Benzotriazole organic compound as well as preparation method and application thereof

Abstract

The invention relates to a benzotriazole organic compound as well as a preparation method and application thereof. The structural general formula of the benzotriazole organic compound is as shown in formula (1): # imgabs0 #, wherein each Ar independently comprises a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; r1 and R2 are respectively and independently selected from substituted or unsubstituted alkyl or substituted or unsubstituted alkoxy; r3 and R4 are respectively and independently selected from halogen, or substituted or unsubstituted alkoxy, or substituted or unsubstituted alkylthio; and R5 is selected from substituted or unsubstituted alkyl. The benzotriazole organic compound can absorb ultraviolet light and convert the ultraviolet light into visible light, is relatively good in stability, can be used as a light conversion agent, is prepared into a photovoltaic adhesive film, is relatively low in water vapor transmittance, is further used for a photovoltaic device, and can improve the efficiency and stability of the photovoltaic device and prolong the service life of the photovoltaic device.

Description

Technical Field

[0001] The present invention relates to the field of organic functional materials, and particularly to a benzotriazole-based organic compound, a preparation method thereof, and an application thereof. Background Art

[0002] As a clean energy source with rich resources and no need for transportation, solar energy is expected to become an alternative to traditional fossil fuels. The development of solar energy collection and conversion technologies has gradually become the focus of research. Photovoltaic devices can directly convert solar energy into electrical energy, which is one of the most effective ways to utilize solar energy. So far, the installed capacity demand for photovoltaic devices globally is still continuously increasing.

[0003] However, the vast majority of photovoltaic devices can only effectively utilize visible light and near-infrared light in sunlight, and have a low utilization efficiency for ultraviolet light (wavelength less than 400 nm) in sunlight. Moreover, the presence of ultraviolet light in sunlight will reduce the service life of photovoltaic devices, especially for heterojunction solar cells (HJT) that are expected to replace passivated emitter and rear cell (PERC) and tunnel oxide passivated contact solar cell (TOPCon) as the third-generation solar cells. In addition, although using an encapsulant film with ultraviolet absorption function can improve the stability of photovoltaic devices, the efficiency of photovoltaic devices drops severely.

[0004] The use of a wavelength conversion film can not only effectively absorb ultraviolet light in sunlight and avoid damage to the service life of photovoltaic devices; at the same time, it can convert ultraviolet light into utilizable visible light, thereby improving the photoelectric conversion efficiency of photovoltaic devices. The technical core of the wavelength conversion film lies in selecting a suitable light conversion agent. Traditional light conversion agents are mainly divided into inorganic and organic light conversion agents. Compared with inorganic light conversion agents, organic light conversion agents have the advantages of low price, many types, and easy performance regulation. Moreover, since the substrate of the wavelength conversion film is usually an organic polymer material, organic light conversion agents often show better dispersibility and compatibility with the substrate, and have less influence on the light transmittance performance of the wavelength conversion film. Although traditional organic light conversion agents can well absorb ultraviolet light and convert it into visible light (usually blue light or sky blue light), thereby improving the efficiency of photovoltaic devices, their stability is poor, and the water vapor transmittance of the corresponding wavelength conversion film is relatively high, thus greatly reducing the service life of photovoltaic devices. Summary of the Invention

[0005] In view of the above problems, the present invention provides a benzotriazole-based organic compound, a preparation method thereof, and an application thereof. The benzotriazole-based organic compound is a novel organic optoelectronic functional material with good stability, which can improve the photovoltaic efficiency and service life of photovoltaic devices.

[0006] The technical solution is as follows:

[0007] One aspect of the present invention provides a benzotriazole-based organic compound, the general structural formula of which is shown in Formula (1):

[0008]

[0009] Wherein each Ar independently includes a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0010] R 1 and R 2 are each independently selected from a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group;

[0011] R 3 and R 4 are each independently selected from a halogen, or a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group;

[0012] R 5 is selected from a substituted or unsubstituted alkyl group.

[0013] In some embodiments, each of the said Ars independently includes a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

[0014] In some embodiments, each of the said Ars is selected from a substituted or unsubstituted six-membered aryl group, a substituted or unsubstituted six-membered heteroaryl group, a substituted or unsubstituted five-membered heteroaryl group.

[0015] In some embodiments, each of the said Ars is independently selected from one of the following groups:

[0016]

[0017] Wherein, * represents a connection site, and X represents O, S or Se.

[0018] In some embodiments, the said R 1 and the said R 2 are each independently selected from a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group.

[0019] In some embodiments, the said R 1 and the said R 2 are each independently selected from one of the following groups:

[0020]

[0021] Wherein, * represents a connection site, n1 ≥ 2.

[0022] In some embodiments, the R 3 and the R 4 are each independently selected from halogen, substituted or unsubstituted C1-C20 alkoxy, or substituted or unsubstituted C1-C20 alkylthio.

[0023] In some embodiments, the R 3 and R 4 are each independently selected from one of the following groups:

[0024]

[0025] wherein, * represents the bonding site, Y represents F, Cl, Br or I, and each R 6 is each independently selected from substituted or unsubstituted C1-C20 straight-chain alkyl, or substituted or unsubstituted C3-C20 branched-chain alkyl.

[0026] In some embodiments, the R 3 and R 4 are each independently selected from one of the following groups:

[0027]

[0028] wherein, * represents the bonding site, and Y represents F, Cl, Br or I.

[0029] In some embodiments, the R 5 is selected from substituted or unsubstituted C1-C20 alkyl.

[0030] In some embodiments, the R 5 is selected from one of the following groups:

[0031]

[0032] wherein, * represents the bonding site, and n 2 ≥ 2.

[0033] In some embodiments, the benzotriazole organic compound as described above has any of the following structures:

[0034]

[0035] The second aspect of the present invention also provides a preparation method of the benzotriazole organic compound as described above, and the technical solution is as follows:

[0036] A preparation method of the benzotriazole organic compound as described above, comprising the following steps:

[0037] Mix compound a, compound b, compound c and a base in a solvent, react, and prepare the benzotriazole organic compound as described in formula (1);

[0038]

[0039] In some embodiments, the molar ratio of the compound (a), the compound (b) to the compound (c) is 1:(1 - 2):(1 - 2).

[0040] In some embodiments, the molar ratio of the base to the compound (a) is (1 - 2):1.

[0041] In some embodiments, the base is potassium carbonate.

[0042] In some embodiments, the solvent is a mixed solvent of 1,4 - dioxane and water.

[0043] In some embodiments, the reaction temperature is 80°C - 100°C and the time is 20 h - 40 h.

[0044] The third aspect of the present invention also provides the application of the benzotriazole organic compound as described above, and the technical solution is as follows:

[0045] A light conversion agent, comprising the benzotriazole organic compound as described above.

[0046] In some embodiments, the absorption wavelength range of the light conversion agent is 280 nm - 400 nm.

[0047] In some embodiments, the maximum absorption peak of the light conversion agent is 320 nm - 380 nm.

[0048] In some embodiments, the photoluminescence range of the light conversion agent is 400 nm - 600 nm.

[0049] In some embodiments, the maximum emission peak of the light conversion agent is 450 nm - 550 nm.

[0050] A photovoltaic adhesive film, comprising the benzotriazole organic compound as described above, or comprising the light conversion agent as described above.

[0051] In some embodiments, the photovoltaic adhesive film further comprises an optically transparent polymer material.

[0052] In some of these embodiments, by mass percentage, the raw materials for preparing the photovoltaic film include 0.01% to 5% of the benzotriazole organic compound or the light conversion agent as described above, and 95% to 99.99% of the polymer material.

[0053] In some of these embodiments, the polymer material is selected from one or more of polyolefin elastomer (POE), ethylene-vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), and silicone resin material.

[0054] In some of these embodiments, the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 to 15).

[0055] A photovoltaic device includes a solar cell, and at least one surface of the solar cell is provided with the photovoltaic film as described above.

[0056] In some of these embodiments, the solar cell includes one or more of a crystalline silicon solar cell, a perovskite solar cell, and a tandem cell composed of a perovskite cell and a crystalline silicon cell.

[0057] In some of these embodiments, the solar cell is a tandem cell sheet composed of a perovskite cell and a crystalline silicon cell. The solar cell includes a first transparent conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a second transparent conductive layer, an N-type doping layer, a first amorphous silicon layer, a silicon wafer, a second amorphous silicon layer, a P-type doping layer, and a third transparent conductive layer, which are sequentially stacked, and a first grid electrode layer and a second grid electrode layer;

[0058] The first grid electrode layer includes a plurality of first grid electrodes arranged at intervals, and each first grid electrode is electrically connected to the first transparent conductive layer;

[0059] The second grid electrode layer includes a plurality of second grid electrodes arranged at intervals, and each second grid electrode is electrically connected to the third transparent conductive layer.

[0060] In some of these embodiments, the photovoltaic device further includes a light-incident surface panel (the light-incident surface is also called the light-incoming surface) and a backlight surface panel. The light-incident surface panel is stacked on the surface of the first transparent conductive layer away from the perovskite active layer, and the backlight surface panel is stacked on the surface of the third transparent conductive layer away from the perovskite active layer;

[0061] The surface of the solar cell is coated with the photovoltaic film.

[0062] In some of these embodiments, the solar cell further includes a first antireflection layer, which is laminated on the surface of the first transparent conductive layer away from the perovskite active layer, and the first grid electrode penetrates through the first antireflection layer to be electrically connected to the first transparent conductive layer;

[0063] The material of the first antireflection layer includes one or more of magnesium fluoride, lithium fluoride, silicon nitride, silicon oxide, and silicon oxynitride.

[0064] In some of these embodiments, the solar cell further includes a second antireflection layer, which is laminated on the surface of the first transparent conductive layer away from the perovskite active layer, and the first grid electrode penetrates through the second antireflection layer to be electrically connected to the first transparent conductive layer;

[0065] The second antireflection layer includes a patterned photovoltaic film;

[0066] By mass percentage, the photovoltaic film includes 0.01% - 5% of the benzotriazole organic compound or the light conversion agent as described above, and 95% - 99.99% of the polymer material;

[0067] And the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 - 15).

[0068] In some of these embodiments, the solar cell further includes a third antireflection layer, which is laminated on the surface of the third transparent conductive layer away from the perovskite active layer, and the second grid electrode penetrates through the third antireflection layer to be electrically connected to the third transparent conductive layer;

[0069] The third antireflection layer includes a patterned photovoltaic film;

[0070] By mass percentage, the photovoltaic film includes 0.01% - 5% of the benzotriazole organic compound or the light conversion agent as described above, and 95% - 99.99% of the polymer material;

[0071] And the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 - 15).

[0072] The present invention has at least the following beneficial effects:

[0073] The benzotriazole organic compound provided by the present invention is based on benzotriazole with specific Ar, R 1 、R 2 、R 3 、R 4and R 5 Group modification can increase the fluorescence characteristics of the product, adjust the absorption spectrum to the ultraviolet region, the fluorescence emission spectrum to the visible region, and R 3 、R 4 The introduction of can adjust the donor-acceptor interaction within the molecule, increase molecular rigidity, improve the oxidation barrier, and enhance the stability of the molecule. Molecular rigidity can also increase the absorption extinction coefficient and fluorescence quantum yield of the compound molecule.

[0074] It can be seen that through the combination of benzotriazole and various substituents, this benzotriazole-based organic compound can absorb ultraviolet light and convert it into visible light, such as blue light or sky blue light. It has good stability, high absorption extinction coefficient and fluorescence quantum yield, and can be used as a light conversion agent. When this benzotriazole-based organic compound is made into a photovoltaic adhesive film, it has the advantages of good light conversion effect, high stability, and low water vapor transmission rate. Further used in photovoltaic devices, it can improve the photovoltaic efficiency and stability of photovoltaic devices and extend the device life.

[0075] After testing, in some examples of the present invention, the absorption wavelength range of this benzotriazole-based organic compound is 280nm - 400nm, the maximum absorption peak is 320nm - 380nm, the photoluminescence range is 400nm - 600nm, and the maximum emission peak is 450nm - 550nm. When it is used in a photovoltaic adhesive film and further used in a photovoltaic device, the photovoltaic efficiency of the photovoltaic device can be increased by more than 1%, and the life can be extended by more than 50%. Brief Description of the Drawings

[0076] Figure 1 It is a schematic structural diagram of a tandem cell composed of a perovskite cell and a crystalline silicon cell shown in an embodiment of the present invention;

[0077] Figure 2 It is a schematic structural diagram of a tandem cell composed of a perovskite cell and a crystalline silicon cell shown in an embodiment of the present invention;

[0078] Figure 3 It is a schematic structural diagram of a tandem cell composed of a perovskite cell and a crystalline silicon cell shown in an embodiment of the present invention;

[0079] Figure 4 It is a schematic structural diagram of a photovoltaic device shown in one embodiment of the present invention;

[0080] Figure 5 It is a schematic structural diagram of a solar cell containing a single-layer patterned antireflection layer shown in one embodiment of the present invention;

[0081] Figure 6 It is a schematic structural diagram of a solar cell containing a double-layer patterned antireflection layer shown in one embodiment of the present invention;

[0082] Figure 7 For the flow chart of the preparation method and the schematic diagram of the intermediate structure of the solar cell containing the double-layer patterned antireflection layer as Figure 6 described;

[0083] Figure 8 For the schematic diagram of the photovoltaic adhesive film structure with pyramid-shaped and hemispherical patterns;

[0084] Figure 9 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 1 of the present invention;

[0085] Figure 10 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 2 of the present invention;

[0086] Figure 11 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 3 of the present invention;

[0087] Figure 12 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 4 of the present invention;

[0088] Figure 13 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 5 of the present invention;

[0089] Figure 14 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 6 of the present invention;

[0090] Figure 15 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 7 of the present invention;

[0091] Figure 16 For the nuclear magnetic resonance hydrogen spectrum of the benzotriazole compound synthesized in Synthesis Example 8 of the present invention;

[0092] Figure 17 For the I-V curve of the solar cell containing the double-layer patterned antireflection layer shown in one device embodiment and the comparative example of the present invention;

[0093] Figure 18 For the external quantum efficiency - wavelength curve of the solar cell containing the double-layer patterned antireflection layer shown in one device embodiment and the comparative example of the present invention. Detailed implementation manners

[0094] The present invention will be further described in detail below in conjunction with specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided so that the disclosure of the present invention can be more thoroughly and comprehensively understood.

[0095] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this invention belongs. The terms used in the description of the present invention in this specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the related listed items.

[0096] In the case of using "including", "having", and "comprising" described herein, it is intended to cover non-exclusive inclusion. Unless a clear limiting term such as "only", "consisting of", etc. is used, another component may also be added.

[0097] In the present invention, the terms "first", "second", and "third" are used only for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first", "second", and "third" may explicitly or implicitly include at least one of such features.

[0098] In the present invention, for orientation terms, if there are terms such as "center", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., indicating the orientation and positional relationship is based on the orientation or positional relationship shown in the drawings. This is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and cannot be construed as limiting the specific protection scope of the present invention.

[0099] When describing the positional relationship, unless otherwise specified, when an element such as a layer, film, or substrate is referred to as being "on" another film layer, it can be directly on the other film layer or there may also be an intermediate film layer. Further, when a layer is referred to as being "under" another layer, it can be directly below or there may be one or more intermediate layers. It can also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or there may also be one or more intermediate layers.

[0100] The terms "preferably", "more preferably", "more preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain cases. However, in the same or other cases, other embodiments may also be preferred. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not available, nor is it intended to exclude other embodiments from the scope of the present invention. That is, in the present invention, "preferably", "more preferably", "more preferably", "more preferably", etc. are only used to describe embodiments or examples with better effects, but do not constitute a limitation on the protection scope of the present invention.

[0101] In the present invention, "further", "even further", "especially", etc. are used for descriptive purposes and indicate differences in content, but should not be construed as a limitation on the protection scope of the present invention.

[0102] In the present invention, the meaning of "at least one" is more than one, such as one, two or more. The meaning of "multiple" or "several" is at least two, such as two, three, etc., and the meaning of "multiple layers" is at least two layers, such as two layers, three layers, etc., unless otherwise specifically defined. In the description of the present invention, the meaning of "several" is at least one, such as one, two, etc., unless otherwise specifically defined.

[0103] When a numerical range is disclosed in the present invention, the above range is considered continuous and includes the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when the range refers to an integer, it includes each integer between the minimum and maximum values of the range. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein. And only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single numerical value itself can be used as a lower limit or upper limit and combined with any other point or single numerical value or combined with other lower limits or upper limits to form a range not explicitly recited.

[0104] Unless otherwise specified, all steps of the present invention can be carried out sequentially or randomly. For example, when the method includes steps (a) and (b), it means that the method can include steps (a) and (b) carried out sequentially, or can also include steps (b) and (a) carried out sequentially. For example, when it is mentioned that the method further includes step (c), it means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b) and (c) in sequence, or can also include steps (a), (c) and (b), or can also include steps (c), (a) and (b), etc.

[0105] Unless otherwise mentioned, terms in the singular form can include the plural form and should not be construed as having a quantity of one.

[0106] For the temperature parameters in the present invention, unless otherwise specified, both constant temperature treatment and treatment within a certain temperature range are allowed. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0107] The weights of the relevant components mentioned in the embodiments of the present invention specification can not only refer to the specific contents of each component, but also represent the proportional relationship of the weights between each component. Therefore, as long as the contents of the relevant components in the embodiments of the present invention specification are enlarged or reduced in proportion, they are within the scope disclosed in the embodiments of the present invention specification. Specifically, the weights mentioned in the embodiments of the present invention specification can be mass units well-known in the chemical field such as μg, mg, g, kg, etc.

[0108] In the present invention, for units involving data ranges, if only the right endpoint is followed by a unit, it means that the units of the left endpoint and the right endpoint are the same. For example, 800~850nm means that the units of both the left endpoint “800” and the right endpoint “850” are nm (nanometers).

[0109] In the present invention, “above” or “below” both include the number itself. For example, below 1 means less than or equal to 1 (≤1), and above 1 means greater than or equal to 1 (≥1).

[0110] In the present invention, “A and B are each independently selected from x, y or z” means that A and B are independent events, and event A does not affect the occurrence of event B. Therefore, when A is selected from x, B can be selected from any one of x, y or z; when A is selected from y, B can be selected from any one of x, y or z; when A is selected from z, B can be selected from any one of x, y or z.

[0111] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or may not be substituted. When the defined group is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: C1-C30 alkyl, cycloalkyl having 3 to 20 ring atoms, heterocyclic group having 3 to 20 ring atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halocarbonyl, formyl, -NRR', cyano, isocyano, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, nitro or halogen, and the above groups may also be further substituted by substituents acceptable in the art; it is understandable that R and R' in -NRR' are each independently substituted by a group acceptable in the art, including but not limited to H, C1-6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclic group having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms; the C1-6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclic group having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms are optionally further substituted by one or more of the following groups: C1-C6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclic group having 3 to 8 ring atoms, halogen, hydroxyl, nitro or amino.

[0112] In the present invention, "the number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound obtained by bonding atoms into a ring (for example, monocyclic compound, fused-ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below under the condition of no special description. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thiophenyl group is 5.

[0113] In the present invention, "alkyl" may represent linear, branched and / or cyclic alkyl. The number of carbon atoms in the alkyl may be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, for example, "C1-9 alkyl" refer to alkyls containing 1 to 9 carbon atoms, and each occurrence may independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantane, etc.

[0114] The term "alkoxy" refers to a group having "-O-alkyl", that is, the alkyl as defined above is connected to the alkyl structure via an oxygen atom. The C1-C20 alkoxy includes C1-C19, C1-C14, C1-C12, C2-C6, C2-C4, C15, C10, C8, C5 and C20 alkoxy, etc. Phrases containing the C1-C20 alkoxy term, suitable examples include but are not limited to: methoxy (-O-CH 3 or -OMe), ethoxy (-O-CH 2 CH 3 or -OEt) and tert-butoxy (-O-C(CH 3 ) 3 or -OtBu).

[0115] The term "alkylthio" represents an alkyl group connected to the rest of the molecule through a sulfur atom, "-S-alkyl", where "alkyl" in the "alkyl group" is defined as above in the present invention. Unless specifically stated otherwise in the specification, the alkylthio may be optionally substituted. Unless otherwise specified, the term "C1-C20 alkylthio" refers to those alkyl groups containing 1 to 20 carbon atoms that are connected to the rest of the parent nucleus molecule through a sulfur atom. The C1-C20 alkylthio includes C1-C19, C1-C14, C1-C12, C2-C6, C2-C4, C15, C10, C8, C5 and C20 alkylthio, etc. Examples of C1-C20 alkylthio include but are not limited to -SCH 3 、-SCH 2 CH 3 、-SCH 2 CH 2 CH 3 、-SCH 2 (CH3) 2 、-SCH 2 CH2 CH 2 CH 3 、 - SCH 2 CH 2 (CH 3 ) 2 、 - SCH 2 CH 2 CH 2 CH 2 CH 3 、 - SCH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、 - SCH 2 (CH 2 CH 2 CH 3 )(CH 2 CH 2 CH 2 CH 3 )。

[0116] "Aryl" or "aromatic group" or "aromatic radical" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, which can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic ring systems, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" refers to a substituted or unsubstituted aryl containing 6 to 40 ring atoms, preferably an aryl having 6 to 30 ring atoms, more preferably an aryl having 6 to 18 ring atoms, particularly preferably an aryl having 6 to 14 ring atoms, and the aryl is optionally further substituted; suitable examples include but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, benzo[a]phenanthrene, dibenzo[a,h]anthracene, tetracene, pyrene, benzo[a]pyrene, acenaphthene, fluorene and their derivatives. It can be understood that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms such as C, N or O atoms), specifically such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aryl.

[0117] "Heteroaryl or heteroaromatic group or heteroaryl" means that on the basis of an aryl group, at least one carbon atom is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a substituted or unsubstituted heteroaryl containing 5 to 40 ring atoms, preferably a heteroaryl having 6 to 30 ring atoms, more preferably a heteroaryl having 6 to 18 ring atoms, particularly preferably a heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted. Suitable examples include, but are not limited to: triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, peridine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and its derivatives.

[0118] In the present invention, "*" connected to a single bond represents a connection site.

[0119] The present invention provides a benzotriazole organic compound, a preparation method and an application thereof, aiming to provide a new type of organic functional material with good stability, which can improve the photovoltaic efficiency and service life of a photovoltaic device.

[0120] The technical solution is as follows:

[0121] A benzotriazole organic compound, the general structural formula of which is shown in formula (1):

[0122]

[0123] Wherein each Ar independently includes a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0124] R 1 and R 2 are independently selected from a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group;

[0125] R 3 and R 4 are independently selected from a halogen, or a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group;

[0126] R 5 is selected from a substituted or unsubstituted alkyl group.

[0127] The benzotriazole organic compound provided by the present invention is based on benzotriazole and has specific Ar, R 1 、R2 , R 3 , R 4 and R 5 group modification can increase the fluorescence properties of the product, adjust the absorption spectrum to the ultraviolet region, and the fluorescence emission spectrum to the visible region, and the R 3 , R 4 introduction can adjust the donor-acceptor interaction within the molecule, increase molecular rigidity, improve the oxidation barrier, and enhance the molecular stability. Molecular rigidity can also increase the absorption extinction coefficient and fluorescence quantum yield of the compound molecule, thus facilitating the improvement of the light conversion efficiency and the conversion efficiency of the photovoltaic device.

[0128] In the present invention, each Ar independently includes a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Further, each of the said Ar independently includes a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Still further, each of the said Ar independently includes a substituted or unsubstituted aryl group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms. Still further, the Ar is selected from a substituted or unsubstituted six-membered aryl group, a substituted or unsubstituted six-membered heteroaryl group, and a substituted or unsubstituted five-membered heteroaryl group.

[0129] In some embodiments, each of the said Ar is independently selected from one of the following groups:

[0130]

[0131] wherein, * represents the connection site, and X represents O, S or Se.

[0132] In some embodiments, each of the said Ar is independently selected from one of the following groups:

[0133]

[0134] wherein, * represents the connection site, and X represents O, S or Se.

[0135] In the present invention, the R 1 and R 2 are independently selected from a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group. Further, the R 1 and R 2 are independently selected from a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group. Without limitation, the R 1 and R 2Independently selected from a substituted or unsubstituted C1-C20 linear alkyl group, or a substituted or unsubstituted C3-C20 branched alkyl group, or a substituted or unsubstituted C3-C20 cyclic alkyl group, or a substituted or unsubstituted C1-C20 linear alkoxy group, or a substituted or unsubstituted C3-C20 branched alkoxy group, or a substituted or unsubstituted C3-C20 cyclic alkoxy group. Preferably, the R 1 and R 2 are independently selected from a C1-C20 linear alkyl group substituted or unsubstituted by R, or a C3-C20 branched alkyl group substituted or unsubstituted by R, a C1-C20 linear alkoxy group substituted or unsubstituted by R, or a C3-C20 branched alkoxy group substituted or unsubstituted by R. Further, the R 1 and R 2 are independently selected from a C1-C10 linear alkyl group substituted or unsubstituted by R, or a C3-C10 branched alkyl group substituted or unsubstituted by R, a C1-C10 linear alkoxy group substituted or unsubstituted by R, or a C3-C10 branched alkoxy group substituted or unsubstituted by R. R 1 and R 2 in R are independently a C1-C6 linear alkyl group, further being methyl, ethyl, n-propyl or n-butyl.

[0136] In some embodiments, the R 1 and the R 2 are independently selected from one of the following groups:

[0137]

[0138] wherein, * represents the connection site, n 1 ≥2.

[0139] In the present invention, R 3 and R 4 are independently selected from a halogen (Group VII element), or a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group; without limitation, further, the R 3 and the R 4 are independently selected from a halogen, a substituted or unsubstituted C1-C20 alkoxy group, or a substituted or unsubstituted C1-C20 alkylthio group. Further, the R 3 and R 4Independently selected from fluorine, chlorine, bromine, iodine, astatine, a substituted or unsubstituted C1-C20 straight-chain alkoxy group, or a substituted or unsubstituted C3-C20 branched-chain alkoxy group, or a substituted or unsubstituted C3-C20 cyclic alkoxy group, or a substituted or unsubstituted C1-C20 straight-chain alkylthio group, or a substituted or unsubstituted C3-C20 branched-chain alkylthio group, or a substituted or unsubstituted C3-C20 cyclic alkylthio group, respectively.

[0140] Preferably, the R 3 and R 4 are each independently selected from one of the following groups:

[0141]

[0142] wherein, * represents the connection site, Y represents F, Cl, Br or I, and each R 6 is independently selected from a substituted or unsubstituted C1-C20 straight-chain alkyl group, or a substituted or unsubstituted C3-C20 branched-chain alkyl group.

[0143] Furthermore, the R 3 and R 4 are each independently selected from

[0144] Each R 6 is independently selected from a C1-C20 straight-chain alkoxy group substituted or unsubstituted by R, or a C3-C20 branched-chain alkoxy group substituted or unsubstituted by R, a C1-C20 straight-chain alkylthio group substituted or unsubstituted by R, or a C3-C20 branched-chain alkylthio group substituted or unsubstituted by R. Further, each R 6 is independently selected from a C1-C10 straight-chain alkoxy group substituted or unsubstituted by R, or a C3-C10 branched-chain alkoxy group substituted or unsubstituted by R, or a C1-C10 straight-chain alkylthio group substituted or unsubstituted by R, or a C3-C10 branched-chain alkylthio group substituted or unsubstituted by R.

[0145] Without limitation, the R in 6 are each independently a C1-C20 straight-chain alkyl group, and the C3-C20 straight-chain alkyl groups are further each independently a C1-C20 straight-chain alkyl group, a C3-C20 branched-chain alkyl group, or a C3-C20 cyclic alkyl group. Further, the R in 6 are each independently a C1-C10 straight-chain alkyl group, a C3-C10 branched-chain alkyl group, or a C3-C10 cyclic alkyl group. Further still, the R in 6 are each independently a C1-C6 straight-chain alkyl group, a C3-C6 branched-chain alkyl group. Still further, the R in 6 are each independently a methyl group, an ethyl group, a n-propyl group or a n-butyl group.

[0146] In some of these embodiments, the R 3 and R 4 are each independently selected from one of the following groups:

[0147]

[0148] wherein, * represents the connection site, and Y represents F, Cl, Br or I.

[0149] In the present invention, the R 5 is selected from substituted or unsubstituted alkyl groups. Preferably, the R 5 is selected from substituted or unsubstituted C1-C20 alkyl groups. Without limitation, the R 5 is selected from substituted or unsubstituted C1-C20 straight-chain alkyl groups, substituted or unsubstituted C3-C20 branched-chain alkyl groups, or substituted or unsubstituted C3-C20 cyclic alkyl groups. Preferably, the R 5 is selected from C1-C20 straight-chain alkyl groups substituted or unsubstituted by R, or C3-C20 branched-chain alkyl groups substituted or unsubstituted by R, or C3-C20 cyclic alkyl groups substituted or unsubstituted by R. Further, the R 5 are each independently selected from C1-C10 straight-chain alkyl groups substituted or unsubstituted by R, or C3-C10 branched-chain alkyl groups substituted or unsubstituted by R, or C3-C10 cyclic alkyl groups substituted or unsubstituted by R.

[0150] Without limitation, the Rs in R 5 are each independently C1-C20 straight-chain alkyl groups, and the C3-C20 straight-chain alkyl groups are further each independently C1-C20 straight-chain alkyl groups, C3-C20 branched-chain alkyl groups, or C3-C20 cyclic alkyl groups. Further, the Rs in R 5 are each independently C1-C10 straight-chain alkyl groups, C3-C10 branched-chain alkyl groups, or C3-C10 cyclic alkyl groups. Still further, the Rs in R 5 are each independently C1-C6 straight-chain alkyl groups, C3-C6 branched-chain alkyl groups. Even further, the Rs in R 5 are each independently methyl, ethyl, n-propyl or n-butyl.

[0151] In some of these embodiments, the R 5 is selected from one of the following groups:

[0152]

[0153] wherein, * represents the connection site, and n 2 ≥2.

[0154] In some of these embodiments, the benzotriazole organic compound of the present invention has any of the following structures:

[0155]

[0156] The present invention also provides a method for preparing the benzotriazole organic compound as described above, comprising the following steps:

[0157] Mix compound (a), compound (b), compound (c) and a base in a solvent, and react to prepare the benzotriazole organic compound of formula (1);

[0158]

[0159] R 1 and R 2 and R 3 and R 4 and R 5 are defined the same as the foregoing description of the benzotriazole organic compound.

[0160] In some embodiments, the molar ratio of compound (a), compound (b), and compound (c) is 1:(1-2):(1-2).

[0161] In some embodiments, the molar ratio of the base to compound (a) is (1-2):1.

[0162] In some embodiments, the base is selected from one or more of potassium carbonate, sodium carbonate, sodium methoxide, sodium ethoxide, and sodium tert-butoxide.

[0163] In some embodiments, the solvent is a mixed solvent of 1,4-dioxane and water.

[0164] In some embodiments, the reaction temperature is 80°C to 100°C, and the time is 20 h to 40 h.

[0165] In some embodiments, the method for preparing the benzotriazole organic compound as described above comprises the following steps:

[0166] Dissolve the 4,7-dibromobenzotriazole derivative shown in formula (a) and the alkylphenylboronic acid shown in formula (b)(c) in 1,4-dioxane, add a base and deionized water, then replace the reaction environment with an inert gas (nitrogen or argon is acceptable), heat to 80°C to 100°C, react for 20 h to 40 h, cool to room temperature, quench with water and extract with dichloromethane, spin dry, and use column chromatography to extract the target product, which is a white powder.

[0167] In some embodiments, the method for preparing the benzotriazole organic compound as described above comprises the following steps:

[0168] Dissolve 1 mmol of 4,7-dibromobenzotriazole derivative and 3 mmol of 4-alkylphenylboronic acid in 10 mL of 1,4-dioxane, add 2 mmol of potassium carbonate and 1 mL of deionized water, then replace the reaction environment with an inert gas (either nitrogen or argon), heat to 95 °C, react for 24 hours, cool to room temperature, quench with water and extract with dichloromethane, rotary evaporate, and use column chromatography to extract the target product, which is a white powder.

[0169] The present invention also provides the application of the benzotriazole organic compound as described above, and the technical solution is as follows:

[0170] A light conversion agent, comprising the benzotriazole organic compound as described above.

[0171] In some embodiments, the absorption wavelength range of the light conversion agent is 280 nm to 400 nm.

[0172] In some embodiments, the maximum absorption peak of the light conversion agent is 320 nm to 380 nm.

[0173] In some embodiments, the photoluminescence range of the light conversion agent is 400 nm to 600 nm.

[0174] In some embodiments, the maximum emission peak of the light conversion agent is 450 nm to 550 nm.

[0175] A photovoltaic adhesive film, comprising the benzotriazole organic compound as described above, or the light conversion agent as described above. This photovoltaic adhesive film can absorb ultraviolet light and convert it into visible light, such as blue light or sky blue light, and has good stability, high absorption extinction coefficient and fluorescence quantum yield, and has the advantages of good light conversion effect, high stability and low water vapor transmission rate. Further used in photovoltaic devices, it can improve the photovoltaic efficiency and stability of photovoltaic devices and extend the device life.

[0176] In some embodiments, the photovoltaic adhesive film further comprises a polymer material with optical transparency. It can be understood that in the present invention, the polymer material with optical transparency refers to a polymer material with a light transmittance ≥ 85% in the visible light range, a refractive index of 1.2 to 1.7, and a neutral density of 0.75 g / cm 3 ~1.2 g / cm 3 Preferably, the polymer material with optical transparency described in the present invention has a light transmittance ≥ 90% in the visible light range, a refractive index of 1.4 to 1.6, and a neutral density of 0.75 g / cm 3 ~1.2 g / cm 3 .

[0177] In some of these embodiments, by mass percentage, the photovoltaic adhesive film comprises 0.01% to 5% of the benzotriazole organic compound or the light conversion agent as described above, and 95% to 99.99% of the polymer material.

[0178] In some of these embodiments, the polymer material is selected from one or more of polyolefin elastomer (POE), ethylene-vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), and silicone resin materials. Further, the silicone resin material is selected from one or more of deacidifying one-component silica gel, alcohol-eliminating one-component silica gel, oxime-eliminating one-component silica gel, hydrogen-containing silicone oil, and vinyl-terminated polydimethylsiloxane.

[0179] In some of these embodiments, the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 to 15). Such a photovoltaic adhesive film has both antireflection and light conversion functions. Without limitation, the hydrogen-containing silicone oil includes one or more of Dow DC182, 184, 186, and Fuller Tian Shan 2538.

[0180] It can be understood that the photovoltaic adhesive film further comprises additives. Further, the additives include one or more of initiators, antioxidants, silane coupling agents, and light stabilizers.

[0181] In some of these embodiments, by mass percentage, the photovoltaic adhesive film comprises 0.01% to 4.95% of the benzotriazole organic compound or the light conversion agent as described above, 95% to 99.94% of the polymer material, and 0.05% to 4.99% of additives.

[0182] In some of these embodiments, by mass percentage, the photovoltaic adhesive film comprises 0.01% to 4.85% of the benzotriazole organic compound or the light conversion agent as described above, 95% to 99.84% of the polymer material, 0.05% to 1.5% of initiator, 0.05% to 1.5% of silane coupling agent, and 0.05% to 1.5% of antioxidant.

[0183] In some of these embodiments, by mass percentage, the photovoltaic adhesive film comprises 0.01% to 4.95% of the benzotriazole organic compound or the light conversion agent as described above, 95% to 99.94% of the polymer material, and 0.05% to 3% of antioxidant.

[0184] The present invention also provides a photovoltaic device, comprising a solar cell, at least one surface of the solar cell being provided with the photovoltaic adhesive film as described above. Without limitation, the surface of the solar cell is coated with the photovoltaic adhesive film as described above, or the photovoltaic adhesive film is disposed on at least one surface of at least one functional layer of the solar cell.

[0185] In some embodiments, the solar cell includes one or more of a crystalline silicon solar cell, a perovskite solar cell, and a tandem cell composed of a perovskite cell and a crystalline silicon cell.

[0186] In some embodiments, the solar cell is a tandem cell sheet composed of a perovskite cell and a crystalline silicon cell, with the perovskite cell serving as the light-incident surface and the crystalline silicon cell serving as the backlight surface. Further, referring to Figure 1 , the solar cell 1 includes a first transparent conductive layer 10, an electron transport layer 20, a perovskite active layer 30, a hole transport layer 40, a second transparent conductive layer 50, an N-type doping layer 60, a first amorphous silicon layer 70, a silicon wafer 80 (or silicon substrate), a second amorphous silicon layer 90, a P-type doping layer 100, and a third transparent conductive layer 110, which are sequentially stacked, as well as a first grid electrode layer and a second grid electrode layer;

[0187] The first grid electrode layer includes a plurality of first grid electrodes 120 disposed at intervals, and each first grid electrode is electrically connected to the first transparent conductive layer;

[0188] The second grid electrode layer includes a plurality of second grid electrodes 130 disposed at intervals, and each second grid electrode is electrically connected to the third transparent conductive layer.

[0189] Preferably, in the present invention, the electrical connection is a physical contact, that is, the electrical connection refers to a circuit connection of physical contact, rather than a wireless communication signal connection.

[0190] In the present invention, without limitation, the material of the first transparent conductive layer includes, but is not limited to, one or more selected from indium tin oxide, aluminum zinc oxide, aluminum indium oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the first transparent conductive layer is 5 nm to 200 nm.

[0191] In the present invention, without limitation, the material of the perovskite active layer includes, but is not limited to, compounds having an ABX 3 structure, wherein the A site is composed of one or more of methylammonium ions, formamidinium ions, and Cs + , the B site is composed of one or more of Sn 2+ and Pb 2+ , and the X site is composed of F - , Cl - , Br - and I -composed of one or more of them. Without limitation, the thickness of the perovskite active layer is 0.6 μm to 2 μm.

[0192] In the present invention, without limitation, the material of the hole transport layer includes but is not limited to one or more selected from nickel oxide, copper oxide, and molybdenum oxide. Without limitation, the thickness of the hole transport layer is 5 nm to 20 nm.

[0193] In the present invention, without limitation, the material of the second transparent conductive layer includes but is not limited to one or more selected from indium tin oxide, aluminum zinc oxide, aluminum indium oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the second transparent conductive layer is 5 nm to 40 nm.

[0194] In the present invention, without limitation, the material of the N-type doping layer includes but is not limited to one or more selected from phosphorus-doped amorphous silicon, phosphorus-doped nanocrystalline silicon (or microcrystalline silicon), and phosphorus-doped carbonated amorphous silicon. Without limitation, the thickness of the N-type doping layer is 3 nm to 10 nm.

[0195] In the present invention, without limitation, the material of the first amorphous silicon layer includes but is not limited to one or more selected from hydrogenated amorphous silicon, hydrogenated silicon oxide, and hydrogenated silicon oxynitride. Without limitation, the thickness of the first amorphous silicon layer is 1 nm to 2 nm.

[0196] In the present invention, without limitation, the thickness of the silicon wafer is 200 μm to 500 μm.

[0197] In the present invention, without limitation, the material of the second amorphous silicon layer includes but is not limited to one or more selected from hydrogenated amorphous silicon, hydrogenated silicon oxide, and hydrogenated silicon oxynitride. Without limitation, the thickness of the second amorphous silicon layer is 1 nm to 2 nm.

[0198] In the present invention, without limitation, the material of the P-type doping layer includes but is not limited to one or more selected from boron-doped amorphous silicon, boron-doped nanocrystalline silicon (or microcrystalline silicon), and boron-doped carbonated amorphous silicon. Without limitation, the thickness of the P-type doping layer is 3 nm to 20 nm.

[0199] In the present invention, without limitation, the material of the third transparent conductive layer includes but is not limited to one or more selected from indium tin oxide, aluminum zinc oxide, aluminum indium oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the third transparent conductive layer is 5 nm to 200 nm.

[0200] See Figure 2, in some embodiments, the solar cell 1 further includes a first antireflection layer 140, the first antireflection layer is stacked on the surface of the first transparent conductive layer away from the perovskite active layer, and the first grid electrode penetrates through the first antireflection layer and is electrically connected to the first transparent conductive layer;

[0201] Without limitation, the material of the first antireflection layer includes one or more of magnesium fluoride, lithium fluoride, silicon nitride, silicon oxide, and silicon oxynitride.

[0202] In the present invention, without limitation, the thickness of the first antireflection layer is 20 nm to 200 nm.

[0203] It can be understood that in the present invention, the electron transport layer can be one layer or two layers. For example, along the direction close to the perovskite active layer, the electron transport layer 20 includes a first electron transport layer 201 and a second electron transport layer 202. The material of the first electron transport layer includes, but is not limited to, one or more selected from semiconductor metal oxides such as tin oxide, zinc oxide, and titanium oxide. The material of the second electron transport layer includes, but is not limited to, one or more selected from C60, C70, PC 61 BM([6,6]-phenyl C 61 butyl methacrylate), PC 71 BM([6,6]-phenyl C 71 butyl methacrylate) - type fullerene derivatives, naphthalene diimide, and perylene diimide - type electron transport materials.

[0204] It can be understood that in order to further enhance the hole - transporting effect, a hole - modifying layer 150 is further provided between the perovskite active layer and the hole - transport layer. Further, the material of the hole - modifying layer includes, but is not limited to, one or more selected from materials with self - assembling properties containing carbazole and phosphoric acid functional groups such as Me - 4PACz (4 - (3,6 - dimethyl - 9H - carbazol - 9 - yl) butyl] phosphoric acid), MeO - 2PACz ((2 - (3,6 - dimethoxy - 9H - carbazol - 9 - yl) ethyl) phosphoric acid), and 2PACz ((2 - (9H - carbazol - 9 - yl) ethyl) phosphoric acid).

[0205] It can be understood that the N - type doping layer is selected from an N - type microcrystalline silicon layer or an N - type amorphous silicon layer, and the P - type doping layer is selected from a P - type microcrystalline silicon layer or a P - type amorphous silicon layer. The first amorphous silicon layer and the second amorphous silicon layer are each independently an intrinsic hydrogenated amorphous silicon layer.

[0206] Refer to Figure 3, the tandem cell composed of a perovskite cell and a crystalline silicon cell according to an embodiment of the present invention includes a first antireflection layer 140, a first transparent conductive layer 10, a first electron transport layer 201, a second electron transport layer 202, a perovskite active layer 30, a hole modification layer 150, a hole transport layer 40, a second transparent conductive layer 50, an N-type doping layer 60, a first amorphous silicon layer 70, a silicon wafer 80, a second amorphous silicon layer 90, a P-type doping layer 100, and a third transparent conductive layer 110, which are sequentially stacked, and a first grid electrode layer and a second grid electrode layer;

[0207] The first grid electrode layer includes a plurality of first grid electrodes 120 arranged at intervals, and each first grid electrode is electrically connected to the first transparent conductive layer;

[0208] The second grid electrode layer includes a plurality of second grid electrodes 130 arranged at intervals, and each second grid electrode is electrically connected to the third transparent conductive layer.

[0209] Preferably, in the present invention, the electrical connection is a physical contact, that is, the electrical connection refers to a circuit connection of physical contact, rather than a wireless communication signal connection.

[0210] Furthermore, Figure 3 The material of the first antireflection layer 140 in the tandem cell includes one or more of magnesium fluoride, lithium fluoride, silicon nitride, silicon oxide, and silicon oxynitride.

[0211] Referring to Figure 4 , the present invention also provides a photovoltaic device, including a light-incident surface panel 210, a solar cell 230, and a backlight surface panel 240 that are sequentially stacked. Among them, the surface of the solar cell is coated with the photovoltaic adhesive film 220 as described above. Furthermore, the solar cell has Figure 1 , Figure 2 or Figure 3 the structure shown.

[0212] In some embodiments, the light-incident surface panel and the backlight surface panel are glass panels.

[0213] The present invention also provides a preparation method of a photovoltaic device as Figure 4 shown:

[0214] Select a glass front plate of the required size, cut the adhesive film containing the light conversion agent to a matching size, lay it on the front plate glass, then lay the battery string with electrical connections, and then lay the second adhesive film and the glass back plate. Laminating in a laminator can obtain a component laminate, and then installing a junction box and a metal frame can obtain Figure 4 the photovoltaic device shown.

[0215] For the antireflection technology of perovskite in the industry, most of them use evaporated MgFx (MgF with a deviation from the stoichiometric ratio, 2 , optionally, 1.5 ≤ x ≤ 2) film layers. However, the output of MgFx is relatively low and the price is relatively high, which is not conducive to the promotion of mass production. For the light conversion technology, most of the industry uses ethylene-vinyl acetate copolymer (EVA) or polyolefin elastomer (POE) film with a light conversion agent added. Moreover, the antireflection technology and the light conversion technology are two independently developed systems without a precedent of combination. In some embodiments of the present invention, the photovoltaic antireflection technology and the light conversion technology are combined. While reducing the reflection of photons on the surface of the battery and increasing the transmittance to improve the device power, it reduces the damage of ultraviolet light to the battery, and converts ultraviolet light into visible light to further improve the device power. In addition, the antireflection raw materials used are rich in sources and can be introduced into mass production for industrial application.

[0216] The technical solution is as follows:

[0217] A photovoltaic device includes a solar cell, and at least one surface of the solar cell is provided with a patterned photovoltaic film as described above. Further, the photovoltaic film is disposed in the antireflection layer of the solar cell to play the roles of antireflection and light conversion. Further preferably, the antireflection layer includes 0.01% - 5% of the benzotriazole organic compound or light conversion agent as described in the present invention, and 95% - 99.99% of the silicone resin material, and the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1: (2 - 15). Such an antireflection layer photovoltaic film has both antireflection and light conversion functions and can be called an antireflection and light conversion photovoltaic film.

[0218] In some of these embodiments, the solar cell includes one or more of a crystalline silicon solar cell, a perovskite solar cell, and a tandem cell composed of a perovskite cell and a crystalline silicon cell.

[0219] In some of these embodiments, the solar cell is a tandem cell composed of a perovskite cell and a crystalline silicon cell, with the perovskite cell as the light-incident surface and the crystalline silicon cell as the backlight surface. Further, referring to Figure 5 , the solar cell includes a second antireflection layer 160, a first transparent conductive layer 10, an electron transport layer 20, a perovskite active layer 30, a hole transport layer 40, a second transparent conductive layer 50, an N-type doping layer 60, a first amorphous silicon layer 70, a silicon wafer 80, a second amorphous silicon layer 90, a P-type doping layer 100, and a third transparent conductive layer 110, which are sequentially stacked, as well as a first grid electrode layer and a second grid electrode layer;

[0220] The first grid electrode 120 penetrates through the second antireflection layer 160 and is electrically connected to the first transparent conductive layer;

[0221] The second gate line electrode 130 is electrically connected to the third transparent conductive layer;

[0222] The second antireflection layer 160 includes a patterned photovoltaic adhesive film as described above. The photovoltaic adhesive film includes 0.01% - 5% of the benzotriazole-based organic compound or light conversion agent, and 95% - 99.99% of the silicone resin material. And the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 - 15).

[0223] Further, referring to Figure 6 , the solar cell includes a second antireflection layer 160, a first transparent conductive layer 10, an electron transport layer 20, a perovskite active layer 30, a hole transport layer 40, a second transparent conductive layer 50, an N-type doping layer 60, a first amorphous silicon layer 70, a silicon wafer 80, a second amorphous silicon layer 90, a P-type doping layer 100, a third transparent conductive layer 110, and a third antireflection layer 170, which are sequentially stacked, and a first gate line electrode layer and a second gate line electrode layer;

[0224] The first gate line electrode 120 penetrates through the second antireflection layer 160 and is electrically connected to the first transparent conductive layer;

[0225] The second gate line electrode 130 penetrates through the third antireflection layer 170 and is electrically connected to the third transparent conductive layer;

[0226] The second antireflection layer 160 includes a patterned photovoltaic adhesive film as described above. The photovoltaic adhesive film includes 0.01% - 5% of the benzotriazole-based organic compound or light conversion agent, and 95% - 99.99% of the silicone resin material. And the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 - 15);

[0227] The third antireflection layer 170 includes a patterned photovoltaic adhesive film as described above. The photovoltaic adhesive film includes 0.01% - 5% of the benzotriazole-based organic compound or light conversion agent, and 95% - 99.99% of the silicone resin material. And the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 - 15).

[0228] Understandably, the second antireflection layer 160 and the third antireflection layer 170 are independent of each other, and their respective compositions may be the same or different. That is, the types of benzotriazole organic compounds in the second antireflection layer 160 and the third antireflection layer 170 may be the same or different, the contents of benzotriazole organic compounds may be the same or different, and similarly, the types of silicone resin materials may be the same or different, the contents of silicone resin materials may be the same or different, the types of hydrogen-containing silicone oil may be the same or different, the types of vinyl-terminated polydimethylsiloxane may be the same or different, and the mass ratio of hydrogen-containing silicone oil to vinyl-terminated polydimethylsiloxane may be the same or different.

[0229] In the present invention, for a photovoltaic device in which the antireflection layer includes a patterned antireflective photovoltaic film, without limitation, the material of the first transparent conductive layer includes, but is not limited to, one or more selected from indium tin oxide, aluminum zinc oxide, indium aluminum oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the first transparent conductive layer is 5 nm to 200 nm. The material of the perovskite active layer includes, but is not limited to, a compound having an ABX 3 structure, where the A site is composed of one or more of methylammonium ions, formamidinium ions, and Cs + , the B site is composed of one or more of Sn 2+ and Pb 2+ , and the X site is composed of F - , Cl - , Br - and I -Composed of one or more of the following. Without limitation, the thickness of the perovskite active layer is 0.6 μm to 2 μm. The materials of the hole transport layer include, but are not limited to, one or more selected from nickel oxide, copper oxide, and molybdenum oxide. Without limitation, the thickness of the hole transport layer is 5 nm to 20 nm. The materials of the second transparent conductive layer include, but are not limited to, one or more selected from indium tin oxide, aluminum zinc oxide, aluminum indium oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the second transparent conductive layer is 5 nm to 40 nm. The materials of the N-type doping layer include, but are not limited to, one or more selected from phosphorus-doped amorphous silicon, phosphorus-doped nanocrystalline silicon (or microcrystalline silicon), and phosphorus-doped carbon-oxide amorphous silicon. Without limitation, the thickness of the N-type doping layer is 3 nm to 10 nm. The materials of the first amorphous silicon layer include, but are not limited to, one or more selected from hydrogenated amorphous silicon, hydrogenated silicon oxide, and hydrogenated silicon oxynitride. Without limitation, the thickness of the first amorphous silicon layer is 1 nm to 2 nm. Without limitation, the thickness of the silicon wafer is 200 μm to 500 μm. The materials of the second amorphous silicon layer include, but are not limited to, one or more selected from hydrogenated amorphous silicon, hydrogenated silicon oxide, and hydrogenated silicon oxynitride. Without limitation, the thickness of the second amorphous silicon layer is 1 nm to 2 nm. The materials of the P-type doping layer include, but are not limited to, one or more selected from boron-doped amorphous silicon, boron-doped nanocrystalline silicon (or microcrystalline silicon), and boron-doped carbon-oxide amorphous silicon. Without limitation, the thickness of the P-type doping layer is 3 nm to 20 nm. The materials of the third transparent conductive layer include, but are not limited to, one or more selected from indium tin oxide, aluminum zinc oxide, aluminum indium oxide, indium cerium oxide, and indium tungsten oxide. Without limitation, the thickness of the third transparent conductive layer is 5 nm to 200 nm.

[0230] Similarly, for a photovoltaic device in which the antireflection layer includes a patterned antireflection photoresist film, the electron transport layer can be one layer or two layers. For example, along the direction closer to the perovskite active layer, the electron transport layer includes a first electron transport layer and a second electron transport layer. The materials of the first electron transport layer include, but are not limited to, one or more selected from semiconductor metal oxides such as tin oxide, zinc oxide, and titanium oxide. The materials of the second electron transport layer include, but are not limited to, one or more selected from C60, C70, PC 61 BM ([6,6]-phenyl C 61 butyrate methyl ester), PC 71 BM ([6,6]-phenyl C 71 butyrate methyl ester) -type fullerene derivatives, naphthalene diimide, and perylene diimide -type electron transport materials.

[0231] Understandably, for a photovoltaic device in which the antireflection layer comprises a patterned antireflective photovoltaic film, in order to further enhance the hole transport effect, a hole modification layer is further provided between the perovskite active layer and the hole transport layer. Further, the material of the hole modification layer includes but is not limited to one or more selected from materials having a self-assembly property containing carbazole and phosphoric acid functional groups such as Me-4PACz (4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid), MeO-2PACz ((2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl)phosphonic acid), and 2PACz ((2-(9H-carbazol-9-yl)ethyl)phosphonic acid).

[0232] Understandably, for a photovoltaic device in which the antireflection layer comprises a patterned antireflective photovoltaic film, the N-type doping layer is selected from an N-type microcrystalline silicon layer or an N-type amorphous silicon layer, and the P-type doping layer is selected from a P-type microcrystalline silicon layer or a P-type amorphous silicon layer. The first amorphous silicon layer and the second amorphous silicon layer are each independently an intrinsic hydrogenated amorphous silicon layer.

[0233] Figure 6 It is a schematic structural diagram of a solar cell containing a double-layer patterned antireflection layer shown in one embodiment of the present invention. Patterned antireflective photovoltaic films are provided on both the second antireflection layer (light incident surface antireflection layer) and the third antireflection layer (backlight surface) of the solar cell.

[0234] Refer to Figure 7 , the present invention also provides a flowchart of a preparation method and a schematic intermediate structure diagram of a solar cell containing a double-layer patterned antireflection layer as described in Figure 6 . The preparation method includes the following steps:

[0235] Texturize the surface of the silicon wafer to obtain a patterned textured surface;

[0236] Prepare a solution of organosilicon resin (PDMS) containing a light conversion agent;

[0237] Fill the PDMS solution containing the light conversion agent on the textured surface, heat, cure, and peel to obtain a patterned photovoltaic film;

[0238] Flatly attach the patterned photovoltaic film to the surface of the solar cell.

[0239] Figure 8 It is a schematic structural diagram of a pyramid photovoltaic film and a hemispherical photovoltaic film. Optionally, Figure 8 the height of the pyramid textured surface shown in a and b is 0.01 μm to 10 μm, and the pyramid size error is less than or equal to 1 μm; Figure 8 the height of the hemispherical textured surface shown in c and d is 0.01 μm to 10 μm, and the size error is less than or equal to 1 μm.

[0240] The present invention will be described below in conjunction with embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims define the scope of the present invention. Under the guidance of the inventive concept of the present invention, those skilled in the art should realize that certain changes made to the embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific Embodiments

[0242] 1. Compound Synthesis Examples

[0243] Synthesis Example 1: Synthesis The steps are as follows:

[0244] Weigh 1 mmol of 4,7-dibromo-5,6-dichloro-2-isobutyl-2H-benzo[d][1,2,3]triazole, 3 mmol of (4-(tert-butyl)phenyl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen, and cycle three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, spin-dry to obtain a crude product. Prepare a chromatographic column using 200 - 300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:4) as the eluent, collect the blue fluorescent part, combine the eluents, and spin-dry to obtain a white solid.

[0245] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.41–7.31 (m, 8H), 3.92 (d, J = 7.0, 2H), 2.34 (dp, J = 13.7, 6.8, 1H), 1.34 (s, 14H), 1.04 (d, J = 6.8, 6H). The 1H NMR spectrum is referred to Figure 9 . MALDI-TOF shows that the mass of the compound is 507.2.

[0246] Combined with the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 1.

[0247] Synthesis Example 2: Synthesis The steps are as follows:

[0248] Weigh 1 mmol of 4,7-dibromo-5,6-difluoro-2-isobutyl-2H-benzo[d][1,2,3]triazole, 3 mmol of (4-(tert-butyl)phenyl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, evaporate to dryness to obtain the crude product. Prepare a chromatography column with 200 - 300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:4) as the eluent, collect the blue fluorescent part, combine the eluents, and evaporate to dryness to obtain a white solid.

[0249] 1 H NMR (500 MHz, Chloroform-d) δ = 7.45–7.39 (m, 4H), 7.39–7.33 (m, 4H), 3.92 (d, J = 7.0, 2H), 2.35 (hept, J = 6.9, 1H), 1.34 (s, 13H), 1.03 (d, J = 6.9, 5H). The 1H NMR spectrum is shown in Figure 10 . MOLDI-TOF shows that the mass of the compound is 476.28.

[0250] Combining the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in this synthesis example.

[0251] Synthesis Example 3: Synthesis of The steps are as follows:

[0252] Weigh 1 mmol of 4,7-dibromo-5,6-difluoro-2-(2-ethylhexyl)-2H-benzo[d][1,2,3]triazole, 3 mmol of (4-(tert-butyl)phenyl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, evaporate to dryness to obtain the crude product. Prepare a chromatography column with 200 - 300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:8) as the eluent, collect the blue fluorescent part, combine the eluents, and evaporate to dryness to obtain a white solid.

[0253] 11H NMR (500 MHz, Chloroform-d) δ = 7.42–7.37 (m, 1H), 7.37–7.32 (m, 1H), 1.55–1.39 (m, 1H), 1.41–1.29 (m, 1H), 1.34 (s, 6H), 0.91 (td, J = 8.0, 0.9, 2H). The 1H NMR spectrum is shown in Figure 11 . MOLDI-TOF shows that the mass of the compound is 531.3.

[0254] Combining the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 3.

[0255] Synthesis Example 4: Synthesis of The steps are as follows:

[0256] Weigh 1 mmol of 4,7-dibromo-5,6-difluoro-2-isobutyl-2H-benzo[d][1,2,3]triazole, 3 mmol of (5-isobutylthiophen-2-yl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen, and cycle three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, and then extract three times with dichloromethane. Combine the organic layers, rotary evaporate to obtain a crude product. Prepare a chromatographic column with 200-300 mesh silica gel, use dichloromethane and petroleum ether (v / v 1:6) as the eluent, collect the blue fluorescence part, combine the eluents, and rotary evaporate to obtain a pale yellow solid.

[0257] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.25 (d, J = 7.5, 1H), 6.86 (d, J = 7.5, 1H), 3.92 (d, J = 7.0, 1H), 2.60 (d, J = 7.0, 2H), 2.35 (dp, J = 13.6, 6.9, 0H), 1.91 (dp, J = 13.7, 6.8, 1H), 1.03 (d, J = 6.8, 3H), 0.96 (d, J = 6.8, 6H). The 1H NMR spectrum is shown in Figure 12 . MOLDI-TOF shows that the mass of the compound is 487.2.

[0258] Combining the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 4.

[0259] Synthesis Example 5: Synthesis of The steps are as follows:

[0260] (1) Synthesis Step 1: Weigh 1 mmol of 4,7-dibromo-5,6-difluoro-2-(2-ethylhexyl)-2H-benzo[d][1,2,3]triazole, 3 mmol of (4-isobutoxyphenyl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, rotary evaporate to obtain the crude product. Prepare a chromatographic column with 200 - 300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:3) as the eluent, collect the blue fluorescent part, combine the eluents, and rotary evaporate to obtain a white solid.

[0261] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.46–7.40 (m, 4H), 7.01–6.95 (m, 4H), 3.91 (dd, J = 12.4, 7.0, 1H), 3.84–3.76 (m, 5H), 2.07 (dt, J = 13.9, 6.8, 3H), 1.56–1.28 (m, 8H), 1.06 (d, J = 6.8, 6H), 1.01 (d, J = 6.8, 6H), 0.91 (td, J = 8.0, 1.6, 6H). The 1H NMR spectrum is shown in Figure 13 . MALDI-TOF shows that the mass of the compound is 563.3.

[0262] Combined with the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in this Synthesis Example 5.

[0263] Synthesis Example 6: Synthesis The steps are as follows:

[0264] Weigh 1 mmol of 4,7-dibromo-2-isobutyl-5,6-dimethoxy-2H-benzo[d][1,2,3]triazole, 3 mmol of (4-(tert-butyl)phenyl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, rotary evaporate to obtain the crude product. Prepare a chromatographic column with 200 - 300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:3) as the eluent, collect the blue fluorescent part, combine the eluents, and rotary evaporate to obtain a white solid.

[0265] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.44–7.34 (m, 3H), 3.90 (d, J = 7.0, 1H), 3.83 (s, 2H), 1.34 (s, 5H), 1.03 (d, J = 6.9, 2H). The 1H NMR spectrum is shown in Figure 14 . MALDI-TOF shows that the mass of the compound is 499.3.

[0266] Combining the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 6.

[0267] Synthesis Example 7: Synthesis of The steps are as follows:

[0268] Weigh 1 mmol of 4,7-dibromo-5,6-diethoxy-2-isobutyl-2H-benzo[d][1,2,3]triazole, 3 mmol of (5-isobutylthiophen-2-yl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract with dichloromethane three times, combine the organic layers, and dry by evaporation to obtain a crude product. Prepare a chromatographic column using 200-300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:4) as the eluent, collect the blue fluorescence part, combine the eluents, and dry by evaporation to obtain a pale yellow solid.

[0269] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.15 (d, J = 7.5, 1H), 6.86 (d, J = 7.5, 1H), 4.17 (q, J = 8.0, 2H), 3.90 (d, J = 7.0, 1H), 2.61 (d, J = 7.0, 2H), 2.35 (dt, J = 13.7, 6.8, 0H), 1.90 (dp, J = 13.6, 6.9, 1H), 1.43 (t, J = 8.0, 3H), 1.04 (d, J = 6.8, 3H), 0.96 (d, J = 6.8, 6H). The 1H NMR spectrum is shown in Figure 15 . MALDI-TOF shows that the mass of the compound is 539.3.

[0270] Combining the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 7.

[0271] Synthesis Example 8: Synthesis of The steps are as follows:

[0272] Weigh 1 mmol of 4,7-dibromo-5,6-diisobutoxy-2-isobutyl-2H-benzo[d][1,2,3]triazole, 3 mmol of (5-isobutylthiophen-2-yl)boronic acid, and 3 mmol of potassium carbonate into a 50 mL two-necked flask. Connect to a vacuum line, evacuate and fill with nitrogen, and cycle three times to ensure an inert gas atmosphere. Then add 10 mL of 1,4-dioxane and 10 mL of deionized water. After stirring well, place the reaction at 95 °C for 24 hours. After the reaction is completed, add 20 mL of deionized water to quench the reaction, then extract three times with dichloromethane. Combine the organic layers, spin-dry to obtain the crude product. Prepare a chromatographic column using 200-300 mesh silica gel, use dichloromethane and petroleum ether (v / v = 1:4) as the eluent, collect the blue fluorescence part, combine the eluents, and spin-dry to obtain a pale yellow solid.

[0273] 1 1H NMR (500 MHz, Chloroform-d) δ = 7.15 (d, J = 7.5, 1H), 6.86 (d, J = 7.5, 1H), 3.91 (dd, J = 9.9, 7.0, 3H), 2.61 (d, J = 7.0, 2H), 2.36 (dt, J = 13.7, 6.8, 0H), 2.09 (dp, J = 13.7, 6.9, 1H), 1.90 (dp, J = 13.6, 6.9, 1H), 1.04 (dd, J = 6.8, 4.0, 9H), 0.96 (d, J = 6.8, 6H). The 1H NMR spectrum is shown in Figure 16 . MALDI-TOF shows that the mass of the compound is 595.3.

[0274] Combined with the results of 1H NMR and mass spectrometry, it can be seen that the target compound was synthesized in Synthesis Example 8 of this example.

[0275] Device Example

[0276] Device Example 1

[0277] This example provides a Figure 3 solar cell as shown in Figure 4 a photovoltaic module as shown in and its preparation method, which are specifically as follows:

[0278] 1. Prepare Figure 3 the solar cell as shown in, the steps are as follows:

[0279] First, clean and texture a 280-μm-thick silicon wafer. Subsequently, fabricate first and second amorphous silicon layers with a thickness of 2 nm in a PECVD process, then fabricate an N-type doped layer with a thickness of 5 nm, and then fabricate a P-type amorphous silicon layer with a thickness of 10 nm. Subsequently, use magnetron sputtering to fabricate a second transparent conductive layer with a thickness of 20 nm on the N-type doped layer, fabricate a third transparent conductive layer with a thickness of 40 nm on the P-type doped layer, and print a second grid line electrode layer thereon. Then, fabricate a hole transport layer with a thickness of 10 nm on the second transparent conductive layer, deposit a 1-nm hole modification layer, then deposit a 0.8-μm-thick perovskite active layer using a solution method, deposit a 20-nm second electron transport layer using thermal evaporation, deposit a 20-nm first electron transport layer using atomic layer deposition, then fabricate an 80-nm-thick first transparent conductive layer on the electron transport layer using magnetron sputtering, and then magnetron sputter 80 nm of MgFx on the surface of the first transparent conductive layer, and print the first grid line electrode layer and the second grid line electrode layer to obtain a solar cell.

[0280] 2. Preparation Figure 4 The photovoltaic module shown is prepared as follows:

[0281] (1) Mix ethylene-vinyl acetate, the benzotriazole compound shown in Synthesis Example 1, tert-butyl peroxycarbonate-2-ethylhexyl ester (TBEC), silane coupling agent KH570, and antioxidant 152, dry to form a film, and prepare a photovoltaic adhesive film, which can be called a light conversion adhesive film;

[0282] Among them, by mass percentage, the light conversion adhesive film includes 99% ethylene-vinyl acetate, 0.2% of the benzotriazole compound shown in Synthesis Example 1, 0.3% of TBEC, 0.3% of silane coupling agent KH570, and 0.2% antioxidant 152;

[0283] (2) Select a glass front plate of the required size, cut the above-mentioned light conversion adhesive film to a matching size, lay it on the front plate glass, then lay a solar cell string with electrical connections, and then lay a second adhesive film and a glass rear plate, and laminate in a laminator to obtain a module laminate, and then install a junction box and a metal frame to obtain Figure 4 the photovoltaic module shown.

[0284] Device Example 2

[0285] This example provides a Figure 3 solar cell shown, Figure 4 the photovoltaic module shown and its preparation method, specifically as follows:

[0286] 1. Preparation Figure 3 The solar cell shown is prepared as in Device Example 1.

[0287] 2. PreparationFigure 4 The photovoltaic module shown has steps that are basically the same as those in Device Example 1, except that:

[0288] By mass percentage, the light conversion film comprises 99.5% ethylene-octene copolymer elastomer and 0.5% of the benzotriazole compound of Synthesis Example 2.

[0289] Device Example 3

[0290] This example provides a Figure 3 solar cell shown, Figure 4 the photovoltaic module shown and its preparation method, specifically as follows:

[0291] 1. Prepare the Figure 3 solar cell shown, and the steps are as in Device Example 1.

[0292] 2. Prepare the Figure 4 photovoltaic module shown, and the steps are basically the same as those in Device Example 1, except that:

[0293] By mass percentage, the light conversion film composition comprises 99% of Dow Corning DC184 silicone polymer resin, 0.5% of the benzotriazole compound of Synthesis Example 3, and 0.5% of antioxidant 152.

[0294] For Device Examples 4 to 8 and Device Comparative Examples 1 to 3, referring to the method of Device Example 1 and the content shown in Table 1, the types of light conversion agents are replaced to prepare different solar cells and photovoltaic modules. Among them, the light conversion agents used in Device Comparative Examples 1 to 3 are purchased from Zhengzhou Alpha Chemical Co., Ltd.

[0295] Perform performance tests on the solar cells and photovoltaic modules of Device Examples 1 to 8 and Device Comparative Examples 1 to 3. The test methods are as follows:

[0296] (1) Light conversion efficiency: The ratio of the number of photons emitting secondary radiation fluorescence to the number of photons absorbing primary radiation of the excitation light per unit time. The results are shown in Table 1.

[0297] (2) Photovoltaic efficiency: Under AM1.5G, 25 °C, use an IV test system to test the efficiency of the photovoltaic cell. The results are shown in Table 1.

[0298] (3) T80 test: Use the AM1.5G simulated xenon lamp spectrum, continuously track the battery at the maximum power point, and measure the time when the battery efficiency decays to 80%. The results are shown in Table 1.

[0299] Table 1

[0300]

[0301]

[0302] As can be seen from Table 1, compared with Device Comparative Examples 1 to 3, Device Examples 1 to 8 respectively use the benzotriazole organic compounds of Synthesis Examples 1 to 8 of the present invention as light conversion agents, and the prepared photovoltaic modules have higher light conversion efficiency, photovoltaic efficiency and lifespan, and Device Example 5 has the highest conversion efficiency and the longest T80.

[0303] Device Example 9

[0304] This example provides a Figure 6 solar cell as shown and its preparation method, the steps are as follows:

[0305] (1) Clean and texture a 280-μm-thick silicon wafer, then fabricate first and second amorphous silicon layers with a thickness of 2 nm in PECVD, then fabricate an N-type doped layer with a thickness of 5 nm, then fabricate a P-type amorphous silicon layer with a thickness of 10 nm, then use magnetron sputtering to fabricate a second transparent conductive layer with a thickness of 20 nm on the N-type doped layer, fabricate a third transparent conductive layer with a thickness of 40 nm on the P-type doped layer, and print a second grid electrode layer thereon, then fabricate a hole transport layer with a thickness of 10 nm on the second transparent conductive layer, deposit a 1-nm hole modification layer, then use the solution method to deposit a 0.8-μm-thick perovskite active layer, use thermal evaporation to deposit a 20-nm second electron transport layer, use atomic layer deposition to deposit a 20-nm first electron transport layer, and then use magnetron sputtering to fabricate a first transparent conductive layer with a thickness of 80 nm on the electron transport layer;

[0306] (2) Weigh 1 g of hydrogen-containing silicone oil (the cross-linking agent component of Dow Corning 184 silicone), add 11 mg of the benzotriazole compound of Synthesis Example 5, then add 10 g of double-bond-terminated PDMS, stir evenly, degas under vacuum to form a transparent solution; select a 10 cm × 10 cm textured silicon wafer with a pyramid height of 0.5 μm, then introduce 10 mL of the above transparent solution onto its surface, use a spin coater to spin coat at a speed of 500 rpm for 60 seconds, then heat the silicon wafer to 120 °C and maintain for 15 minutes to complete curing, then cool to room temperature and peel off to obtain a photovoltaic adhesive film with a pyramid structure;

[0307] (3) Attach the smooth surface of the above photovoltaic adhesive film to the surface of the first transparent conductive layer and the surface of the third transparent conductive layer, respectively serving as the second antireflection layer and the third antireflection layer;

[0308] (4) Print the first grid electrode layer and the second grid electrode layer to obtain Figure 6 the solar cell as shown.

[0309] Device Comparative Example 4

[0310] Device Comparative Example 4 is basically the same as Device Example 9, except that, by mass percentage, both the second antireflection layer and the third antireflection layer are composed of 99.9% EVA and 0.1% UV-329.

[0311] The IV and EQE performances of the solar cells prepared from Device Example 9 and Device Comparative Example 4 were tested, and the results are as Figure 17 and Figure 18 shown. Among them, Figure 17 is the I-V diagram of Device Example 9 and Device Comparative Example 4. As can be seen from Figure 17 , Device Example 9 has an obvious increase in short-circuit current density, thus improving the cell efficiency. Figure 18 is the EQE diagram of Device Example 9 and Device Comparative Example 4. As can be seen from Figure 18 , compared with Device Comparative Example 4, Device Example 9 has an obvious improvement in the short-wave direction, and the overall QE response is also improved due to the presence of the antireflection film, and the short-circuit current density is increased.

[0312] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0313] The above-described embodiments only represent several implementation manners of the present invention, but should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A benzotriazole organic compound, characterized in that, its structural general formula is shown as formula (1): wherein each Ar independently includes a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heteroaromatic group; R 1 and R 2 are each independently selected from substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy; R 3 and R 4 are each independently selected from halogen, substituted or unsubstituted alkoxy, or substituted or unsubstituted alkylthio; R 5 Selected from substituted or unsubstituted alkyl groups.

2. The benzotriazole organic compound according to claim 1, characterized in that, each of said Ar independently includes a substituted or unsubstituted aromatic group with 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group with 5 to 30 ring atoms.

3. The benzotriazole organic compound according to claim 2, characterized in that, each of said Ar is independently selected from a substituted or unsubstituted six-membered aromatic group, a substituted or unsubstituted six-membered heteroaromatic group, or a substituted or unsubstituted five-membered heteroaromatic group.

4. The benzotriazole organic compound according to claim 3, characterized in that, each of said Ar is independently selected from one of the following groups: wherein, * represents the connection site, and X represents O, S or Se.

5. The benzotriazole organic compound according to any one of claims 1 to 4, characterized in that, The said R 1 and the said R 2 are each independently selected from substituted or unsubstituted C1-C20 alkyl groups, or substituted or unsubstituted C1-C20 alkoxy groups.

6. The benzotriazole organic compound according to claim 5, characterized in that, The said R 1 and the said R 2 are each independently selected from one of the following groups: Among them, * represents the connection site, and n 1 ≥ 2.

7. The benzotriazole organic compound according to any one of claims 1 to 4, characterized in that, The R 3 and the R 4 are each independently selected from a halogen, a substituted or unsubstituted C1-C20 alkoxy group, or a substituted or unsubstituted C1-C20 alkylthio group.

8. The benzotriazole organic compound according to claim 7, characterized in that, Said R 3 and R 4 are each independently selected from one of the following groups: Among them, * represents a linking site, Y represents F, Cl, Br or I, and each R 6 is independently selected from a substituted or unsubstituted C1-C20 straight-chain alkyl group, or a substituted or unsubstituted C3-C20 branched-chain alkyl group.

9. The benzotriazole organic compound according to any one of claims 1 to 4, characterized in that, Said R 5 is selected from substituted or unsubstituted C1-C20 alkyl groups.

10. The benzotriazole organic compound according to claim 9, characterized in that, The said R 5 selected from one of the following groups: Among them, * represents the connection site, and n 2 ≥ 2.

11. The benzotriazole organic compound according to claim 1, characterized in that, has one of the following structures:

12. A preparation method of the benzotriazole organic compound according to any one of claims 1 to 11, characterized in that, comprises the following steps: Mixing compound (a), compound (b), compound (c) and a base in a solvent, reacting to prepare the benzotriazole organic compound; R 1 、R 2 、R 3 、R 4 and R 5 are defined in the same way as any one of claims 1 to 11.

13. A light conversion agent, characterized in that, comprises the benzotriazole organic compound according to any one of claims 1 to 11.

14. The light conversion agent according to claim 13, characterized in that, the light conversion agent has at least one of the following characteristics: (1) The absorption wavelength range is 280nm - 400nm; (2) The maximum absorption peak is 320nm - 380nm.

15. The light conversion agent according to claim 13 or 14, characterized in that, the light conversion agent has at least one of the following characteristics: (1) The range of photoluminescence is 400nm - 600nm; (2) The maximum emission peak is 450nm - 550nm.

16. A photovoltaic adhesive film, characterized in that, comprises the benzotriazole organic compound according to any one of claims 1 to 11, or the light conversion agent according to any one of claims 13 to 15.

17. The photovoltaic adhesive film according to claim 16, characterized in that, its composition further includes an optically transparent polymer material.

18. The photovoltaic adhesive film according to claim 17, characterized in that it satisfies one or more combinations of the following (1) to (2): (1) By mass percentage, the photovoltaic adhesive film comprises 0.01% to 5% of the benzotriazole organic compound according to any one of claims 1 to 11 or the light conversion agent according to any one of claims 13 to 15, and 95% to 99.99% of the polymer material; (2) The polymer material is selected from one or more of polyolefin elastomer, ethylene-vinyl acetate copolymer, polyvinyl butyral, and silicone resin material.

19. The photovoltaic adhesive film according to claim 18, characterized in that the silicone resin material is a mixture composed of hydrogen-containing silicone oil and vinyl-terminated polydimethylsiloxane in a mass ratio of 1:(2 to 15).

20. A photovoltaic device, characterized in that it includes a solar cell, and at least one surface of the solar cell is provided with the photovoltaic adhesive film according to any one of claims 16 to 19.

21. The photovoltaic device according to claim 20, characterized in that the solar cell includes one or more of a crystalline silicon solar cell, a perovskite solar cell, and a tandem cell composed of a perovskite cell and a crystalline silicon cell.

22. The photovoltaic device according to claim 21, characterized in that the solar cell is a tandem cell composed of a perovskite cell and a crystalline silicon cell, and the solar cell includes a first transparent conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a second transparent conductive layer, an N-type doping layer, a first amorphous silicon layer, a silicon wafer, a second amorphous silicon layer, a P-type doping layer, and a third transparent conductive layer that are sequentially stacked, as well as a first grid electrode layer and a second grid electrode layer; the first grid electrode layer includes a plurality of first grid electrodes arranged at intervals, and each first grid electrode is electrically connected to the first transparent conductive layer; the second grid electrode layer includes a plurality of second grid electrodes arranged at intervals, and each second grid electrode is electrically connected to the third transparent conductive layer.

23. The photovoltaic device according to claim 22, characterized in that the photovoltaic device further includes a light-incident surface panel and a light-back surface panel, the light-incident surface panel is stacked on the surface of the first transparent conductive layer away from the perovskite active layer, and the light-back surface panel is stacked on the surface of the third transparent conductive layer away from the perovskite active layer; the surface of the solar cell is coated with the photovoltaic adhesive film.

24. The photovoltaic device according to claim 22 or 23, characterized in that the solar cell further includes a first antireflection layer, the first antireflection layer is stacked on the surface of the first transparent conductive layer away from the perovskite active layer, and the first grid electrode penetrates through the first antireflection layer and is electrically connected to the first transparent conductive layer; the material of the first antireflection layer includes one or more of magnesium fluoride, lithium fluoride, silicon nitride, silicon oxide, and silicon oxynitride.

25. The photovoltaic device according to claim 22, characterized in that The solar cell further includes a second antireflection layer, which is laminated on the surface of the first transparent conductive layer away from the perovskite active layer, and the first grid electrode penetrates through the second antireflection layer to be electrically connected to the first transparent conductive layer; The second antireflection layer includes the patterned photovoltaic adhesive film as claimed in claim 19.

26. According to the photovoltaic device as claimed in claim 25, wherein, the solar cell further includes a third antireflection layer, which is laminated on the surface of the third transparent conductive layer away from the perovskite active layer, and the second grid electrode penetrates through the third antireflection layer to be electrically connected to the third transparent conductive layer; The third antireflection layer includes the patterned photovoltaic adhesive film as claimed in claim 19.

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