Non-conjugated acceptor-receptor type pyrene diimide-based polymers, methods of making, cathode interfacial materials, and semiconductor devices

Abstract

The present application relates to the technical field of cathode interface materials, in particular to a non-conjugated acceptor-acceptor type pyrene diimide polymer, a preparation method thereof, a cathode interface material and a semiconductor device. The non-conjugated acceptor-acceptor type pyrene diimide polymer comprises a pyrene diimide unit and a conjugated acceptor unit polymerized with the pyrene diimide in a non-conjugated manner, and the conjugated acceptor unit is selected from the pyrene diimide unit or other electron-deficient acceptor units; the ultraviolet-visible light absorption range of the other electron-deficient acceptor units is 250-650 nm. When the non-conjugated acceptor-acceptor type pyrene diimide polymer is used as a cathode interface material, it not only has a lower LUMO level, but also increases the ultraviolet-visible light absorption range, thereby widening the light absorption range of the solar cell device and improving the short-circuit current density of the solar cell device.

Description

Technical Field

[0001] This invention relates to the field of cathode interface materials technology, and more specifically, to non-conjugated acceptor-acceptor type pyrene diimide polymers, their preparation methods, cathode interface materials, and semiconductor devices. Background Technology

[0002] Organic solar cells (OSCs) are an effective way to solve environmental pollution and the energy crisis, and represent a new generation of green energy technology with significant industrial prospects. OSCs typically consist of an anode, an anode interface layer, an active layer, a cathode interface layer, and a cathode. Among these, the cathode interface layer, as a crucial component of OSCs, plays a vital role in reducing the contact barrier between the active layer and the cathode, regulating the light field distribution, and enhancing device stability. Therefore, developing high-performance cathode interfacial materials (CIMs) is a key step in promoting the practical application of OSCs.

[0003] Currently, most common cathode interface materials can form good contact between the active layer and the electrode and effectively reduce the electrode work function. However, most of these cathode interface materials have a higher LUMO energy level than high-efficiency narrow-bandgap active layer acceptor materials (such as Y6 and its derivatives) (≈-4.0 eV). This poses a certain obstacle to electron extraction by the cathode interface material in auxiliary electrodes and limits its thick film fabrication. Furthermore, most cathode interface materials also suffer from weak absorption or excessive overlap between their absorption range and the active layer, making it difficult for them to broaden the light absorption range of solar cell devices and thus increase the short-circuit current density. Therefore, it is crucial to develop cathode interface materials with lower LUMO energy levels that complement the light absorption of common active layers.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide non-conjugated acceptor-acceptor type pyrene diimide polymers, their preparation methods, cathode interface materials, and semiconductor devices. The non-conjugated acceptor-acceptor type pyrene diimide polymers provided in this invention, when used as cathode interface materials, not only possess a lower LUMO energy level but also increase the ultraviolet light absorption range, thereby broadening the light absorption range of solar cell devices and ultimately improving the short-circuit current density of solar cell devices.

[0006] This invention is implemented as follows:

[0007] In a first aspect, the present invention provides a non-conjugated receptor-receptor type pyrene diimide polymer, comprising a pyrene diimide unit and a conjugated receptor unit non-conjugated with the pyrene diimide, wherein the conjugated receptor unit is selected from the pyrene diimide unit or other electron-deficient receptor units; the other electron-deficient receptor units have an ultraviolet light absorption range of 250 nm-650 nm.

[0008] Secondly, the present invention provides a method for preparing the non-conjugated receptor-receptor type pyrene diimide polymer described in the foregoing embodiments, comprising non-conjugated polymerization of pyrene diimide units and conjugated receptor units.

[0009] Thirdly, the present invention provides a cathode interface material comprising the non-conjugated acceptor-acceptor type pyrene diimide polymer described in the foregoing embodiments.

[0010] Fourthly, the present invention provides a semiconductor device prepared by means of the cathode interface material described in the foregoing embodiments.

[0011] The present invention has the following beneficial effects: The embodiments of the present invention provide a novel non-conjugated acceptor-acceptor type pyrene diimide polymer, which achieves a low LUMO energy level in the cathode interface material by non-conjugating polymerization of pyrene diimide units and conjugated acceptor units. Furthermore, the non-conjugated connection helps to maximize the retention of the absorption range of pyrene diimide units and conjugated acceptor units, thereby broadening the light absorption range of solar cell devices and further improving the short-circuit current density of the devices. Attached Figure Description

[0012] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0013] Figure 1 The spectrum showing the test molecular weight of the non-conjugated receptor-receptor type pyrene diimide polymer provided in Example 1 of the present invention;

[0014] Figure 2 The spectra of the non-conjugated receptor-receptor type pyrene diimide polymers provided in Examples 2-4 of this invention are for testing molecular weight.

[0015] Figure 3 The detection result diagram provided in Detection Example 1 of the present invention;

[0016] Figure 4 The detection result diagram provided in Detection Example 2 of the present invention;

[0017] Figure 5 This is a diagram showing the detection results provided in Example 3 of the present invention;

[0018] Figure 6 This is a diagram showing the detection results provided in Example 4 of the present invention;

[0019] Figure 7 The detection result diagram provided in Detection Example 5 of the present invention;

[0020] Figure 8 The image shows the detection results provided in Example 6 of this invention. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0022] In a first aspect, embodiments of the present invention provide a non-conjugated receptor-receptor type pyrene diimide polymer, comprising a pyrene diimide unit and a conjugated receptor unit non-conjugated with the pyrene diimide, wherein the conjugated receptor unit is selected from the pyrene diimide unit or other electron-deficient receptor units; wherein the ultraviolet light absorption range of the other electron-deficient receptor units is 250nm-650nm, for example 250nm-350nm, 500nm-650nm, 450nm-600nm, and 250nm-400nm.

[0023] This invention employs pyrene diimide units as the basic structure, and non-conjugated polymers are formed with units of similar ultraviolet absorption range, constructing a series of non-conjugated AA-type polymer cathode interface materials. These polymer cathode interface materials exhibit low LUMO energy levels while retaining the absorption range of both the pyrene diimide unit and the conjugated acceptor unit, thereby broadening the light absorption range of solar cell devices and further improving the short-circuit current density.

[0024] Furthermore, the non-conjugated receptor-receptor type pyrene diimide polymers are selected from compounds with the following structural formulas:

[0025]

[0026] Wherein, A is selected from any one of the groups shown in the following structural formulas:

[0027]

[0028]

[0029] For example, preferably

[0030] R1 is selected from any one of halogen, hydroxyl, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, and substituted or unsubstituted alkyleneoxyalkyl; preferably, R1 is selected from any one of halogen, hydroxyl, hydrogen, substituted or unsubstituted C1-C40 straight-chain alkyl, substituted or unsubstituted C1-C40 branched alkyl, substituted or unsubstituted C5-C40 aryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C2-C40 heterocyclic, and substituted or unsubstituted C2-C40 alkyleneoxyalkyl; for example, R1 is selected from halogen, hydroxyl, hydrogen, and tert-butyl; more preferably, tert-butyl.

[0031] R2 to R18 are each independently selected from any one of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, and substituted or unsubstituted alkyleneoxyalkyl; R2 to R18 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C40 straight-chain alkyl, substituted or unsubstituted C1-C40 branched alkyl, substituted or unsubstituted C5-C40 aryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C2-C40 heterocyclic, and substituted or unsubstituted C2-C40 alkyleneoxyalkyl; for example, R2 to R18 are each independently selected from hydrogen or C1-C5 unsubstituted straight-chain alkyl; most preferably n-propyl.

[0032] It should be noted that R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, and R18 can use the same or different substituents.

[0033] X is selected from any one of halogen, hydroxyl, carboxylate, sulfonate, thiocyanate, borate ion and imide salt ion; for example, X is selected from any one of F, Cl, Br, I, CHCOO, OTf, OH, HSO4, BF4 and Tf2N; preferably, X represents any one of F, Cl, Br and I.

[0034] X1 to X11 are each independently selected from halogen or cyano groups; X12 to X23 are each independently selected from any one or more of O, S and NH; Y is selected from any one of amine, phosphine, phosphorus-containing heterocycle and nitrogen-containing heterocycle.

[0035] x and y can be any ratio. For example, x and y can be any values ​​between 1 and 10, or more preferably any values ​​between 1 and 5.

[0036] Specifically, the non-conjugated receptor-receptor type pyrene diimide polymer is selected from any one of the compounds shown in the following structural formulas:

[0037]

[0038]

[0039] Where n represents any value between 10 and 30, x represents any value between 1 and 10, preferably any value between 1 and 3; y represents any value between 1 and 10, preferably any value between 1 and 3.

[0040] It should be noted that the substituted or unsubstituted C1-C40 straight-chain alkyl groups mentioned above can be methyl, ethyl, n-propyl, or even n-butyl, n-pentyl, and n-hexyl, etc. The substituted or unsubstituted C1-C40 branched alkyl groups can be isopropyl, isobutyl, tert-butyl, or even isopentyl and tert-pentyl, etc. The substituted or unsubstituted C5-C40 aryl groups can be phenyl, thiophene, imidazole, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorenyl, pyrimidinyl, pyridazinyl, quinolinyl, pyrimidinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, cyclophosphinyl, triazinyl, naphthidinyl, pyrimidinylpyrimidinyl, thiophene, benzothiophene, dibenzothiophene, furanyl, benzofuranyl, dibenzofuranyl, azadibenzofuranyl, azadibenzothiophene, 9,9-dimethylfluorenyl, carbazoleyl, arylamine, etc. The substituted or unsubstituted C1-C40 alkoxy groups can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecylalkoxy, dodecylalkoxy, tridecylalkoxy, tetradecylalkoxy, pentadecylalkoxy, hexadecylalkoxy, heptadecylalkoxy, heptadecylalkoxy, and also octadecylalkoxy, nonadecylalkoxy, and eicosylalkoxy. The substituted or unsubstituted C3-C40 cycloalkyl groups can be cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, and also cycloheptyl, cycloheptanetrienyl, and cyclooctyl. The substituted or unsubstituted C2-C40 heterocyclic group can be selected from pyrrolidinyl, azacyclobutyl, oxacyclobutyl, pyrazolinyl, imidazolinyl, imidazolinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, tetrahydrofuranyl, piperazinyl, piperidinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl and hexahydroachenginyl, and can also be selected from heterocyclic groups such as 4-piperidinoneyl, tetrahydropyranyl, 1,3-dioxalyl, morpholinyl, thiomorpholinyl, thiomorpholinyl sulfoxide, thiomorpholinyl sulfone and tetrahydro1,1-dioxothiophene.

[0041] Substituted or unsubstituted C2-C40 alkyleneoxyalkyl refers to the group obtained by removing one hydrogen atom from a "C1C50 alkoxy".

[0042] In a second aspect, embodiments of the present invention provide a method for preparing a non-conjugated receptor-receptor type pyrene diimide polymer, comprising non-conjugated polymerization of pyrene diimide units and conjugated receptor units;

[0043] Preferably, the synthesis is carried out according to the following synthesis path:

[0044]

[0045] The reaction involves mixing x mol of compound 1, y mol of compound 2, x + y mol of compound 3, and 2(x + y) L of solvent and reacting them at 50–80 °C under an inert gas atmosphere. Specifically, compound 1 (x mol), compound 2 (y mol), compound 3 (x + y mol), and 2(x + y) L of trifluoroethanol (TFE) solvent are added to a Schlenk tube. The reaction mixture is heated to 50–80 °C and stirred for 48 h under a nitrogen atmosphere. After cooling, the product is precipitated with dichloromethane.

[0046] Thirdly, embodiments of the present invention provide a cathode interface material comprising the non-conjugated acceptor-acceptor type pyrene diimide polymer described in the foregoing embodiments.

[0047] Fourthly, the present invention provides a semiconductor device prepared using the cathode interface material described in the foregoing embodiments. The semiconductor device includes an optoelectronic device; the optoelectronic device includes any one of electroluminescence, field-effect transistors, photodetectors, and solar cell devices.

[0048] The solar cell device includes an organic solar cell device; the organic solar cell device includes a cathode interface layer, wherein the cathode interface layer is prepared using the cathode interface material described above.

[0049] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0050] Example 1

[0051] This invention provides a method for preparing a non-conjugated receptor-receptor type pyrene diimide polymer, comprising:

[0052] Perform the synthesis according to the following synthesis path:

[0053]

[0054] Specifically, PyDIN (311 mg, 0.5 mmol), 1,3-dibromopropane (100.9 mg, 0.5 mmol), and 2 mL of trifluoroethanol (TFE) solvent were added to a 10 mL Schlenk tube. The reaction mixture was heated to 70 °C and stirred under a nitrogen atmosphere for 48 h. After cooling, the mixture was precipitated with dichloromethane to give a yellow solid polymer PPyDIN-C3 (yield 90%).

[0055] The characterization spectrum of polymer PPyDIN-C3 is shown in [reference needed]. Figure 1 The characterization data are as follows: Using hexafluoroisopropanol (HFIP) as the eluent, gel permeation chromatography (GPC) was used to characterize the molecular weight of the yellow solid polymer: M n= 8.01 kg mol -1 M w = 33.23 kg mol -1 NMR data: 9.33-9.49 (m, 4H), 4.01-4.17 (s, 4H), 3.60-3.75 (m, 4H), 3.35-3.48 (m, 4H), 3.12-3.35 (m, 12H), 2.42-2.56 (s, 4H), 1.86-2.01 (m, 4H), 1.52-1.60 (m, 4H). It can be seen that the desired non-conjugated receptor-receptor type pyrene diimide polymer was synthesized in this embodiment.

[0056] Examples 2-4

[0057] All embodiments of the present invention provide a method for preparing non-conjugated receptor-receptor type pyrene diimide polymers, comprising:

[0058] Perform the synthesis according to the following synthesis path:

[0059]

[0060] PyDIN (x mmol), NDIN (y mmol) (x+y=0.5mmol), 1,3-dibromopropane (100.9 mg, 0.5 mmol), and 2 mL of trifluoroethanol (TFE) solvent were added to a 10 mL Schlenk tube. The reaction mixture was heated to 70 °C and stirred under a nitrogen atmosphere for 48 h. After cooling, the mixture was precipitated with dichloromethane to give a yellow solid polymer (yield 93%).

[0061] Example 2: The yellow solid polymer with x / y = 3 / 1 was designated PPyN31. The molecular weight of this yellow solid polymer was characterized by gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP) as the eluent: M n =13.48 kg mol -1 M w =35.91 kgmol -1 .

[0062] Example 3: The yellow solid polymer with x / y = 1 / 1 is designated PPyN11. The molecular weight of this yellow solid polymer was characterized by gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP) as the eluent: M n = 21.33 kg mol -1 M w =59.19 kgmol -1 .

[0063] Example 4: The yellow solid polymer with x / y = 1 / 3 was designated PPyN13. The molecular weight of this yellow solid polymer was characterized by gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP) as the eluent: M n = 37.85 kg mol -1 M w = 114.46 kg mol -1 .

[0064] The spectra of the non-conjugated receptor-receptor type pyrene diimide polymers used in Examples 2-4 are shown below. Figure 2 .

[0065] Example 5

[0066] This invention provides a method for preparing a non-conjugated receptor-receptor type pyrene diimide polymer, comprising:

[0067] Perform the synthesis according to the following synthesis path:

[0068]

[0069] t-PyDIN (0.25 mmol), BTN (0.25 mmol), 1,3-dibromopropane (100.9 mg, 0.5 mmol), and 2 mL of trifluoroethanol (TFE) solvent were added to a 10 mL Schlenk tube. The reaction mixture was heated to 70 °C and stirred under a nitrogen atmosphere for 48 h. After cooling, the mixture was precipitated with dichloromethane to give an orange-yellow solid polymer PPyB11 (yield 90%).

[0070] Example 6

[0071] This invention provides a method for preparing a non-conjugated receptor-receptor type pyrene diimide polymer, comprising:

[0072] Perform the synthesis according to the following synthesis path:

[0073]

[0074] Specifically, t-PyDIN (311 mg, 0.5 mmol), 2,2'-dibromodiethyl ether (116 mg, 0.5 mmol), and 2 mL of trifluoroethanol (TFE) solvent were added to a 10 mL Schlenk tube. The reaction mixture was heated to 70 °C and stirred under a nitrogen atmosphere for 48 h. After cooling, the mixture was precipitated with dichloromethane to give a yellow solid polymer PPyDIN-O (yield 93%).

[0075] Detection Example 1

[0076] The t-PyDIN and PPyDIN-C3 of Example 1 were tested. See the results below. Figure 3 See Table 1.

[0077] Figure 3 In the figure, a represents the UV-Vis absorption spectra of t-PyDIN and PPyDIN-C3; Figure 3 In the figure, b represents the cyclic voltammetry curves of t-PyDIN and PPyDIN-C3; Figure 3 In the diagram, c represents the energy level diagrams for t-PyDIN and PPyDIN-C3. Figure 3 In the image, d represents the electron paramagnetic resonance (EPR) maps of t-PyDIN and PPyDIN-C3. Figure 3 In the image, e represents the ultraviolet photoelectron spectrum of t-PyDIN; Figure 3 f represents the ultraviolet photoelectron spectra of Ag and PPyDIN-C3.

[0078] Table 1 Optical and electrochemical analysis data for t-PyDIN and PPyDIN-C3

[0079]

[0080] According to Table 1 and Figure 3 It is known that (1) the main light absorption range of t-PyDIN is 350nm-500nm, which can form good complementary absorption with the current high-performance active layer materials. The LUMO energy level of t-PyDIN is -3.57eV. In this embodiment of the invention, the Menshutkin reaction is used to react t-PyDIN and 1,3-dibromopropane to obtain the PPyDIN-C3 polymer. According to Figure 3 As shown in Figure a, PPyDIN-C3 exhibits absorption in the ranges of approximately 280 to 320 nm and 350 to 500 nm, indicating that this non-conjugated linking preserves the unique absorption range of the small molecule t-PyDIN. PPyDIN-C3 possesses the characteristic of forming a complementary light absorption with current high-performance active layer materials.

[0081] (2) According to Figure 3 As shown in Figure c, the LUMO energy level of PPyDIN-C3 is -3.75 eV. Compared to the LUMO energy level of the small molecule t-PyDIN (-3.57 eV), the LUMO energy level of the PPyDIN-C3 polymer is lower, indicating that the acceptor-acceptor non-conjugated polymerization method can significantly reduce the LUMO energy level of the molecule. The lower LUMO energy level of PPyDIN-C3 is more conducive to electron transport and extraction, which is beneficial for preparing thickness-insensitive cathode interface layers.

[0082] (3) According to Figure 3As can be seen from d, the PPyDIN-C3 cathode interface material exhibits a paramagnetic signal centered at 3510G in the electron paramagnetic resonance (EPR) diagram. This indicates that PPyDIN-C3 possesses self-doping properties. This self-doping effect promotes the formation of an interface dipole between the active layer and the electrode, which can effectively reduce the work function of the electrode and promote electron transport in photovoltaic devices. According to Figure 3 As shown in e and f, the work function of the silver (Ag) electrode modified with t-PyDIN decreased from 4.64 eV to 4.10 eV, while that modified with PPyDIN-C3 decreased from 4.64 eV to 3.92 eV. PPyDIN-C3 polymer is an organic cationic electrolyte material with a cation in its main chain and an added free anion. The resulting interfacial dipole can significantly reduce the work function of Ag. This is beneficial for forming ohmic contacts at the metal / organic semiconductor interface and enhancing the built-in electric field, thereby facilitating the generation and extraction of free charges in the device.

[0083] Detection Example 2

[0084] The photovoltaic performance of organic solar cells based on t-PyDIN or PPyDIN-C3 cathode interface materials was investigated using a forward device structure of ITO / PEDOT:PSS / active layer / CIL / Ag. Wide bandgap polymer donor PBDB-T-2F and narrow bandgap small molecule acceptor Y6 were selected as the photoactive layer materials, and t-PyDIN or PPyDIN-C3 were used as the cathode interface materials, respectively. A photovoltaic device without a cathode interface layer was also fabricated as a control group.

[0085] The device fabrication process is as follows: (1) The indium tin oxide (ITO) glass substrate was wiped with a dilute detergent solution and ethanol in sequence, and then ultrasonically cleaned with deionized water, acetone and isopropanol for 20 minutes in sequence. Before use, the ITO glass substrate was dried with a high-purity nitrogen gun. After that, it was treated in an ultraviolet-ozone cleaner for 20 minutes. (2) Preparation of hole transport layer: Under room temperature conditions, the hole transport layer PEDOT:PSS (Clevios PVP AI 4083) aqueous solution was filtered with a 0.45μm aqueous filter membrane, spread evenly on the surface of the ITO substrate, and obtained ITO / PEDOT:PSS under spin coating conditions of 4800rpm and 20s. Finally, the ITO / PEDOT:PSS was annealed on a heating stage at 150℃ for 15 minutes and then transferred to a glove box in a nitrogen atmosphere to prepare the active layer. (3) Preparation of the active layer: For the binary system with PBDB-T-2F:Y6 as the active layer, the total concentration of the active layer blend solution in this binary system is 13.2 mg / mL. -1The solution was prepared according to a donor-acceptor mass ratio of 1:1.2. For the preparation of the active layer solution: the solvent was redistilled chloroform, and the additive was 1-chloronaphthalene, accounting for 0.5% of the total volume. The active layer solution was stirred at room temperature for 6 hours in a glove box under nitrogen atmosphere. On the surface of the ITO / PEDOT:PSS substrate, the spin coating speed was 3000 rpm and the time was 30 s. After the active layer film was prepared, the spin-coated film was placed on a constant temperature heating table at 110℃ for heat annealing for 10 minutes. (4) Preparation of the cathode interface layer: Cathode interface layer solutions of different concentrations were prepared. The solvent used for the cathode interface material was trifluoroethanol. The solution was stirred at room temperature for several minutes until the cathode interface material was completely dissolved. Then, after filtration with an organic filter membrane, the cathode interface layer was spin-coated onto the active layer film at a spin coating speed of 3000 rpm. (5) Evaporation of silver (Ag) electrode: The Ag metal electrode was prepared by vacuum evaporation. 60 nm of silver was deposited in a vacuum evaporation chamber as the cathode of the battery. The effective area of ​​the final device was 4 mm². 2 .

[0086] The JV curves and EQE curves of the tested devices, as well as the JV curves of devices with PPyDIN-C3 cathode interface layers at different film thicknesses.

[0087] See results Figure 4 Tables 2 and 3, among which Figure 4 In the figure, 'a' represents the JV curve of the optimal device based on the t-PyDIN cathode interface layer. Figure 4 In the figure, b represents the JV curve of the optimal device based on the PPyDIN-C3 cathode interface layer. Figure 4 In the diagram, 'c' represents the EQE curve of the optimal device based on the PPyDIN-C3 cathode interface layer. Figure 4 In the figure, d represents the JV curve of devices based on t-PyDIN cathode interface layers with different film thicknesses. Figure 4 In the figure, 'e' represents the JV curve of devices based on PPyDIN-C3 cathode interface layers with different film thicknesses.

[0088] Table 2 shows the results at 1000W m -2 Optimal device parameters based on different cathode interface materials were determined using PBDB-T-2F:Y6 as the active layer under simulated sunlight irradiation at AM 1.5G.

[0089]

[0090] Table 3 shows the results at 1000W m -2 Device parameters of the PPyDIN-C3 cathode interface layer with different film thicknesses under simulated sunlight irradiation at AM 1.5G, using PBDB-T-2F:Y6 as the active layer.

[0091]

[0092] according to Figure 4 As shown in b and Table 2, the device using PPyDIN-C3 as the cathode interface layer exhibits a high energy conversion efficiency of 16.85%, while the device without a cathode interface layer has an efficiency of only 11.62%. Figure 4 As shown in Figure a and Table 2, the photoelectric conversion efficiency of the device using t-PyDIN as the cathode interface layer is 16.44%. The organic photovoltaic device using PPyDIN-C3 as the cathode interface layer is significantly higher than the device without a cathode interface layer, and also higher than the device using t-PyDIN as the cathode interface layer.

[0093] according to Figure 4 As shown in c, the external quantum efficiency (EQE) of devices based on PPyDIN-C3 as the cathode interface material exceeds 80% in the 500-790 nm range, demonstrating efficient charge transport and extraction processes within the devices. In particular, devices using PPyDIN-C3 as the cathode interface material exhibit even higher EQE responses in the 300-500 nm range, which can be attributed to the strong absorption properties of PPyDIN-C3 in this range. The complementary light absorption characteristics between the active layer and the PPyDIN-C3 cathode interface material contribute to a EQE of 26.70 mA / cm² for devices based on the PPyDIN-C3 cathode interface. -2 The short-circuit current density is higher than that of the cathode with t-PyDIN interface layer (26.35 mA / cm²). -2 ) and without a cathode interface layer (25.50 mA cm) -2 The short-circuit current density of the device is shown in the figure. The integrated current density is consistent with the short-circuit current density obtained from the J-V curve test.

[0094] according to Figure 4 As shown in d and Table 3, the photoelectric conversion efficiency of the device is 16.44% when the t-PyDIN cathode interface material is 8 nm thick. When the thickness of the t-PyDIN cathode interface material increases to 24 nm, the device efficiency is only 6.66%, which is about 40% of the highest photoelectric conversion efficiency (16.44%). This indicates that the raw material t-PyDIN cathode interface material is thickness-sensitive and is not suitable for use at larger film thicknesses.

[0095] In contrast, according to Figure 4As shown in Table 3, the PPyDIN-C3 cathode interface material exhibits high photoelectric conversion efficiency across a wide thickness range from 6 nm to 121 nm. When the thickness of the PPyDIN-C3 cathode interface material increases to 121 nm, the device efficiency is 14.31%, approximately 85% of the highest photoelectric conversion efficiency (16.85%). As shown in Table 3, the open-circuit voltage (Voc) does not decrease significantly with increasing PPyDIN-C3 cathode interface material thickness, especially at a thickness of 121 nm, where the open-circuit voltage remains at 0.863 V. This can be attributed to the lower LOMO energy level of the PPyDIN-C3 cathode interface material compared to the raw material t-PyDIN.

[0096] Detection Example 3

[0097] The yellow solid polymers PPyN31, PPyN11, and PPyN13 prepared in Examples 2-4 were analyzed. See the results below. Figure 5 And Table 4.

[0098] Figure 5 In the figure, 'a' represents the UV-Vis absorption spectra of PPyN31, PPyN11, and PPyN13. Figure 5 In the figure, b represents the cyclic voltammetry curves of PPyN31, PPyN11, and PPyN13; Figure 5 In the diagram, 'c' represents the energy level diagrams for PPyN31, PPyN11, and PPyN13. Figure 5 In the diagram, d represents the electron paramagnetic resonance (EPR) maps of PPyN31, PPyN11, and PPyN13. Figure 5 In the figure, 'e' represents the ultraviolet photoelectron spectra of PPyN31, PPyN11, and PPyN13.

[0099] Table 4 Optical and electrochemical analysis data of PPyN31, PPyN11 and PPyN13

[0100]

[0101] according to Figure 5 As shown in Table 4, in this embodiment of the invention, 4,5,9,10-pyrene diimide derivative t-PyDIN and naphthalene diimide derivative NDIN are used to react with 1,3-dibromopropane in Menschuktin to form A1-A2 type polymers to prepare organic cathode interface materials with lower LUMO energy levels that are complementary to the light absorption of current high-performance active layers. Furthermore, the absorption range and energy level of the material are precisely adjusted by regulating the ratio of t-PyDIN and NDIN units.

[0102] according to Figure 5As shown in section a, the absorption peaks of PPyN31, PPyN11, and PPyN13 at approximately 310 nm can be attributed to the π-π* transition of the pyrene unit, the absorption peak at approximately 387 nm to the π-π* transition of the NDIN unit, and the adsorption peak at approximately 420 nm to the n-π* transition of the polar double bond in the t-PyDIN imide moiety. It is evident that the acceptor-acceptor polymers using non-conjugated t-PyDIN and NDIN retain the UV-Vis absorption characteristics of the monomers t-PyDIN and NDIN. The main absorption range of PPyN31, PPyN11, and PPyN13 is 275 nm–500 nm, exhibiting complementary light absorption characteristics to current high-performance active layer materials. This helps to broaden the light absorption range of organic solar cell devices and improve the photocurrent of the devices.

[0103] according to Figure 5 As shown in sections b and c, the energy levels of these polymer cathode interface materials were tested and calculated using electrochemical cyclic voltammetry (CV). Based on the reduction potential, the lowest unoccupied molecular orbital (LUMO) energy levels of PPyN31, PPyN11, and PPyN13 are -3.76, -4.17, and -4.10 eV, respectively. The acceptor-acceptor polymerization method significantly reduces the LUMO energy levels of the molecules; the LUMO energy levels of PPyN11 and PPyN13 are even lower than those of highly efficient narrow bandgap acceptor materials (such as Y6 and its derivatives) (≈-4.0 eV), resulting in better energy level alignment at the cathode interface and more favorable electron transport.

[0104] according to Figure 5 As shown in Figure d, the cathode interface materials of PPyN31, PPyN11, and PPyN13 exhibit a paramagnetic signal centered at 3510G in the electron paramagnetic resonance (EPR) plot. This is due to the effective self-doping effect caused by charge transfer between the strongly electron-withdrawing imide groups and the quaternary ammonium salt. At the same mass, the paramagnetic signal of the cathode interface materials of PPyN31, PPyN11, and PPyN13 increases sequentially. This is because the naphthalimide framework has stronger electron-withdrawing properties compared to the pyrene imide framework, which is consistent with the trend of the LUMO energy levels of PPyN31, PPyN11, and PPyN13.

[0105] according to Figure 5 As can be seen from e, the work function of the Ag electrode modified with PPyN31, PPyN11 and PPyN13 decreased from 4.64 eV to 3.80, 3.84 and 3.94 eV, respectively. The cathode interface materials of PPyN31, PPyN11 and PPyN13 significantly reduced the work function of the Ag electrode, which is beneficial to the formation of ohmic contacts at the metal / organic semiconductor interface and the enhancement of the built-in electric field, thereby facilitating the generation and extraction of free charges in the device.

[0106] Detection Example 4

[0107] The photovoltaic performance of organic solar cell devices based on the cathode interface materials PPyN31, PPyN11, and PPyN13 of Examples 2-4 was studied using the forward device structure of ITO / PEDOT:PSS / active layer / CIL / Ag.

[0108] Wide bandgap polymer donor PBDB-T-2F and narrow bandgap small molecule acceptor Y6 were selected as photoactive layer materials, and PPyN31, PPyN11, and PPyN13 were used as cathode interface materials. The device fabrication method is the same as that in Detection Example 2.

[0109] The JV curves and EQE curves of the tested devices, as well as the JV curves of devices with different film thicknesses of PPyN31 cathode interface layer.

[0110] See results Figure 6 Tables 5 and 6. Among them... Figure 6 In the graph, 'a' represents the JV curve. Figure 6 In the graph, b represents the EQE curve. Figure 6 In the figure, c represents the JV curve of the PPyN31 cathode interface layer under different film thicknesses.

[0111] Table 5 shows the results at 1000W m -2 Optimal device parameters based on different cathode interface layers, using PBDB-T-2F:Y6 as the active layer under simulated sunlight irradiation at AM 1.5G.

[0112]

[0113] Table 6 shows the values ​​at 1000W m -2 Device parameters of the PPyN31 cathode interface layer with different film thicknesses under simulated sunlight irradiation at AM 1.5G, using PBDB-T-2F:Y6 as the active layer.

[0114]

[0115] according to Figure 6As shown in Figure a and Table 5, after device optimization, the PPyN31-based device achieved a photoelectric conversion efficiency of 17.12%, which is one of the highest photoelectric conversion efficiencies based on the PM6:Y6 binary system. Meanwhile, devices using PPyN11 and PPyN13 as cathode interface layers exhibited photoelectric conversion efficiencies of 16.53% and 17.06%, respectively, both significantly higher than the efficiency of devices without a cathode interface layer (11.68%). It can be seen that PPyN31, PPyN11, and PPyN13, these three cathode interface materials, play a crucial role in improving the photovoltaic performance of organic solar cell devices.

[0116] according to Figure 6 As shown in Figure b and Table 5, the external quantum efficiency (EQE) response of devices based on these cathode interface materials exceeds 80% in the 510-790 nm range, demonstrating efficient charge transport and extraction processes within the devices. The complementary light absorption characteristics between the active layer and these three cathode interface materials result in EQE values ​​of 25.57, 25.45, and 25.07 mA cm⁻¹ for devices based on these cathode interfaces. -2 The short-circuit current density is shown. The integrated current density is in excellent agreement with the short-circuit current density obtained from J-V curve testing. These results demonstrate that PPyN31, PPyN11, and PPyN13 can broaden the absorption range of the device and provide an efficient photoelectric conversion process.

[0117] Taking PPyN31 polymer cathode interface material as an example, this study investigates the film thickness sensitivity of acceptor-acceptor type cathode interface materials formed by t-PyDIN and NDIN. Detailed device parameters of the PPyN31 cathode interface layer at different film thicknesses are summarized in Table 6. The results show that when the thickness of the PPyN31 cathode interface layer is 12 nm, the device exhibits a high photoelectric conversion efficiency of 17.12%. When the thickness of the PPyN31 cathode interface layer increases to 75 nm, the photoelectric conversion efficiency remains at 16.49%, maintaining above 96% of the optimal device efficiency. When the thickness of the PPyN31 cathode interface layer further increases to 86 nm, the photoelectric conversion efficiency remains at 15.58%, maintaining above 90% of the optimal device efficiency.

[0118] Case 5

[0119] The orange-yellow solid polymer PPyB11 prepared in Example 5 was tested. Results are shown below. Figure 7 Tables 7 and 8.

[0120] Figure 7 In the image, 'a' represents the UV-Vis absorption spectrum of PPyB11. Figure 7 In the figure, b represents the cyclic voltammetry curve of PPyB11; Figure 7In the figure, c represents the JV curve of the optimal device based on the PPyB11 cathode interface layer in the PBDB-T-2F:Y6 system.

[0121] Table 7 Optical and electrochemical analysis and device data for PPyB11.

[0122]

[0123] according to Figure 7 As shown in Table 7, in the embodiments of the present invention, 4,5,9,10-pyrene diimide derivative t-PyDIN and benzothiadiazole derivative BTN are used to form A1-A2 type polymers by reacting with Menschuktin of 1,3-dibromopropane to prepare organic cathode interface materials with lower LUMO energy levels that are complementary to the light absorption of current high-performance active layers.

[0124] according to Figure 7 As shown in section a, the absorption peak of PPyB11 at approximately 304 nm can be attributed to the π-π* transition of the pyrene unit and the π-π* transition of the benzodithiazole, while the adsorption peak at approximately 423 nm should be attributed to the n-π* transition of the polar double bond in the t-PyDIN imide moiety and the polaron absorption of the BTN unit. It is evident that the acceptor-acceptor polymer using non-conjugated t-PyDIN and BTN retains the UV-Vis absorption characteristics of the monomers t-PyDIN and BTN. The main absorption range of PPyB11 is 280 nm–500 nm, exhibiting complementary light absorption characteristics to current high-performance active layer materials. This helps to broaden the light absorption range of organic solar cell devices and improve the photocurrent of the devices.

[0125] according to Figure 7 As shown in section b, the energy levels of the PPyB11 polymer cathode interface material were tested and calculated using electrochemical cyclic voltammetry (CV). Based on the reduction potential, the lowest unoccupied molecular orbital (LUMO) energy level of PPyB11 is -4.15 eV. The acceptor-acceptor polymerization method significantly reduces the LUMO energy level of the molecule. The LUMO energy level of PPyB11 is lower than that of highly efficient narrow bandgap acceptor materials (such as Y6 and its derivatives) (≈-4.0 eV), enabling barrier-free electron transport and extraction at the cathode interface.

[0126] The photovoltaic performance of an organic solar cell device based on the PPyB11 cathode interface material of Example 5 was studied using a forward device structure of ITO / PEDOT:PSS / active layer / CIL / Ag.

[0127] Wide bandgap polymer donor PBDB-T-2F and narrow bandgap small molecule acceptor Y6 were selected as the photoactive layer materials, and PPyB11 was used as the cathode interface material. The device fabrication method is the same as that in Detection Example 2.

[0128] The JV curve of the test device. See the results below. Figure 7 And Table 8. Among them... Figure 7 In the middle, 'c' represents the JV curve.

[0129] Table 8 shows the results at 1000W m -2 Optimal device parameters based on PPyB11 cathode interface layer with PBDB-T-2F:Y6 as the active layer under simulated sunlight irradiation at AM 1.5G.

[0130]

[0131] according to Figure 7 As shown in Figure c and Table 8, after device optimization, the PPyB11-based device achieved a photoelectric conversion efficiency of 16.61%, which is higher than the efficiency of the device without a cathode interface layer (11.62%). It can be seen that the PPyB11 cathode interface material significantly improves the photoelectric conversion efficiency of organic solar cell devices. This should be attributed to the lower LUMO energy level of the acceptor-acceptor type PPyB11 cathode interface material, which promotes electron extraction from the cathode and suppresses charge recombination.

[0132] Case 6

[0133] The PPyDIN-O yellow solid polymer prepared in Example 6 was tested. See the results below. Figure 8 Tables 9 and 10.

[0134] Figure 8 In the image, 'a' represents the UV-Vis absorption spectrum of PPyDIN-O. Figure 8 In the figure, b represents the cyclic voltammetry curve of PPyDIN-O; Figure 8 In the figure, c represents the JV curve of the optimal device based on the PPyDIN-O cathode interface layer in the PBDB-T-2F:Y6 system.

[0135] Table 9 shows the optical and electrochemical analysis and device data for PPyDIN-O.

[0136]

[0137] according to Figure 8As shown in Table 9, in the embodiments of the present invention, the 4,5,9,10-pyrene diimide derivative t-PyDIN is used to form a acceptor-acceptor type polymer by reacting with Menschuktin of 2,2'-dibromodiethyl ether to prepare an organic cathode interface material with a lower LUMO energy level that is complementary to the light absorption of the current high-performance active layer.

[0138] according to Figure 8 As shown in section a, the absorption peak of PPyDIN-O at approximately 304 nm can be attributed to the π-π* transition of the pyrene unit and the π-π* transition of the benzodithiazole, while the adsorption peak at approximately 425 nm should be attributed to the n-π* transition of the polar double bond in the t-PyDIN imide moiety. It is evident that the PPyDIN-O polymer retains the UV-Vis absorption characteristics of the monomer t-PyDIN. The main absorption range of PPyDIN-O is 275 nm–466 nm, exhibiting complementary light absorption characteristics to current high-performance active layer materials. This helps to broaden the light absorption range of organic solar cell devices and improve the photocurrent of the devices.

[0139] according to Figure 8 As shown in section b, the energy levels of the PPyDIN-O polymer cathode interface material were tested and calculated using electrochemical cyclic voltammetry (CV). Based on the reduction potential, the lowest unoccupied molecular orbital (LUMO) energy level of PPyDIN-O is -3.77 eV. Adopting an acceptor-acceptor polymerization method can yield cathode interface materials with lower LUMO energy levels, which is beneficial for electron extraction at the device cathode interface.

[0140] The photovoltaic performance of an organic solar cell device based on the PPyDIN-O cathode interface material of Example 6 was studied using a forward device structure of ITO / PEDOT:PSS / active layer / CIL / Ag.

[0141] Wide bandgap polymer donor PBDB-T-2F and narrow bandgap small molecule acceptor Y6 were selected as the photoactive layer materials, and PPyDIN-O was used as the cathode interface material. The device fabrication method is the same as that described in Detection Example 2.

[0142] The JV curve of the test device. See the results below. Figure 8 And Table 10. Among them... Figure 8 In the middle, 'c' represents the JV curve.

[0143] Table 10 shows the results at 1000W m -2 Optimal device parameters based on the PPyDIN-O cathode interface layer, using PBDB-T-2F:Y6 as the active layer, under simulated sunlight irradiation at AM 1.5G.

[0144]

[0145] according to Figure 8 As shown in Figure c and Table 10, after device optimization, the PPyDIN-O-based device achieved a photoelectric conversion efficiency of 16.77%, which is higher than the efficiency of the device without a cathode interface layer (11.62%). It can be seen that the PPyDIN-O cathode interface material significantly improves the photoelectric conversion efficiency of organic solar cell devices. This should be attributed to the acceptor-acceptor type PPyDIN-O cathode interface material having a lower LUMO energy level and a light absorption range complementary to the active layer, which promotes electron extraction from the cathode and improves the light utilization efficiency of the device.

[0146] As can be seen, the cathode interface material provided in this embodiment of the invention achieves the highest thick-film efficiency retention performance for cathode interface materials with a film thickness exceeding 80 nm. This characteristic is attributed to the acceptor-acceptor non-conjugated cathode interface material provided in this embodiment of the invention, which exhibits complementary absorption and energy level matching with the active layer material. Therefore, even in the case of a thick film, it does not significantly affect the light absorption and charge transport performance of the device. Thus, the non-conjugated acceptor-acceptor type pyrene diimide polymer provided in this embodiment of the invention offers an efficient design strategy for large-area and thick-film electronic devices, possessing enormous commercial potential.

[0147] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A non-conjugated receptor-receptor type pyrene diimide polymer, characterized in that, The non-conjugated receptor-receptor type pyrene diimide polymer is selected from any one of the compounds shown in the following structural formulas: or Where n represents any value between 10 and 30; x represents any value between 1 and 10; and y represents any value between 1 and 10.

2. The non-conjugated receptor-receptor type pyrene diimide polymer according to claim 1, characterized in that, x represents any value between 1 and 3, and y represents any value between 1 and 3.

3. A cathode interface material, characterized in that, It includes the non-conjugated receptor-receptor type pyrene diimide polymer as described in claim 1.

4. A semiconductor device, characterized in that, It is prepared using the cathode interface material described in claim 3.

5. The semiconductor device according to claim 4, characterized in that, The semiconductor device includes an optoelectronic device.

6. The semiconductor device according to claim 5, characterized in that, The optoelectronic device includes any one of electroluminescence, field-effect transistor, photodetector device and solar cell device.

7. The semiconductor device according to claim 6, characterized in that, The solar cell device includes an organic solar cell device.

8. The semiconductor device according to claim 7, characterized in that, The organic solar cell device includes a cathode interface layer, wherein the cathode interface layer is prepared using the cathode interface material described in claim 3.

9. The semiconductor device according to claim 8, characterized in that, The thickness of the cathode interface layer is 6-121 nm.

Images