Organic photovoltaic active layer and preparation method thereof, organic photovoltaic device and electronic device

Abstract

The invention relates to an organic photovoltaic active layer and a preparation method thereof, an organic photovoltaic device and an electronic device, the organic photovoltaic active layer comprises a donor material, an acceptor material and an additive, and the additive comprises a deuterated thermal activation delayed fluorescence material derivative conforming to a preset chemical general formula. The additive can induce ordering of donor and acceptor structures, enhance free charge transfer and reduce trap auxiliary recombination; in the energy transfer process from the additive to the donor and the acceptor, high-energy excitons are effectively utilized to excite the donor and the acceptor again, additional excitons are generated, the service life is prolonged, and a charge transfer state is formed on the interface of the donor and the acceptor, so that the probability of charge dissociation is increased. The synergistic effect of the two effectively converts photon energy and reduces non-radiative recombination, thereby being beneficial to improving the energy conversion efficiency and stability of the obtained organic photovoltaic device.

Description

Technical Field

[0001] The present application relates to the field of display technology, and in particular to an organic photovoltaic active layer and a preparation method thereof, an organic photovoltaic device and an electronic apparatus. Background Art

[0002] Organic photovoltaics (OPVs) use organic materials to achieve photoelectric conversion and have broad development and application prospects. With the widespread application of OPVs, improving their photoelectric conversion efficiency and stability has become a key issue. Summary of the Invention

[0003] In view of this, the present application provides an organic photovoltaic active layer and a preparation method thereof to solve at least one of the above technical problems. In addition, the present application also provides an organic photovoltaic device and an electronic device.

[0004] To achieve the above objectives, in a first aspect, the present application provides an organic photovoltaic active layer, comprising: a donor material, an acceptor material, and an additive, wherein the additive comprises a deuterated thermally activated delayed fluorescent material derivative, and the deuterated thermally activated delayed fluorescent material derivative has the general chemical formula of Formula I: Formula I consists of a core and a substituent M, at least one of which includes D, and the substituent M is substituted from R8 to R 11 In any one of the formulas , the substituent M is selected from H, D, formula II and formula III, and formula II and formula III are: wherein at most two of A1 to A4 are N, and the rest are C; X is selected from one of C, O and S. When X is C, the general chemical formula of formula III also includes R 20 , R 20 Connected to X; R1~R 11 Each is independently selected from one of H, D, -CH3, -SiH3 and -CF3, and when the parent nucleus includes D, R1 to R 11 At least one of which includes D; R 12 ~R 20Each is independently selected from H, D, halogen, CF3, -CN, -OR', -Si(R')2, -N(R')2, -P(R')2, -C(O)R', -C(O)OR', -C(O)NR', ​​-SOR', -SO2R', -SO3R', -P(O)(R')2, -P(O)(OR')R', -P(O)(OR')2, C1-C40 alkyl, C2-C wherein R' in the same group is the same or different and R' is selected from one of H, D, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl and C1-C40 haloalkyl, and when the substituent M includes D, R 12 ~R 20 At least one of includes D; or R 12 ~R 19 Any two adjacent groups in the group further form with the ring atoms to which they are connected: one of a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, and an 11-14 membered fused tricyclic aryl or heteroaryl group, and when the substituent M includes D, R 12 ~R 19 At least one of includes D.

[0005] Based on the first aspect, in some possible implementations, the deuterated thermally activated delayed fluorescent material derivative includes one or more of E1 to E20.

[0006] Based on the first aspect, in some possible implementations, the donor material includes one or more of poly 3-hexylthiophene (P3HT), PM6, and PBDB-T.

[0007] Based on the first aspect, in some possible implementations, the acceptor material includes one or more of a fullerene derivative (PCBM), ITIC, and BTP-4F.

[0008] Based on the first aspect, in some possible implementations, the mass percentage of the deuterated thermally activated delayed fluorescent material derivative in the organic photovoltaic active layer is 2.2% to 6.4%.

[0009] Based on the first aspect, in some possible implementations, the mass ratio of the donor material, the acceptor material, and the deuterated thermally activated delayed fluorescent material derivative is 1:1.2:(0.05-0.15).

[0010] Based on the first aspect, in some possible implementations, the thickness of the organic photovoltaic active layer is 100 nm to 110 nm.

[0011] In a second aspect, the present application provides a method for preparing an organic photovoltaic active layer, comprising: providing a deuterated M1 precursor and a deuterated M2 precursor; mixing the deuterated M1 precursor, the deuterated M2 precursor, Pd2(dba)3, NaOtBu, P(tBu)3 and toluene, and heating the mixture under a nitrogen atmosphere to allow the deuterated M2 precursor to replace R8 to R 11 to obtain a crude product; purifying the crude product to obtain a deuterated thermally activated delayed fluorescent material derivative; mixing a donor material, an acceptor material and an additive, wherein the additive includes a deuterated thermally activated delayed fluorescent material derivative, and adding the mixture to an organic photovoltaic active layer.

[0012] In a third aspect, the present application provides an organic photovoltaic device comprising a substrate layer, an anode, a hole transport layer, an active layer, an electron transport layer and a cathode, wherein the active layer comprises the above-mentioned organic photovoltaic active layer.

[0013] In a fourth aspect, the present application provides an electronic device comprising the above-mentioned organic photovoltaic device.

[0014] The additives used in this application can induce structural ordering of the donor and acceptor, enhancing free charge transport and reducing trap-assisted recombination. The energy transfer process from the additive to the donor and acceptor effectively utilizes high-energy excitons to re-excite the donor and acceptor, generating additional excitons and extending their lifetime. This creates a charge transfer state at the donor-acceptor interface, thereby increasing the probability of charge dissociation. This synergistic effect effectively converts photon energy and reduces non-radiative recombination, thereby improving the energy conversion efficiency and stability of the resulting organic photovoltaic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a schematic structural diagram of an organic photovoltaic device provided in one embodiment of the present application.

[0016] Figure 2 This is a schematic structural diagram of an organic photovoltaic device provided in another embodiment of the present application.

[0017] Figure 3 This is the H NMR spectrum of the additive DPA-QAO provided in Comparative Example 1 of the present application.

[0018] Figure 4 This is the NMR carbon spectrum of the additive DPA-QAO provided in Comparative Example 1 of this application.

[0019] Figure 5 This is the mass spectrum of the additive DPA-QAO provided in Comparative Example 1 of this application.

[0020] Figure 6 This is a hydrogen NMR spectrum of the deuterated additive DPA-QAO(D)E1 provided in one embodiment of the present application.

[0021] Figure 7 This is a hydrogen nuclear magnetic spectrum of the deuterated additive DPA(D)-QAO E2 provided in one embodiment of the present application.

[0022] Figure 8 This is a hydrogen NMR spectrum of the deuterated additive DPA(D)-QAO(D)E3 provided in one embodiment of the present application.

[0023] Figure 9 JV curves of the organic photovoltaic device performance provided in Example 1 and Comparative Example 4-1 of the present application.

[0024] Description of main component symbols

[0025] Organic Photovoltaic Devices 100

[0026] Base layer 110

[0027] Anode 120

[0028] Hole transport layer 130

[0029] Active layer 140

[0030] Donor material 141

[0031] Receptor material 142

[0032] Additive 143

[0033] Electron transport layer 150

[0034] cathode 160

[0035] The following specific implementation methods will further illustrate the present application in conjunction with the above-mentioned drawings. DETAILED DESCRIPTION

[0036] The embodiments of the present application are described in detail below. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and should not be understood as limiting the present application; it should be noted that, unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present application belongs; the embodiments of the present application and the features in the embodiments can be combined with each other unless there is a conflict; many specific details are set forth in the following description to facilitate a full understanding of the present application, and the embodiments described are only part of the embodiments of the present application, not all of the embodiments.

[0037] In the various embodiments of the present application, for ease of description and not limitation, the term "connection" used in the patent specification and claims of the present application is not limited to physical or mechanical connections, whether direct or indirect. "Up," "down," "above," "below," "left," "right," etc. are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship also changes accordingly.

[0038] The term H in this application represents hydrogen, D represents deuterium, C represents carbon, O represents oxygen, S represents sulfur, P represents phosphorus, N represents nitrogen, and Si represents silicon.

[0039] The term "halogen" herein refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0040] The terms "alkyl", "alkoxy", "haloalkyl" and any substituent containing the "alkyl" portion of the present application include branched or straight-chain alkyl groups optionally with at least one substituent, optionally interrupted by at least one heteroatom, preferably C1-C40 alkyl, C1-C20 alkyl, more preferably C1-C8 alkyl, and particularly preferably C1-C6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, n-hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, etc. In addition, the alkyl group is optionally substituted with one or more substituents, preferably halogen, more preferably F, C1-C20 haloalkyl, C1-C8 haloalkyl, C1-C4 haloalkyl, and most preferably CF3, perfluoroethyl, trifluoroethyl, perfluoropropyl, and perfluorobutyl.

[0041] The term "alkenyl" in this application includes branched or straight-chain alkenyl groups optionally with at least one substituent and optionally interrupted by at least one heteroatom, preferably C2-C40 alkenyl groups, C1-C20 alkenyl groups, more preferably C2-C8 alkenyl groups, and particularly preferably C2-C6 alkenyl groups, for example: ethenyl, propenyl, butenyl, pentenyl, etc.

[0042] The term "alkynyl" in the present application includes branched or straight-chain alkynyl groups optionally with at least one substituent and optionally interrupted by at least one heteroatom, preferably C2-C40 alkynyl, C2-C20 alkynyl, more preferably C2-C8 alkynyl, and particularly preferably C2-C6 alkynyl, for example: ethynyl, propynyl, butynyl, pentynyl, etc.

[0043] The term "cycloalkyl" in this application includes substituted or unsubstituted saturated cycloalkyl groups, which may contain a monocyclic ring of 4-8, preferably 56 ring atoms, or a polycyclic ring system of 6-40, preferably 6-20, 6-13, more preferably 9-13 ring atoms. Specific examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, bicyclo[2.2.1]heptyl, bicyclo[2,2,2]octyl, etc.

[0044] The term "heterocycloalkyl" in the present application refers to a cycloalkyl group containing 1 to 4 heteroatoms selected from N, O, and S as cycloalkyl backbone atoms and carbon atoms as the remaining cycloalkyl backbone atoms. The heterocycloalkyl group can be a 3-, 4-, 5-, 6-, 7-, or 8-membered monocyclic heterocycloalkyl group or a polycyclic system having 6-40, preferably 6-20, 6-13, and more preferably 9-13 ring atoms, for example: morpholinyl, thiomorpholinyl, etc.

[0045] The term "aryl" as used herein refers to an organic group derived from an aromatic hydrocarbon by removing a hydrogen atom, and may comprise a single ring of 4-8, preferably 5-6, ring atoms, or a fused ring system of 6-40, preferably 6-20, 6-13, and more preferably 9-13 ring atoms. Examples include phenyl, naphthyl, diphenyl, anthracenyl, tetrahydronaphthyl, indenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, pyrenyl, naphthacene, and fluoranthenyl.

[0046] The term "heteroaryl" herein refers to an aryl group containing 1 to 4 heteroatoms selected from N, O, S, and P as aromatic ring backbone atoms and carbon atoms as the remaining aromatic ring backbone atoms. The heteroaryl group may be a 5-, 6-, 7-, or 8-membered monocyclic heteroaryl group or a polycyclic heteroaryl group fused to one or more benzene rings, which may be partially saturated. The polycyclic heteroaryl group may contain 6-40, preferably 6-20, and more preferably 9-13 ring atoms. For example: monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.; polycyclic heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinolizinyl, quinoxalyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc.

[0047] The term "carboxyl" herein refers to "Ra-COO-", wherein Ra refers to alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, and each group is as defined above.

[0048] The term "substituted" herein refers to being optionally substituted with at least one substituent, for example, monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, and the like.

[0049] An embodiment of the present application provides an organic photovoltaic device, which includes a substrate layer, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode.

[0050] The base layer provides mechanical support, and glass or flexible polymer materials are commonly used. Glass materials (such as ITO glass) provide light transmittance, and flexible polymer materials (such as PET) provide good support effects. The anode collects holes and has a certain light transmittance and low resistance. For example, a transparent conductive material (such as indium tin oxide) can be used. The hole transport layer promotes the transfer of holes from the active layer to the anode and blocks the backflow of electrons. For example, a conductive polymer (PEDOT:PSS) or metal oxide (MoO3) can be used. The electron transport layer promotes the transfer of electrons to the cathode and blocks the backflow of holes. For example, polymer film layers such as ZnO and TiO2 or PDINN can be used. The cathode collects electrons. For example, metal electrodes such as Al and Ag can be used.

[0051] The active layer includes an organic photovoltaic active layer, which includes: a donor material, an acceptor material and an additive, wherein the additive includes a deuterated thermally activated delayed fluorescent material derivative, and the chemical formula of the deuterated thermally activated delayed fluorescent material derivative is Formula I: Formula I consists of a core and a substituent M, at least one of which includes D, and the substituent M is substituted from R8 to R 11 In any one of the formulas , the substituent M is selected from H, D, formula II and formula III, and formula II and formula III are: wherein at most two of A1 to A4 are N, and the rest are C; X is selected from one of C, O and S. When X is C, the general chemical formula of formula III also includes R 20 , R 20 Connected to X; R1~R 11 Each is independently selected from one of H, D, -CH3, -SiH3 and -CF3, and when the parent nucleus includes D, R1 to R 11 At least one of which includes D; R 12 ~R 20Each is independently selected from H, D, halogen, CF3, -CN, -OR', -Si(R')2, -N(R')2, -P(R')2, -C(O)R', -C(O)OR', -C(O)NR', ​​-SOR', -SO2R', -SO3R', -P(O)(R')2, -P(O)(OR')R', -P(O)(OR')2, C1-C40 alkyl, C2-C wherein R' in the same group is the same or different and R' is selected from one of H, D, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl and C1-C40 haloalkyl, and when the substituent M includes D, R 12 ~R 20 At least one of includes D; or R 12 ~R 19 Any two adjacent groups in the group further form with the ring atoms to which they are connected: one of a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, and an 11-14 membered fused tricyclic aryl or heteroaryl group, and when the substituent M includes D, R 12 ~R 19 At least one of includes D.

[0052] In related technologies, light is absorbed by the active layer to generate excitons (electron-hole pairs). The donor material and acceptor material in the organic photovoltaic active layer can separate the electrons and holes in the excitons, and move the holes to the anode and the electrons to the cathode, thereby realizing photoelectric conversion. However, the conversion efficiency and stability of existing donor-acceptor materials need to be improved.

[0053] The additives used in this application can induce structural ordering of the donor and acceptor, enhancing free charge transport and reducing trap-assisted recombination. The energy transfer process from the additive to the donor and acceptor effectively utilizes high-energy excitons to re-excite the donor and acceptor, generating additional excitons and extending their lifetime. This creates a charge transfer state at the donor-acceptor interface, thereby increasing the probability of charge dissociation. This synergistic effect effectively converts photon energy and reduces non-radiative recombination, thereby improving the energy conversion efficiency and stability of the resulting organic photovoltaic device.

[0054] In some embodiments, the deuterated thermally activated delayed fluorescent material derivative may be one or more of the following substances, wherein M2 is a substituent:

[0055]

[0056] In some embodiments, the deuterated thermally activated delayed fluorescent material derivative can be one or more of the following substances, wherein M1 is a parent nucleus:

[0057]

[0058] In some embodiments, the deuterated thermally activated delayed fluorescent material derivative includes one or more of E1 to E20, and the chemical formulas of E1 to E20 are as follows:

[0059]

[0060] In some embodiments, the donor material includes one or more of poly 3-hexylthiophene (P3HT), PM6, and PBDB-T.

[0061] In some embodiments, the acceptor material includes one or more of a fullerene derivative (PCBM), ITIC, and BTP-4F.

[0062] In some embodiments, the weight percentage of the deuterated thermally activated delayed fluorescent material derivative in the organic photovoltaic active layer is 2.2% to 6.4%. For example, the weight percentage of the deuterated thermally activated delayed fluorescent material derivative in the organic photovoltaic active layer can be 2.2%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.6%, 4.8%, 5%, 5.4%, 5.8%, 6.2%, 6.4%, or any value within a range formed by any two of the foregoing values. Controlling the weight percentage of the deuterated thermally activated delayed fluorescent material derivative in the organic photovoltaic active layer within the foregoing range is beneficial for further improving the active layer's ability to utilize light energy, while slowing down the photodegradation of the active layer, ultimately improving the energy conversion efficiency and stability of the device.

[0063] In some embodiments, the mass ratio of the donor material, the acceptor material, and the deuterated thermally activated delayed fluorescent material derivative is 1:1.2:(0.05-0.15). For example, the mass ratio of the donor material, the acceptor material, and the deuterated thermally activated delayed fluorescent material derivative can be 1:1.2:0.05, 1:1.2:0.06, 1:1.2:0.07, 1:1.2:0.08, 1:1.2:0.09, 1:1.2:0.1, 1:1.2:0.11, 1:1.2:0.12, 1:1.2:0.13, 1:1.2:0.14, 1:1.2:0.15, or any value within the range formed by any two of the above values. Controlling the mass ratio of the donor material, acceptor material, and deuterated thermally activated delayed fluorescent material derivative within the aforementioned range further improves the ordering of the acceptor structure, further enhances free charge transport, and reduces trap-assisted recombination. It also facilitates the generation of more excitons, further increasing the probability of charge dissociation. When the mass ratio is controlled within the aforementioned range, the synergistic effects of these two aspects are enhanced, further improving the energy conversion efficiency and stability of the resulting organic photovoltaic device.

[0064] In some embodiments, the thickness of the organic photovoltaic active layer is between 100 nm and 110 nm. For example, the thickness of the organic photovoltaic active layer can be 100 nm, 101 nm, 102 nm, 103 nm, 104 nm, 105 nm, 106 nm, 107 nm, 108 nm, 109 nm, 110 nm, or any value within a range formed by any two of the foregoing values. Controlling the thickness of the organic photovoltaic active layer of the present application within the foregoing range is beneficial for maintaining the stability of the organic photovoltaic active layer in the organic photovoltaic device.

[0065] In some embodiments, the organic photovoltaic device described above may be Figure 1 The organic photovoltaic device 100 includes a substrate layer 110, an anode 120, a hole transport layer 130, an active layer 140, an electron transport layer 150, and a cathode 160 stacked in sequence. Light is usually incident from the substrate layer 110 and the anode 120. In other embodiments, see Figure 2 The organic photovoltaic device 100 includes a substrate layer 110 , a cathode 160 , an electron transport layer 150 , an active layer 140 , a hole transport layer 130 and an anode 120 , which are stacked in sequence. Light is usually incident from the anode 120 .

[0066] One embodiment of the present application further provides a method for preparing an organic photovoltaic active layer, comprising:

[0067] Step 1: providing a deuterated M1 precursor and a deuterated M2 precursor.

[0068] In some embodiments, taking the M1 precursor as 3-iodoquinolino[3,2,1-de]acridine-5,9-dione as an example, the preparation method of the deuterated M1 precursor may include:

[0069] S1: Deuterated aniline reacts with deuterated methyl 2-iodobenzoate in the presence of a catalyst, and the reaction is purified by column chromatography and recrystallization to obtain deuterated 2,2'-(phenylazodiyl)dibenzoate.

[0070] S2: Deuterated dimethyl 2,2'-(phenylazodiyl) dibenzoate and acetonitrile are mixed, dissolved, and then N-iodosuccinimide acetonitrile solution is added dropwise. The reaction is stirred to cause the reaction. The reaction is terminated with sodium hydroxide solution. The mixture is extracted with an organic solvent, washed with water, dried, filtered, and concentrated to obtain deuterated dimethyl 2,2'-(4-iodophenylimino) dibenzoate.

[0071] S3: Deuterated 2,2'-(4-iodophenylimino)dimethyl benzoate is reacted with sodium hydroxide in a mixed solvent of ethanol and water, refluxed, cooled, adjusted with dilute hydrochloric acid, precipitated, filtered, washed, and dried to obtain a solid; the dried solid is dissolved in an organic solvent under nitrogen, refluxed, cooled, added with aluminum chloride, refluxed again, terminated with water, extracted with an organic solvent, concentrated, washed, and recrystallized to obtain 3-iodoquinolino[3,2,1-de]acridine-5,9-dione.

[0072] In some embodiments, taking diphenylamine as an example, the preparation method of the deuterated M2 precursor may include:

[0073] P1: Mix deuterated aniline, deuterated bromobenzene and potassium tert-butoxide in toluene and heat to obtain deuterated diphenylamine.

[0074] Step 2: Mix the deuterated M1 precursor, the deuterated M2 precursor, Pd2(dba)3, NaOtBu, P(tBu)3 and toluene, and heat under nitrogen atmosphere to allow the deuterated M2 precursor to replace R8~R in the deuterated M1 precursor. 11 Any one of them can give a crude product.

[0075] In some embodiments, the crude product can be obtained by heating to reflux under a nitrogen atmosphere, cooling and filtering, and concentrating under reduced pressure.

[0076] Step 3: Purify the crude product to obtain a deuterated thermally activated delayed fluorescent material derivative.

[0077] In some embodiments, the purification comprises silica gel column chromatography purification. In some embodiments, the silica gel column chromatography purification uses n-hexane and ethyl acetate, and the ratio of n-hexane to ethyl acetate is 5:1.

[0078] Step 4: mixing the donor material, the acceptor material and the additive, wherein the additive includes a deuterated thermally activated delayed fluorescent material derivative, into the organic photovoltaic active layer.

[0079] The present invention will be explained below in conjunction with the embodiments. It will be understood by those skilled in the art that the following examples are only used to explain the present invention and are not to be construed as limiting the present invention. Unless otherwise indicated, the reagents, software, and instruments not specifically described in the following examples are all conventional commercially available products or open source.

[0080] The present application prepares a basic organic photovoltaic active layer, using 1.0 g of PM6 as a donor material and 1.2 g of BTP-4F as an acceptor material, which is recorded as Comparative Example 4-1.

[0081] Example 1:

[0082] (1) An organic photovoltaic active layer, based on the basic organic photovoltaic active layer of Comparative Example 4-1, further using 0.05 g of deuterated 3-(diphenylamino)-5H,9H-quinolino[3,2,1-de]acridine-5,9-dione (E4) as an additive, that is, the donor material:acceptor material:additive (mass ratio) = 1:1.2:0.05, wherein the preparation method of E4 comprises:

[0083] Step 1: reacting deuterated aniline with deuterated methyl 2-iodobenzoate in the presence of copper catalyst, followed by purification by column chromatography and recrystallization to obtain deuterated 2,2'-(phenylazodiyl)dibenzoate.

[0084] Step 2: Mix the obtained deuterated dimethyl 2,2'-(phenylazodiyl) dibenzoate with 30 mL of acetonitrile, add 2.7 g of N-iodosuccinimide acetonitrile solution dropwise after dissolution, stir at room temperature for 2 hours to allow the reaction to occur, then add 10 mL of 0.1 M sodium hydroxide solution to terminate the reaction, extract with dichloromethane, wash with water, dry with anhydrous magnesium sulfate, filter and concentrate to obtain deuterated 2,2'-(4-iodophenylimino) dibenzoic acid dimethyl ester.

[0085] Step 3: reacting the obtained deuterated 2,2'-(4-iodophenylimino)bisbenzoic acid dimethyl ester with sodium hydroxide in a mixed solvent of ethanol and water, refluxing, adjusting the pH with dilute hydrochloric acid after cooling, precipitating, filtering, washing and drying to obtain a solid; dissolving the dried solid in dichloromethane under nitrogen, adding dichlorothionyl and DMF, refluxing for 3 hours, adding aluminum chloride after cooling, refluxing again, adding water to terminate the reaction, extracting with dichloromethane, concentrating, washing with n-hexane, and recrystallizing with tetrahydrofuran to obtain deuterated 3-iodoquinolino[3,2,1-de]acridine-5,9-dione.

[0086] Step 4: Mix deuterated aniline, deuterated bromobenzene and potassium tert-butoxide in toluene and heat to obtain deuterated diphenylamine.

[0087] Step 5: The obtained deuterated 3-iodoquinolino[3,2,1-de]acridine-5,9-dione is mixed with the obtained deuterated diphenylamine, tris(dibenzylideneacetone)dipalladium, and sodium tert-butoxide in toluene, heated to reflux, cooled and filtered, and concentrated under reduced pressure to obtain a crude product, which is purified by silica gel column chromatography (n-hexane:ethyl acetate = 5:1) to obtain deuterated 3-(diphenylamino)-5H,9H-quinolino[3,2,1-de]acridine-5,9-dione as a yellow solid.

[0088] (2) An organic photovoltaic device, the preparation method of which comprises:

[0089] An organic photovoltaic device was assembled using a glass sheet as a substrate, ITO glass as an anode, PEDOT:PSS as a hole transport layer, the organic photovoltaic active layer obtained in (1) as an active layer, PDINN as an electron transport layer, and silver as a cathode.

[0090] Example 2:

[0091] The difference from Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.1 g, so that the donor material:acceptor material:additive (mass ratio)=1:1.2:0.1.

[0092] Example 3:

[0093] The difference from Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.15 g, so that the donor material:acceptor material:additive (mass ratio)=1:1.2:0.15.

[0094] Example 4:

[0095] The difference from Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.02 g, so that the donor material:acceptor material:additive (mass ratio)=1:1.2:0.02.

[0096] Example 5:

[0097] The difference from Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.2 g, so that the donor material:acceptor material:additive (mass ratio) = 1:1.2:0.2.

[0098] In the present application, a basic organic photovoltaic active layer was prepared again, using 1.0 g of PM6 as a donor material and 1.2 g of BTP-4F as an acceptor material, which was recorded as Comparative Example 4-2.

[0099] Comparative Example 1:

[0100] (1) An organic photovoltaic active layer, based on the basic organic photovoltaic active layer of Comparative Example 4-2, further using 0.05 g of 3-(diphenylamino)-5H,9H-quinolino[3,2,1-de]acridine-5,9-dione as an additive, that is, the donor material:acceptor material:additive (mass ratio) = 1:1.2:0.05, wherein the preparation method of 3-(diphenylamino)-5H,9H-quinolino[3,2,1-de]acridine-5,9-dione differs from that of Example 1 in that: in the first step, aniline and methyl 2-iodobenzoate are used as reaction raw materials.

[0101] (2) An organic photovoltaic device was obtained based on the obtained organic photovoltaic active layer using the same method as in Example 1.

[0102] Comparative Example 2:

[0103] The difference from Comparative Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.1 g, so that the donor material:acceptor material:additive (mass ratio)=1:1.2:0.1.

[0104] Comparative Example 3:

[0105] The difference from Comparative Example 1 is that in the organic photovoltaic active layer, the amount of the additive is adjusted to 0.15 g, so that the donor material:acceptor material:additive (mass ratio)=1:1.2:0.15.

[0106] Taking Comparative Example 1 as an example, the present application used a nuclear magnetic resonance spectrometer to perform nuclear magnetic analysis on the additive, and also used an electrospray mass spectrometer to perform mass spectrometry analysis on the additive. Figure 3 、 Figure 4 and Figure 5 This indicates that the additive in Comparative Example 1 is not deuterated. Figure 6 、 Figure 7 and Figure 8 This indicates that the additives E1, E2 and E3 of the present application have been deuterated. On this basis, E4 used in Example 1 is a more completely deuterated product.

[0107] The present application also conducted performance tests on the organic photovoltaic devices of Examples 1-5 and Comparative Examples 1-4. The test methods include: JV curve test. The test results are shown in Tables 1 and Figure 9 .

[0108] Table 1. Performance test results of organic photovoltaic devices of Examples 1-5 and Comparative Examples 1-4 of the present application

[0109]

[0110] In the organic photovoltaic devices of Examples 1-5 of the present application, the active layer includes a donor material, an acceptor material, and a deuterated thermally activated delayed fluorescent material derivative. The deuterated thermally activated delayed fluorescent material derivative, as an additive, can induce structural ordering of the donor and acceptor, enhancing free charge transport and reducing trap-assisted recombination. The energy transfer process from the additive to the donor and acceptor effectively utilizes high-energy excitons to re-excite the donor and acceptor, generating additional excitons, extending the lifetime, forming a charge transfer state at the donor-acceptor interface, and thereby increasing the probability of charge dissociation. The synergistic effect of the above two effectively converts photon energy and reduces non-radiative recombination, thereby improving the energy conversion efficiency and stability of the resulting organic photovoltaic device.

[0111] Therefore, based on the basic organic photovoltaic active layer of Comparative Example 4-1, Examples 1-5 use deuterated thermally activated delayed fluorescent material derivatives, such as Figure 9As shown, the open-circuit voltage (Voc) and short-circuit current density (Jsc) of the organic photovoltaic devices were significantly improved. The increased Jsc indicates that the device has enhanced its ability to capture light energy and generate charge, while the increased Voc indicates that the device can provide a higher voltage when open-circuited, thereby significantly improving the device's power conversion efficiency (PCE). Furthermore, the fill factor (FF) of the organic photovoltaic devices of Examples 1-5 was significantly improved, indicating that internal losses (such as resistance and recombination) in the devices were reduced, which is beneficial for improving device stability.

[0112] In addition, in Examples 1-5 of the present application, Examples 1-3 further control the mass ratio of the bulk material, the acceptor material, and the deuterated thermally activated delayed fluorescent material derivative (or control the mass proportion of the deuterated thermally activated delayed fluorescent material derivative) within a preset range, thereby further improving the Voc and Jsc of the resulting organic photovoltaic device, thereby further improving the PCE of the resulting organic photovoltaic device. At the same time, the FF of the resulting organic photovoltaic device is further improved, indicating that the device has better stability.

[0113] In comparison, based on the basic organic photovoltaic active layer of Comparative Example 4-2, Comparative Examples 1-3 use non-deuterated thermally activated delayed fluorescent materials as additives. Among them, the improvement of Voc, Jsc, FF and PCE of the organic photovoltaic devices of Comparative Examples 1-2 is not as good as that of the embodiment, and the Voc, Jsc, FF and PCE of the organic photovoltaic device of Comparative Example 3 even decrease. This shows that the energy conversion efficiency and stability of the organic photovoltaic devices of Comparative Examples 1-3 are not as good as those of Examples 1-3.

[0114] The above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit the present application. Although the present application has been described in detail with reference to the above preferred embodiments, those skilled in the art should understand that modifications or equivalent replacements of the technical solutions of the present application should not depart from the spirit and scope of the technical solutions of the present application.

Claims

1. An organic photovoltaic active layer, characterized in that The organic photovoltaic active layer includes: a donor material, an acceptor material, and an additive, wherein the additive includes a deuterated thermally activated delayed fluorescent material derivative, and the deuterated thermally activated delayed fluorescent material derivative has a general chemical formula of Formula I: The formula I is composed of a core and a substituent M, at least one of the core and the substituent M includes D, and the substituent M is substituted from R8 to R 11 Any one of , the substituent M is selected from one of H, D, Formula II and Formula III, and the Formula II and the Formula III are: Among them, at most two of A1 to A4 are N, and the rest are C; X is selected from one of C, O and S. When X is C, the chemical formula of formula III also includes R 20 , R 20 Connected to X; R1~R 11 Each is independently selected from one of H, D, -CH3, -SiH3 and -CF3, and when the parent nucleus includes D, R1 to R 11 At least one of includes D; R 12 ~R 20 Each is independently selected from H, D, halogen, CF3, -CN, -OR', -Si(R')2, -N(R')2, -P(R')2, -C(O)R', -C(O)OR', -C(O)NR', ​​-SOR', -SO2R', -SO3R', -P(O)(R')2, -P(O)(OR')R', -P(O)(OR')2, C1-C40 alkyl, C2-C4 wherein R' in the same group is the same or different and R' is selected from one of H, D, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl and C1-C40 haloalkyl, and when the substituent M includes D, R 12 ~R 20 At least one of includes D; or R 12 ~R 19 Any two adjacent groups in the group further form with the ring atoms to which they are connected: one of a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, and an 11-14 membered fused tricyclic aryl or heteroaryl group, and when the substituent M includes D, R 12 ~R 19 At least one of includes D.

2. The organic photovoltaic active layer according to claim 1, wherein The deuterated thermally activated delayed fluorescent material derivative includes one or more of E1 to E20.

3. The organic photovoltaic active layer according to claim 1, wherein The donor material includes one or more of poly (3-hexylthiophene), PM6 and PBDB-T.

4. The organic photovoltaic active layer according to claim 1, wherein The acceptor material includes one or more of fullerene derivatives, ITIC and BTP-4F.

5. The organic photovoltaic active layer according to claim 1, wherein The mass proportion of the deuterated thermally activated delayed fluorescent material derivative in the organic photovoltaic active layer is 2.2% to 6.4%.

6. The organic photovoltaic active layer according to claim 1, wherein The mass ratio of the donor material, the acceptor material and the deuterated thermally activated delayed fluorescent material derivative is 1:1.2:(0.05-0.15).

7. The organic photovoltaic active layer according to claim 1, wherein The thickness of the organic photovoltaic active layer is 100 nm to 110 nm.

8. A method for preparing an organic photovoltaic active layer, characterized in that: The preparation method comprises: Providing a deuterated M1 precursor and a deuterated M2 precursor; The deuterated M1 precursor, the deuterated M2 precursor, Pd2(dba)3, NaOtBu, P(tBu)3 and toluene are mixed and heated under a nitrogen atmosphere to allow the deuterated M2 precursor to replace R8 to R 11 Any one of them, to obtain a crude product; purifying the crude product to obtain a deuterated thermally activated delayed fluorescent material derivative; A donor material, an acceptor material and an additive are mixed, wherein the additive includes the deuterated thermally activated delayed fluorescent material derivative to obtain the organic photovoltaic active layer.

9. An organic photovoltaic device, characterized in that The organic photovoltaic device comprises a substrate layer, an anode, a hole transport layer, an active layer, an electron transport layer and a cathode, wherein the active layer comprises the organic photovoltaic active layer according to any one of claims 1 to 7.

10. An electronic device, characterized in that: The organic photovoltaic device according to claim 9 is included.

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