High-entropy self-assembled hole transport layer, preparation method and application thereof

Abstract

The application belongs to the field of perovskite solar cells, and specifically discloses a high-entropy self-assembled hole transport layer, a preparation method and application thereof. The high-entropy self-assembled hole transport layer is formed by mixing three or more self-assembled molecules with a general formula of A-L-T on a conductive substrate to form a high-entropy self-assembled hole transport layer film, wherein A is an anchoring group, L is a connecting unit, and T is a terminal group. The self-assembled molecules differ in chemical structure, including at least one of a terminal group, a substituent group, a connecting unit length, an anchoring group or a molecular topological structure. The application constructs a high-entropy system by mixing multiple components, utilizes the coexistence of multiple intermolecular interactions to inhibit long-range order and retain short-range order, and makes the hole transport layer maintain structural stability under external stress. The photoelectric device based on the hole transport layer has the advantages of high photoelectric conversion efficiency and excellent long-term running stability.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cells, and in particular to a high-entropy self-assembled hole transport layer, its preparation method, and its application. Background Technology

[0002] In recent years, inverted perovskite solar cells (PSCs) and organic solar cells (OSCs) have attracted widespread attention due to their advantages such as low-temperature processing, low hysteresis, and ease of stacking and integration. The hole transport layer (HTL) is a key component of inverted PSCs and OSCs, responsible for extracting holes, blocking electrons, adjusting the work function of the transparent conductive oxide (TCO), and improving the quality of the active layer film. Self-assembled molecules, due to their ultrathin thickness (2-10 nm), solution-processability, tunable interfacial dipoles, and defect passivation capabilities, have become alternatives to traditional hole transport materials (such as PEDOT:PSS and NiO). X It is a strong candidate for PTAA, Spiro-OMeTAD. A typical self-assembled molecule consists of three parts: anchoring group (such as phosphonic acid, carboxylic acid), linking unit (such as alkylene, phenylene) and terminal group (such as carbazole, triphenylamine, phenothiazine, etc.).

[0003] Numerous SAM molecules have been reported in the literature, including but not limited to: carbazoles: 2PACz, 3PACz, 4PACz, MeO-2PACz, Me-4PACz, CbzNaph, CbzPh, CbzBT, CbzBF, etc.; triphenylamines: MPA-CPA, MPA-Ph-CA, PPA, PPAOMe, TPA-3CPA, etc.; phenothiazine / phenoxazine / phenoselenine derivatives: Br-2EPT, Br-2EPO, Br-2EPSe, Th-2EPT, PTZ1-3, etc.; acridine derivatives: 4PADMeAC, etc. However, existing technologies still have the following significant drawbacks: Single-component SAM materials are prone to structural collapse under thermal stress: Single-component self-assembling molecules have a strong tendency to self-assemble, forming a relatively ordered stacked structure. Under high temperature (85°C) or thermal cycling conditions, this ordered structure gradually collapses, leading to the collapse of the π-π stacked structure and the destruction of hole transport channels. The effectiveness of the two-component mixing strategy is limited: Existing studies have attempted to mix two self-assembled molecules, but their stacking patterns remain relatively simple, failing to form a truly high-entropy system. Furthermore, the conductivity of single-component self-assembled films decreases significantly after aging, and while binary mixing systems show some improvement, they still cannot meet the long-term stability requirements for commercial applications.

[0004] Lack of systematic high-entropy structure design methods: Existing technologies have not yet proposed strategies to systematically enhance the configurational entropy of hybrid SAM systems by regulating various non-covalent interactions between molecules (π-π, CH···π, CH···O, CH···S, etc.).

[0005] Therefore, there is an urgent need to develop a new hole transport material system that can maintain structural stability under external stress and has excellent hole extraction capabilities. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a high-entropy self-assembled hole transport layer, its preparation method, and its application.

[0007] To achieve the above objectives, the present invention is implemented according to the following technical solution: The first technical solution provided by this invention is a high-entropy self-assembled hole transport layer, which is formed on a conductive substrate by mixing three or more self-assembled molecules to form a high-entropy self-assembled hole transport layer film; the self-assembled molecules have the following general formula: A — L — T; Wherein: A is the anchoring group, independently selected from one of phosphonic acid, carboxylic acid, boric acid, sulfonic acid, cyanoacrylic acid, cyanophosphonic acid, catechol, and silyl group; L is the linking unit, selected from one of alkylene with 1-8 carbon atoms, arylene with 6-20 ring carbon atoms, and heteroarylene with 5-12 ring atoms; T is the terminal group, independently selected from one of alkyl, ammonium salt, cyano, phosphonic acid, carboxylic acid, amino, trifluoromethyl, arylene with 6-20 ring carbon atoms, and heteroarylene with 5-12 ring atoms; The three or more self-assembled molecules in the mixture differ in at least one of the following aspects: The terminal groups have different chemical structures, the same core but different substituents, the same conjugated skeleton but different linker lengths, the same terminal groups but different anchoring groups, and different molecular topologies.

[0008] Furthermore, the terminal group is selected from one of the following compounds: carbazole, triphenylamine, phenothiazine, phenotoxazine, phenoteneselenomethazine, acridine, fluorene, thiophene, polycyclic aromatic hydrocarbons, and phthalocyanine compounds.

[0009] Preferably, the self-assembled molecule comprises: ; The molecules listed above are merely examples, and the present invention is not limited thereto. Any self-assembled molecule having anchoring groups, linking units, and terminal groups, as long as it has different intermolecular interaction characteristics and stacking tendency from other molecules in the high-entropy system, can be used as a component of the high-entropy self-assembled hole transport layer required by the present invention.

[0010] The second technical solution provided by this invention is a method for preparing the above-mentioned high-entropy self-assembled hole transport layer, comprising the following steps: S1. Dissolve three or more of the self-assembled molecules in an organic solvent to form a mixed solution of 0.01-100 mM; S2. The mixed solution is deposited onto a cleaned and ultraviolet ozone-treated conductive substrate to form a thin film; S3. Anneal the film at 50-200℃ for 1-60 minutes to obtain a high-entropy self-assembled hole transport layer film.

[0011] Preferably, the organic solvent is selected from methanol, ethanol, isopropanol, tert-butanol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and ethylene glycol monomethyl ether.

[0012] Preferably, in step S1, three or more of the self-assembled molecules are mixed in an equimolar ratio.

[0013] Preferably, the conductive substrate is selected from fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), and nickel oxide (NiO). x One or more combinations of molybdenum oxide (MoO3) and tin oxide (SnO2).

[0014] Preferably, in step S2, the mixed solution is deposited on the conductive substrate by one of the following methods: spin coating, blade coating, slot coating, inkjet printing, dip coating, immersion coating, and vacuum evaporation.

[0015] The third technical solution provided by this invention is the application of the above-mentioned high-entropy self-assembled hole transport layer in the fabrication of perovskite solar cell devices, characterized in that the hole transport layer of the perovskite solar cell device is made of the high-entropy self-assembled hole transport layer thin film.

[0016] Preferably, the perovskite solar cell is an inverted perovskite solar cell.

[0017] Compared with the prior art, the present invention has the following significant advantages: (1) Significantly improved structural stability: By constructing a high-entropy self-assembled hole transport layer, this invention effectively suppresses the formation of long-range ordered structures by utilizing the coexistence of multiple intermolecular interactions and diverse stacking modes, thus maintaining the structural stability of the film under external stresses such as heat, light, and machinery. Experiments show that the π-π satellite peaks of the single-component CbzNaph film completely disappear after aging at 85℃ for 100 hours, while the π-π satellite peaks of the M3 film of the high-entropy self-assembled hole transport layer of this invention are still clearly distinguishable under the same conditions, indicating that the π-π stacking structure is not destroyed.

[0018] (2) Enhanced or maintained hole transport performance: The high-entropy self-assembled hole transport layer of this invention significantly extends the lifespan of the device under high temperature, continuous light irradiation, and humid heat environments while maintaining or even improving the hole extraction and transport capabilities. The conductivity of the M3 film is 9.2 μS / cm, which is higher than that of any single component (CbzNaph: 7.25 μS / cm), and it only decreases by 0.72 μS / cm after aging, while CbzNaph decreases by 3.63 μS / cm.

[0019] (3) Significantly improved device efficiency: The inverted perovskite solar cell fabricated using the high-entropy self-assembled hole transport layer of the present invention achieves excellent photoelectric performance. In the embodiments, the device based on the M3 high-entropy self-assembled hole transport layer has an open-circuit voltage of 1.202V, a short-circuit current density of 26.40mA / cm², a fill factor of 86.67%, and a photoelectric conversion efficiency of up to 27.50%.

[0020] (4) Significantly improved long-term operational stability: The inverted perovskite solar cell prepared using the high-entropy self-assembled hole transport layer of the present invention maintains an efficiency of over 98% (M3) of the initial value after 1000 hours of maximum power point tracking at 85°C, which is significantly better than the single-component comparative device (88%). The high-entropy system significantly enhances its resistance to thermal stress, thermal cycling, and photothermal aging through the increase of configurational entropy. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of an inverted planar heterojunction perovskite solar cell provided in an embodiment of the present invention; wherein: 1, a transparent conductive substrate ITO; 2, a high-entropy self-assembled hole transport layer; 3, a perovskite light-absorbing layer; 4, an electron transport layer (C 60 5. Copper or silver electrodes.

[0022] Figure 2 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M1 in Embodiment 1 of the present invention.

[0023] Figure 3The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M2 in Embodiment 2 of the present invention.

[0024] Figure 4 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M3 in Embodiment 3 of the present invention.

[0025] Figure 5 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M4 in Embodiment 4 of the present invention.

[0026] Figure 6 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M5 in Embodiment 5 of the present invention.

[0027] Figure 7 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M6 in Embodiment 6 of the present invention.

[0028] Figure 8 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M7 in Embodiment 7 of the present invention.

[0029] Figure 9 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M8 in Embodiment 8 of the present invention.

[0030] Figure 10 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on the high-entropy self-assembled hole transport layer M9 in Embodiment 9 of the present invention.

[0031] Figure 11 The JV curve and photovoltaic parameter diagram are shown for the perovskite solar cell based on single-component CbzNaph in Example 10 of the present invention. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention.

[0033] The following embodiments exemplify the fabrication of several typical high-entropy self-assembled hole transport layers, and the fabricated high-entropy self-assembled hole transport layers are used in inverted planar heterojunction perovskite solar cells. Figure 1This is a schematic diagram of the structure of the inverted planar heterojunction perovskite solar cell involved in the present invention, which includes, from bottom to top: a transparent conductive substrate FTO1, a high-entropy self-assembled hole transport layer 2, a perovskite light-absorbing layer 3, an electron transport layer (C60) 4, and a copper or silver electrode 5.

[0034] Example 1: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: The etched transparent conductive substrate FTO was ultrasonically treated in cleaning agent, deionized water, anhydrous ethanol, acetone and isopropanol for 15 minutes in sequence. After being removed, it was dried with clean air and placed in an oven to dry at 120°C for 8 hours, followed by UV / ozone treatment for 30 minutes.

[0035] 2) Preparation of high-entropy self-assembled hole transport layer M1: ; 2PACz / MeO-2PACz / CbzNaph were weighed in a 1:1:1 molar ratio and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), resulting in a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The resulting mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M1) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0036] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0037] 5) Fabrication of copper or silver electrodes: In 1×10 -6Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0038] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 2 As shown, by Figure 2 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.197V, and the short-circuit current density is 25.84mA / cm². 2 The fill factor is 87.05%, and the photoelectric conversion efficiency is 26.92%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 93% of the initial value.

[0039] Example 2: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Preparation of high-entropy self-assembled hole transport layer M2: ; CbzNaph / CbzBF / CbzBT were weighed in a 1:1:1 molar ratio and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), resulting in a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The resulting mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M2) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0040] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0041] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0042] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 3 As shown, by Figure 3 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.194V, and the short-circuit current density is 25.52mA / cm². 2 The fill factor is 88.43%, and the photoelectric conversion efficiency is 26.95%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 95% of the initial value.

[0043] Example 3: Reference Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Preparation of high-entropy self-assembled hole transport layer M3: ; CbzNaph / JJ88 / JJ89 were weighed in a 1:1:1 molar ratio and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), resulting in a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The resulting mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M3) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0044] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0045] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0046] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 4 As shown, by Figure 4 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.202V, and the short-circuit current density is 26.40mA / cm². 2 The fill factor is 86.67%, and the photoelectric conversion efficiency is 27.50%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 98% of the initial value.

[0047] Example 4: Reference Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of a high-entropy self-assembled hole transport layer M4: ; Weigh 2PACz / MeO-2PACz / Me-4PACz / CbzNaph in a molar ratio of 1:1:1:1 and dissolve them in a mixed solvent of ethanol and DMF (volume ratio 4:1) to a total concentration of 2.0 mM. Sonicate for 10 minutes to ensure complete dissolution. Spin-coat the above mixed solution onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. A high-entropy self-assembled hole transport layer film with a thickness of approximately 5 nm (denoted as M4) is obtained. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0048] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0049] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0050] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 5 As shown, by Figure 5 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.200V, and the short-circuit current density is 26.38mA / cm². 2 The fill factor is 85.74%, and the photoelectric conversion efficiency is 27.13%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 98% of the initial value.

[0051] Example 5: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of a high-entropy self-assembled hole transport layer M5: ; 2PACz / 3PACz / 4PACz / 5PACz were weighed in a molar ratio of 1:1:1:1 and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), with a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M5) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0052] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0053] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0054] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 6 As shown, by Figure 6It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.186V, and the short-circuit current density is 25.66mA / cm². 2 The fill factor is 86.74%, and the photoelectric conversion efficiency is 26.41%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 94% of the initial value.

[0055] Example 6: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of the high-entropy self-assembled hole transport layer M6: ; 2PACz / MeO-2PACz / 3PATAT-C3 was weighed in a 1:1:1 molar ratio and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), resulting in a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The resulting mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M6) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0056] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0057] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0058] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 7 As shown, by Figure 7 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.193V, and the short-circuit current density is 25.40mA / cm². 2 The fill factor is 86.99%, and the photoelectric conversion efficiency is 26.37%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 91% of the initial value.

[0059] Example 7: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of a high-entropy self-assembled hole transport layer M7: ; Weigh 2PACz / MeO-2PACz / DC-PA / IAHA in a molar ratio of 1:1:1:1 and dissolve them in a mixed solvent of ethanol and DMF (volume ratio 4:1) to a total concentration of 2.0 mM. Sonicate for 10 minutes to ensure complete dissolution. Spin-coat the above mixed solution onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. A high-entropy self-assembled hole transport layer film with a thickness of approximately 5 nm (denoted as M7) is obtained. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0060] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0061] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0062] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 8 As shown, by Figure 8 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.172V, and the short-circuit current density is 25.93mA / cm². 2 The fill factor is 83.82%, and the photoelectric conversion efficiency is 25.47%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 91% of the initial value.

[0063] Example 8: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of the high-entropy self-assembled hole transport layer M8: ; Br-2EPO / Br-2EPT / Br-2EPSe were weighed in a 1:1:1 molar ratio and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1), resulting in a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M8) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0064] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0065] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0066] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 9 As shown, by Figure 9 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.171V, and the short-circuit current density is 25.91mA / cm². 2 The fill factor is 85.22%, and the photoelectric conversion efficiency is 25.85%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 89% of the initial value.

[0067] Example 9: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Fabrication of the high-entropy self-assembled hole transport layer M9: ; MPA-CPA / 2PATPA / PATPA were weighed at a molar ratio of 1:1:1 and dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1) to a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The mixture was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. This yielded a high-entropy self-assembled hole transport layer film (denoted as M9) with a thickness of approximately 5 nm. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0068] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0069] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0070] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 10 As shown, by Figure 10 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.198V, and the short-circuit current density is 25.41mA / cm². 2 The fill factor is 87.67%, and the photoelectric conversion efficiency is 26.70%. The device operates at 85... o After 1000 hours of maximum power testing, the efficiency remains above 92% of the initial value.

[0071] Comparative example: Refer to Figure 1 The structure shown is used to fabricate an inverse planar heterojunction perovskite solar cell: 1) Cleaning the transparent conductive substrate FTO: Same as in Example 1; 2) Preparation of self-assembled hole transport layer CbzNaph: ; CbzNaph was dissolved in a mixed solvent of ethanol and DMF (volume ratio 4:1) to a total concentration of 2.0 mM. The solution was sonicated for 10 minutes to ensure complete dissolution. The solution was then spin-coated onto FTO at 4000 rpm for 30 seconds, followed by annealing at 100°C for 10 minutes. A CbzNaph film with a thickness of approximately 5 nm was obtained. 3) Preparation of perovskite light-absorbing layer: All ABX3 types have a perovskite structure, where A is any organic cation, such as formamidinium (FA) or methylamine (MA); B is any metal cation, such as lead or tin; and X is any halide anion, such as chlorine, bromine, or iodine. ABX3 is prepared by dissolving it in solvents such as DMF or DMSO. It is then spin-coated onto ITO in two steps: 1000 rpm for 10 s and 6000 rpm for 20 s. With 5 seconds remaining, chlorobenzene is dropped onto the center of the substrate, and the film is annealed at 100 °C for 0.5 hours.

[0072] 4) Fabrication of the electron transport layer: In 1×10 -6 Under a vacuum of Pa, C 60 It is deposited on the surface of perovskite.

[0073] 5) Fabrication of copper or silver electrodes: In 1×10 -6 Copper or silver electrodes were deposited by evaporation at a vacuum level of 0.3 Å / s, with the electrode thickness controlled to be ~100 nm; the effective area of ​​the fabricated planar heterojunction perovskite solar cell was 0.1 cm². 2 .

[0074] 6) Testing: At AM 1.5G (100mW / cm) 2 Under simulated lighting conditions, the JV characteristics were tested using a Keithley 2400 digital source table. The results are as follows: Figure 11 As shown, by Figure 11 It can be seen that the open-circuit voltage of the inverted planar heterojunction perovskite solar cell prepared in this embodiment is 1.196V, and the short-circuit current density is 25.22mA / cm². 2 The fill factor is 87.19%, and the photoelectric conversion efficiency is 26.29%. The device operates at 85... o After C has been tested at maximum power for 1000 hours, the efficiency remains above 88% of the initial value.

[0075] In summary, this invention effectively suppresses the formation of long-range ordered structures by constructing a high-entropy self-assembled hole transport layer and utilizing the coexistence of multiple intermolecular interactions and diverse stacking modes, thus maintaining the structural stability of the film under external stresses such as heat, light, and mechanical stress. The results of the above embodiments show that the π-π satellite peaks of the single-component CbzNaph film completely disappear after aging at 85℃ for 100 hours, while the π-π satellite peaks of the high-entropy self-assembled hole transport layer M3 film of this invention remain clearly distinguishable under the same conditions, indicating that the π-π stacking structure is not destroyed.

[0076] The high-entropy self-assembled hole transport layer of this invention significantly extends the lifespan of devices under high temperature, continuous light irradiation, and humid heat environments while maintaining or even improving hole extraction and transport capabilities. The conductivity of the M3 film is 9.2 μS / cm, higher than any single component (CbzNaph: 7.25 μS / cm), and decreases by only 0.72 μS / cm after aging, while CbzNaph decreases by 3.63 μS / cm.

[0077] The inverted perovskite solar cell fabricated using the high-entropy self-assembled hole transport layer of this invention achieves excellent photoelectric performance. In the embodiments, the device based on the M3 high-entropy self-assembled hole transport layer has an open-circuit voltage of 1.202V, a short-circuit current density of 26.40mA / cm², a fill factor of 86.67%, and a photoelectric conversion efficiency of up to 27.50%.

[0078] The inverted perovskite solar cell fabricated using the high-entropy self-assembled hole transport layer of this invention maintains an efficiency of over 98% (M3) of the initial value after 1000 hours of maximum power point tracking at 85°C, significantly outperforming the single-component comparative device (88%). The high-entropy system significantly enhances its resistance to thermal stress, thermal cycling, and photothermal aging through the increase in configurational entropy.

[0079] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A high-entropy self-assembling hole transport layer, characterized in that, A high-entropy self-assembled hole transport layer film is formed on a conductive substrate by mixing three or more self-assembled molecules; the self-assembled molecules have the following general formula: A — L — T; Wherein: A is the anchoring group, independently selected from one of phosphonic acid, carboxylic acid, boric acid, sulfonic acid, cyanoacrylic acid, cyanophosphonic acid, catechol, and silyl group; L is the linking unit, selected from one of alkylene with 1-8 carbon atoms, arylene with 6-20 ring carbon atoms, and heteroarylene with 5-12 ring atoms; T is the terminal group, independently selected from one of alkyl, ammonium salt, cyano, phosphonic acid, carboxylic acid, amino, trifluoromethyl, arylene with 6-20 ring carbon atoms, and heteroarylene with 5-12 ring atoms; The three or more self-assembled molecules in the mixture differ in at least one of the following aspects: The terminal groups have different chemical structures, the same core but different substituents, the same conjugated skeleton but different linker lengths, the same terminal groups but different anchoring groups, and different molecular topologies.

2. The high-entropy self-assembled hole transport layer according to claim 1, characterized in that, The terminal group is selected from one of the following compounds: carbazole, triphenylamine, phenothiazine, phenotoxazine, phenotylene, acridine, fluorene, thiophene, polycyclic aromatic hydrocarbons, and phthalocyanine compounds.

3. The high-entropy self-assembled hole transport layer according to claim 1, characterized in that, The self-assembled molecules include: 。 4. A method for preparing a high-entropy self-assembled hole transport layer as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. Dissolve three or more of the self-assembled molecules in an organic solvent to form a mixed solution of 0.01-100 mM; S2. The mixed solution is deposited onto a cleaned and ultraviolet ozone-treated conductive substrate to form a thin film; S3. Anneal the film at 50-200℃ for 1-60 minutes to obtain a high-entropy self-assembled hole transport layer film.

5. The method for preparing a high-entropy self-assembled hole transport layer according to claim 4, characterized in that, The organic solvent is selected from one of methanol, ethanol, isopropanol, tert-butanol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and ethylene glycol monomethyl ether.

6. The method for preparing a high-entropy self-assembled hole transport layer according to claim 4, characterized in that, In step S1, three or more of the self-assembled molecules are mixed in an equimolar ratio.

7. The method for preparing a high-entropy self-assembled hole transport layer according to claim 4, characterized in that, The conductive substrate is selected from fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), and nickel oxide (NiO). x One or more combinations of molybdenum oxide (MoO3) and tin oxide (SnO2).

8. The method for preparing a high-entropy self-assembled hole transport layer according to claim 4, characterized in that, In step S2, the mixed solution is deposited on the conductive substrate by one of the following methods: spin coating, blade coating, slot coating, inkjet printing, dip coating, immersion coating, and vacuum evaporation.

9. The application of a high-entropy self-assembled hole transport layer as described in any one of claims 1-3 in the fabrication of perovskite solar cell devices, characterized in that, The hole transport layer of the perovskite solar cell device is made of the high-entropy self-assembled hole transport layer film.

10. The application of the high-entropy self-assembled hole transport layer according to claim 9 in the fabrication of perovskite solar cell devices, characterized in that, The perovskite solar cell is an inverted perovskite solar cell.

Images