2 Each independently is C 1 ～C 30 Alkyl radical, C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl or C 1 ～C 30 An alkyl heteroaryl group;
R 3 and R 4 Each independently is unsubstituted or substituted by R 0 Substituted C 1 ～C 30 Alkyl radical, C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl group, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl radicals or C 1 ～C 30 An alkoxy heteroaryl group;
R 0 is C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl group, C 1 ～C 30 Alkyl heteroaryl, C 1 ～C 30 Alkoxyaryl radicals or C 1 ～C 30 An alkoxy heteroaryl group;
R 5 is C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group;
R 6 and R 7 Each independently is H, F, cl, R 8 、-CN、-OR 9 、-SR 10 、-C(＝O)OR 11 Aryl or heteroaryl;
R 8 to R 11 Are each unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Straight, branched or cyclic alkyl, unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkenyl, or unsubstituted or substituted by at least one R 12 Substituted C 4 ～C 30 Alkynyl, R 12 Is halogen or-CN;
EG is
Z 1 To Z 3 Each independently is H, F, cl, br, R 8 、-CN、-OR 9 、-SR 10 -OR C (= O) OR 11 。
2. The copolymer of claim 1, wherein the SMA 2 Is a group of the fused ring structure.
3. The copolymer of claim 2, wherein the fused ring structure group is a five-membered fused ring derivative group, a seven-membered fused ring derivative group, or a nine-membered fused ring derivative group.
4. The copolymer of claim 3, wherein the five-membered fused ring derivative group is
The seven-membered fused ring derivative group is
The nine-membered fused ring derivative group is
U is NQ 23 、C(Q 24 ) 2 Or Si (Q) 25 ) 2 ，Q 1 To Q 22 Each independently H, C 1 ～C 30 Alkyl radical, C 1 ～C 30 Alkoxy radical, C 1 ～C 30 Alkylaryl or C 1 ～C 30 Alkyl heteroaryl, Q 23 To Q 25 Each independently H, C 1 ～C 30 Alkyl or C 1 ～C 30 An alkoxy group.
5. The copolymer of claim 1, wherein the group of the non-fused ring structure is
R 13 Is 2-ethylhexyl, R 14 Is 2-hexyldecyl.
6. The copolymer of claim 1, wherein pi 1 And pi 2 Each independently is
V is S, O or Se, R 17 To R 18 Definitions of the above-mentioned R 6 The same definition, n is an integer of 0 to 12.
7. An active layer comprising the copolymer of claim 1.
8. The active layer of claim 7, wherein the active layer comprises an electron donor material and an electron acceptor material, the electron acceptor material comprising the copolymer.
9. The active layer of claim 8, wherein said electron acceptor material further comprises a fullerene derivative.
10. The active layer of claim 9, wherein the electron acceptor material further comprises a fullerene derivative, the fullerene derivative being PC 60 BM or PC 70 BM。
11. An organic photovoltaic element comprising the copolymer of claim 1.
12. The organic photovoltaic device according to claim 11, wherein the organic photovoltaic device comprises a substrate, a first electrode laminated on the substrate, an electron transport layer laminated on the first electrode, an active layer laminated on the electron transport layer, a hole transport layer laminated on the active layer, and a second electrode laminated on the hole transport layer, and the active layer comprises the copolymer.
13. The organic photovoltaic device according to claim 11, wherein the organic photovoltaic device comprises a substrate, a first electrode laminated on the substrate, a hole transport layer laminated on the first electrode, an active layer laminated on the hole transport layer, an electron transport layer laminated on the active layer, and a second electrode laminated on the electron transport layer, and the active layer comprises the copolymer.
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| CN111499840A (en) * | 2020-04-30 | 2020-08-07 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN112225882A (en) * | 2020-09-11 | 2021-01-15 | 华南理工大学 | N-type polymer containing non-condensed ring acceptor unit and preparation method and application thereof |
| CN112521404A (en) * | 2020-11-18 | 2021-03-19 | 位速科技股份有限公司 | Seven-membered fused ring compound, electron acceptor material mixture, preparation method of electron acceptor material mixture and organic photovoltaic cell |
| CN113061235A (en) * | 2021-03-22 | 2021-07-02 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN114044885A (en) * | 2021-10-12 | 2022-02-15 | 中国科学院大学 | Polymer electron acceptor material containing non-covalent fused ring acceptor unit and application thereof |
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| CN110862518A (en) * | 2019-10-15 | 2020-03-06 | 华南理工大学 | Multi-component copolymer based on multi-component condensed ring structure and application of multi-component copolymer in organic photoelectric device |
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