Europium, terbium, and samarium nanopolymers enhance polymer solar cells and their methods

Abstract

This invention discloses a polymer solar cell with synergistic enhancement of europium, terbium, and samarium nanoclusters and its method. The polymer solar cell is fabricated by simultaneously doping rare-earth europium, terbium, and samarium nanoclusters into the ZnO electron transport layer and transparent electrode. This invention achieves synergistic modification of the electron transport layer and transparent cathode by simultaneously doping europium, terbium, and samarium nanoclusters into the ZnO electron transport layer and transparent electrode. Europium, terbium, and samarium rare-earth elements possess excellent optical properties; their co-doping can synergistically regulate the energy level structure of the ZnO electron transport layer and transparent electrode, fill surface defects, reduce the probability of hole-electron recombination in the device, and improve electron mobility and electron injection efficiency.

Description

Technical Field

[0001] This invention relates to the intersection of hybrid material preparation and organic photovoltaic technology, specifically to a flexible semi-transparent polymer solar cell with synergistic effects of europium, terbium, and samarium nanoaggregates and its preparation method. Background Technology

[0002] Polymer solar cells, with their unique advantages such as lightweight, flexibility, solution-processability, and ease of large-area fabrication, have shown great application potential and broad development prospects in emerging fields such as flexible electronics, wearable smart devices, portable energy, building-integrated photovoltaics, and indoor low-light utilization. Among them, flexible semi-transparent polymer solar cells not only inherit the flexibility, lightweight, and solution-processability of traditional polymer solar cells, but also possess excellent visible light transmittance and tunable optical performance. This makes them suitable for special application scenarios such as curved carriers, transparent doors and windows, agricultural greenhouse photovoltaic structures, and wearable optoelectronic devices, thus becoming one of the most valuable research directions in the field of polymer photovoltaics in recent years. However, in the performance optimization process of semi-transparent polymer solar cells, there is always an inherent mutual constraint between visible light transmittance and photoelectric conversion efficiency. Improving the light absorption capacity of the active layer to enhance photoelectric conversion efficiency often leads to a significant decrease in visible light transmittance; conversely, pursuing high transmittance requires thinning the active layer and reducing light absorption, resulting in a significant decrease in short-circuit current density and photoelectric conversion efficiency. This contradiction between efficiency and transmittance has become a key bottleneck restricting the practical application of semi-transparent devices. Therefore, by employing strategies such as rational material design, interface engineering, and spectral selectivity optimization, it is possible to effectively improve photoelectric conversion efficiency while ensuring high visible light transmittance, thereby balancing the trade-off between the two. This is of vital scientific significance and application value for promoting flexible semi-transparent polymer solar cells from laboratory research to large-scale and large-area practical applications.

[0003] The electron transport layer is the core functional layer of flexible, semi-transparent organic solar cells, directly determining the cell's charge transport efficiency, optical transmittance, and mechanical stability. Zinc oxide (ZnO), a commonly used electron transport material in polymer solar cells, possesses advantages such as high electron mobility, good energy level matching, simple fabrication process, and environmental friendliness, making it widely used in the fabrication of electron transport layers for solar cells. However, pure ZnO electron transport layers suffer from numerous surface defects and a high probability of charge recombination. Furthermore, its flexible bending process is prone to cracking, affecting the long-term stability of polymer solar cells. Rare earth elements europium (Eu), terbium (Tb), and samarium (Sm), due to their unique electronic configurations—the 4f layer of their outer electrons being shielded by the 5s and 5p electron layers—possess excellent optical properties and electron transport characteristics. Doping these elements into semiconductor materials can effectively control the material's energy level structure, reduce surface defects, and improve charge transport efficiency. Simultaneously, europium ions, terbium ions, and samarium ions are combined with the transparent top electrode material of semi-transparent polymer solar cells to improve their photoelectric conversion efficiency while maintaining the excellent transparency of the battery device.

[0004] Therefore, developing a preparation method that can achieve synergistic modification of the electron transport layer and transparent electrode, solve the problem of rare earth nanoparticle agglomeration, and improve the photoelectric performance, optical transmittance, and flexibility stability of semi-transparent polymer solar cells has become a pressing technical challenge in the field of flexible semi-transparent polymer solar cells. Summary of the Invention

[0005] This invention aims to address the shortcomings of existing technologies by proposing a polymer solar cell with synergistic enhancement of europium, terbium, and samarium nanoclusters and its method. The method employs self-assembly technology, utilizing block polymers induced by europium, terbium, and samarium ions to form uniform nanoclusters. By simultaneously doping europium, terbium, and samarium nanoclusters in the ZnO electron transport layer and transparent electrode, the photoelectric conversion efficiency and light utilization of the semi-transparent polymer solar cell are synergistically improved.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows: A method for preparing a polymer solar cell with synergistic enhancement of europium, terbium, and samarium nanoclusters involves simultaneously doping rare-earth europium nanoclusters, rare-earth terbium nanoclusters, and rare-earth samarium nanoclusters into a ZnO electron transport layer and a transparent electrode to prepare the polymer solar cell.

[0007] The preparation method described above, the preparation method of ZnO electron transport layer blend solution: rare earth europium nanopolymer powder, rare earth terbium nanopolymer powder, rare earth samarium nanopolymer powder and ZnO in a mass ratio of 1:1:1:57, add methanol as solvent, and prepare a blend solution with a concentration of 1 mg / mL.

[0008] The preparation method for the rare earth europium nanopolymers, rare earth terbium nanopolymers, or rare earth samarium nanopolymers is as follows: Amphiphilic block polymers PS-b-PAA, europium chloride / terbium / samarium chloride, Phen, and aacac are taken in a molar ratio of 1:1:1:3. DMF is added as the reaction solvent, and the mixture is placed in an oil bath at 60°C and reacted continuously for 6 hours to obtain a mixed solution of terbium nanopolymers. The reaction solution is washed with ethanol, centrifuged to remove the supernatant, and dried in a vacuum drying oven at 45°C for 8 hours to obtain rare earth europium / terbium / samarium nanopolymer powder.

[0009] The preparation method described above includes the preparation of the transparent electrode solution: a 1 mg / L AgNO3 aqueous solution is prepared and mixed with transparent conductive ink at a ratio of 1:9. Rare earth europium, terbium, and samarium nanoaggregates are weighed and added to the mixed AgNO3 transparent conductive ink at a ratio of (1-3):(1-3):(1-3). The mixture is stirred thoroughly at room temperature for 2 hours to prepare a light energy conversion type highly conductive transparent electrode solution with a concentration of 0.75 mg / mL.

[0010] The preparation method specifically includes the following steps: 1) The flexible conductive transparent substrate material was placed in an isopropanol solution and cleaned using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment.

[0011] 2) A layer of europium-terbium-samarium nanopolymer co-doped ZnO electron transport layer blend solution is coated onto a flexible conductive transparent film to obtain the electron transport layer, followed by annealing. 3) Coat the electron transport layer obtained in step 2) with an active layer solution composed of donor and acceptor polymers to obtain the active layer, and anneal it; after annealing, continue to coat the active layer with a hole transport layer. 4) Coat a layer of the transparent electrode solution onto the surface of the hole transport layer to complete the fabrication of europium, terbium, and samarium nanoclusters co-doped flexible semi-transparent polymer solar cells.

[0012] In the preparation method described above, the flexible conductive transparent substrate material is a PET film or a PEN film coated with ITO.

[0013] The preparation method described above involves a hydrothermal process to prepare ZnO, using zinc acetate dihydrate or zinc nitrate hexahydrate as the ZnO precursor, which is dissolved in deionized water. Under thorough stirring, 10-35% concentrated ammonia solution is slowly added until the precipitate just disappears (pH≈10), which constitutes the precursor solution. After the addition is complete, the mixed solution is transferred to a high-pressure reactor and placed in a constant-temperature drying oven at 60-210℃ for continuous heating. After the reaction is complete, the sample is allowed to cool naturally to room temperature, then repeatedly washed with deionized water, filtered, and dried to obtain ZnO.

[0014] In the preparation method described above, the conductive ink is silver nanowires or a mixture of silver nanowires and a conductive polymer solution.

[0015] In the preparation method described above, the hole transport layer is a solution formed from a PEDOT:PSS conductive polymer solution or other metal oxides.

[0016] The preparation method described herein uses a coating speed of 5-90 mm / s and an annealing temperature of 70-120℃.

[0017] The beneficial effects of this invention are: The europium-terbium-samarium nano-aggregate synergistic flexible semi-transparent polymer solar cell of the present invention employs a transparent electrode doped with europium-terbium-samarium nano-aggregates in a light-converting, highly conductive inversion polymer solar cell. This improves electron injection efficiency while maintaining high light transmittance, thereby increasing the short-circuit current density of the device. J SC As shown in Table 1, the performance parameters of the device are as follows: The photoelectric conversion efficiency (PCE) of the large-area blade-coated device reaches 6.09%, and the average transmittance (AVT) remains at 40%. The light utilization efficiency (LUE) is calculated using the formula: LUE = PCE × AVT / 100, reaching 2.4%. Compared to undoped blade-coated basic polymer solar cells, the blade-coated doped polymer solar cells obtained using the method of this invention can achieve a 20% increase in efficiency while maintaining the corresponding transmittance.

[0018] In this invention, europium, terbium, and samarium nanoaggregates are simultaneously doped into the ZnO electron transport layer and the transparent electrode, achieving synergistic modification of the electron transport layer and the transparent cathode. Europium, terbium, and samarium rare earth elements have excellent optical properties, and their co-doping can synergistically regulate the energy level structure of the ZnO electron transport layer and the transparent electrode, fill surface defects, reduce the probability of hole-electron recombination in the device, and improve electron mobility and electron injection efficiency. Attached Figure Description

[0019] Figure 1 This is a synthetic route diagram of the rare earth nanoaggregates described in this invention.

[0020] Figure 2 This is a TEM image of the ZnO preparation method described in this invention.

[0021] Figure 3 This is a TEM image of the europium-terbium-samarium nanoaggregates co-doped with the ZnO electron transport layer described in this invention.

[0022] Figure 4 This is an image showing the water contact angle of the europium-terbium-samarium nanoaggregates co-doped with the ZnO electron transport layer in Example 9 of this invention.

[0023] Figure 5 This is an AFM height diagram of the co-doped ZnO electron transport layer of europium, terbium, and samarium nanoclusters described in Example 9 of the present invention.

[0024] Figure 6 This is a schematic diagram illustrating the structural principle of the flexible semi-transparent polymer solar cell described in this invention.

[0025] Figure 7 The graphs show the open-circuit voltage and short-circuit current density of the undoped flexible semi-transparent polymer solar cells and the europium-terbium-samarium nanoaggregate co-doped flexible semi-transparent polymer solar cells described in Examples 5 and 9 of this invention.

[0026] Figure 8 The external quantum efficiency curves are shown for the undoped flexible semi-transparent polymer solar cells and the europium-terbium-samarium nanoaggregate co-doped flexible semi-transparent polymer solar cells described in Examples 5 and 9 of this invention.

[0027] Figure 9 The transmission spectra are those of the undoped flexible semi-transparent polymer solar cells and the europium-terbium-samarium nanoaggregate co-doped flexible semi-transparent polymer solar cells described in Examples 5 and 9 of this invention.

[0028] Figure 10 The CIE color charts are for the undoped flexible semi-transparent polymer solar cells and the europium-terbium-samarium nanoaggregate co-doped flexible semi-transparent polymer solar cells described in Examples 5 and 9 of this invention. Detailed Implementation

[0029] The present invention will be described in detail below with reference to specific embodiments.

[0030] Example 1: Preparation of the amphiphilic block polymer PS-b-PAA (1) Preparation of polystyrene (PS) chains: Weigh 0.104 g of reversible addition-fragmentation chain transfer agent (RAFT) and 0.016 g of initiator AIBN and place them in a round-bottom flask. Add 30 mL of dioxane as a solvent to the flask, and then rapidly add 10.4 g of styrene monomer to the flask. After the addition is complete, seal the mouth of the flask with a rubber stopper. Purge the flask with nitrogen for 40 min to remove the air inside the flask, and heat the flask at a temperature of 60°C to 80°C for 6 hours under nitrogen atmosphere. After the reaction is complete, pour the reaction solution into a beaker, add excess methanol to wash, and obtain PS by precipitation. Then place the PS in a vacuum drying oven and dry at 60°C for 8 hours to remove the organic solvent.

[0031] (2) Preparation of amphiphilic block polymer PS-b-PAA: Weigh 5.0 g of the product PS from step (1) and 0.016 g of initiator AIBN and put them into a round-bottom flask. Add 40 mL of dioxane as a solvent to the flask and shake the flask until the PS is completely dissolved. Then add the acrylic monomer and seal the mouth of the flask with a rubber stopper. Then purge the flask with nitrogen for 45 minutes to remove the air in the flask. Place the flask under nitrogen atmosphere in an oil bath at 80°C and heat for 8 hours. Pour the solution after reaction into a beaker and add excess petroleum ether to wash it. Precipitate to obtain PS-b-PAA. Place the beaker in a vacuum drying oven and dry at 60°C for 8 hours to remove the organic solvent and obtain pure PS-b-PAA powder.

[0032] Example 2: Preparation of rare earth europium nanoaggregates The amphiphilic block polymers PS-b-PAA, europium chloride, Phen, and TAA prepared in Example 1 were taken in a molar ratio of 1:1:1:3 and placed in a flask. DMF was added as a reaction solvent, and the flask containing the reaction solution was placed in an oil bath at 60°C and reacted for 6 hours to obtain a mixed solution of europium nanoparticles. The solution after reaction was washed with ethanol, centrifuged to remove the supernatant, and dried in a vacuum drying oven at 45°C for 8 hours to obtain rare earth europium nanoparticle powder.

[0033] Example 3: Preparation of rare earth terbium nanoaggregates The amphiphilic block polymer PS-b-PAA, terbium chloride, Phen, and acac prepared in Example 1 were placed in a flask in a molar ratio of 1:1:1:3. DMF was added as a reaction solvent, and the flask containing the reaction solution was placed in an oil bath at 60°C and reacted for 6 hours to obtain a mixed solution of terbium nanoparticles. The solution was washed with ethanol, centrifuged to remove the supernatant, and dried in a vacuum drying oven at 45°C for 8 hours to obtain rare earth terbium nanoparticle powder.

[0034] Example 4: Preparation of rare earth samarium nanoaggregates The amphiphilic block polymer PS-b-PAA, samarium chloride, Phen, and acac prepared in Example 1 were taken in a molar ratio of 1:1:1:3 and placed in a flask. DMF was added as a reaction solvent, and the flask containing the reaction solution was placed in an oil bath at 60°C and reacted for 6 hours to obtain a mixed solution of samarium nanoparticles. The solution after reaction was washed with ethanol, centrifuged to remove the supernatant, and dried in a vacuum drying oven at 45°C for 8 hours to obtain rare earth samarium nanoparticle powder.

[0035] Example 5: Fabrication of Flexible Semi-Transparent Polymer Solar Cells (1) Weigh ZnO and put it into a glass bottle. Add methanol as a solvent to prepare a ZnO solution with a concentration of 1 mg / mL.

[0036] (2) The donor material PM6 and acceptor material Y6 of the polymer solar cell are placed in a glass bottle, and chlorobenzene is added as a solvent. The mass ratio of PM6 to Y6 is 1:1.2, and a blend solution with a concentration of 16 mg / mL is prepared. The blend solution is heated and stirred at 45°C for 5-7 hours.

[0037] (3) The flexible transparent PET film coated with ITO was cleaned in an isopropanol solution using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment for 5-10 minutes to improve the adhesion of the substrate material.

[0038] (4) Place the cleaned flexible transparent PET film from step (3) on the substrate of the coating machine, start the scraper to coat a layer of ZnO solution prepared in step (1) as an electron transport layer, the coating speed is 40 mm / s, and after the coating is completed, place it on the heating table and anneal at 120°C for 20 min.

[0039] (5) Add 1% by volume of 1,8-diiodooctane (DIO) as an additive to the donor-acceptor blend solution prepared in step (2), continue stirring the blend solution for 30 minutes, and then coat the donor-acceptor blend solution onto the electron transport layer prepared in step (4) to obtain an active layer film. The coating speed is 30 mm / s. After the coating is completed, anneal at 100°C for 15 minutes on a heating stage.

[0040] (6) A mixed solution of PEDOT:PSS and molybdenum trioxide (mass ratio of PEDOT:PSS and molybdenum trioxide is 9:1) is coated onto the active layer film prepared in step (5) as a hole transport layer at a coating speed of 40 mm / s.

[0041] (7) Prepare an aqueous solution of 1 mg / L AgNO3 and mix it with transparent conductive ink (purchased from Hunan Nasheng Electronic Technology Co., Ltd., model: AP20, the same below) at a ratio of 1:9. Stir at room temperature for 2 hours and then coat it onto the surface of the hole transport layer prepared in step (6) at a coating speed of 45 mm / s to obtain a flexible coated polymer solar cell.

[0042] Compared with common solar cell devices, the flexible semi-transparent polymer solar cell prepared in this invention has a flexible substrate and high transparency, and can be fabricated on a large area. The performance parameters of the semi-transparent organic solar cell are shown in Table 1. The conversion efficiency of the flexible semi-transparent polymer solar cell reaches 4.92%, while the average transmittance remains at 40.32%, and the light utilization rate reaches 2.0%.

[0043] Example 6: Fabrication of flexible semi-transparent polymer solar cells doped with europium nanoclusters (1) Weigh europium nanoparticle powder and ZnO and put them into a glass bottle. Add methanol as a solvent. The mass ratio of europium nanoparticles to ZnO is 1:19. Prepare a blended solution with a concentration of 1 mg / mL.

[0044] (2) The donor material PM6 and acceptor material Y6 of the polymer solar cell are placed in a glass bottle, and chlorobenzene is added as a solvent. The mass ratio of PM6 to Y6 is 1:1.2, and a blend solution with a concentration of 16 mg / mL is prepared. The blend solution is heated and stirred at 45°C for 5-7 hours.

[0045] (3) Prepare an aqueous solution of 1 mg / L AgNO3 and mix it with transparent conductive ink at a ratio of 1:9. Weigh europium nano-aggregates and add them to the transparent conductive ink mixed with AgNO3. Stir thoroughly at room temperature for 2 hours to prepare a europium nano-aggregate doped conductive ink solution with a concentration of 0.75 mg / mL.

[0046] (4) The flexible transparent PET film coated with ITO was cleaned in an isopropanol solution using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment for 5-10 minutes to improve the adhesion of the substrate material.

[0047] (5) Place the cleaned flexible transparent PET film from step (4) on the substrate of the coating machine, start the scraper to coat a layer of europium nano-aggregate doped ZnO mixed solution prepared in step (1) as an electron transport layer, with a coating speed of 40 mm / s. After the coating is completed, place it on the heating table and anneal at 120 ℃ for 20 min.

[0048] (6) Add 1% by volume of 1,8-diiodooctane (DIO) to the donor-acceptor blend solution prepared in step (2) as an additive, continue stirring the blend solution for 30 minutes, and then coat the donor-acceptor blend solution onto the electron transport layer prepared in step (5) as an active layer film. The coating speed is 30 mm / s. After the coating is completed, anneal at 100°C for 15 minutes on a heating table.

[0049] (7) A mixed solution of PEDOT:PSS and molybdenum trioxide (mass ratio of PEDOT:PSS and molybdenum trioxide is 9:1) is coated onto the active layer film prepared in step (6) as a hole transport layer at a coating speed of 40 mm / s.

[0050] (8) The europium nano-aggregate doped conductive ink prepared in step (3) is scraped onto the surface of the hole transport layer prepared in step (7) as a transparent electrode. The scraping speed is 45 mm / s, and europium nano-aggregate doped flexible scraped polymer solar cell is obtained.

[0051] Compared with common solar cell devices, the europium nano-aggregate-doped flexible semi-transparent polymer solar cell prepared in this invention has a flexible substrate and high transparency, and can be fabricated on a large area. The performance parameters of the semi-transparent organic solar cell are shown in Table 1. Finally, the conversion efficiency of the europium nano-aggregate-doped flexible semi-transparent polymer solar cell reached 5.41%, while the average transmittance remained at 40.46%, and the light utilization rate reached 2.2%.

[0052] Example 7: Fabrication of terbium nanoclusters-doped flexible semi-transparent polymer solar cells (1) Weigh an appropriate amount of terbium nano-aggregate powder and ZnO and put them into a glass bottle. Add methanol as a solvent. The mass ratio of terbium nano-aggregate to ZnO is 1:19. Prepare a blended solution with a concentration of 1 mg / mL.

[0053] (2) Weigh the donor material PM6 and acceptor material Y6 of the polymer solar cell and put them into a glass bottle. Add chlorobenzene as a solvent. The mass ratio of PM6 to Y6 is 1:1.2. Prepare a blend solution with a concentration of 16 mg / mL. Heat and stir the blend solution at 45 °C for 5-7 hours.

[0054] (3) Prepare an aqueous solution of 1 mg / L AgNO3 and mix it with transparent conductive ink at a ratio of 1:9. Weigh rare earth terbium nanoparticles and add them to the mixed AgNO3 transparent conductive ink. Stir thoroughly at room temperature for 2 hours to prepare a terbium nanoparticle-doped conductive ink solution with a concentration of 0.75 mg / mL.

[0055] (4) The flexible transparent PET film coated with ITO was cleaned in an isopropanol solution using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment for 5-10 minutes to improve the adhesion of the substrate material.

[0056] (5) Place the cleaned flexible transparent PET film from step (4) on the substrate of the coating machine, start the scraper to coat a layer of terbium nano-aggregate doped ZnO mixed solution prepared in step (1) as an electron transport layer, with a scraping speed of 40 mm / s. After the coating is completed, place it on the heating table and anneal at 120 ℃ for 20 min.

[0057] (6) Add 1% by volume of 1,8-diiodooctane (DIO) as an additive to the donor-acceptor blend solution prepared in step (2), continue stirring the blend solution for 30 minutes, and then coat the donor-acceptor blend solution onto the electron transport layer prepared in step (5) at a coating speed of 30 mm / s. After coating, anneal at 100°C for 15 minutes on a heating stage.

[0058] (7) A mixed solution of PEDOT:PSS and molybdenum trioxide (mass ratio of PEDOT:PSS and molybdenum trioxide is 9:1) is coated onto the active layer film prepared in step (6) as a hole transport layer at a coating speed of 40 mm / s.

[0059] (8) The terbium nano-aggregate doped conductive ink prepared in step (3) is scraped onto the surface of the hole transport layer prepared in step (7) as a transparent electrode. The scraping speed is 45 mm / s, and the terbium nano-aggregate doped flexible scraped polymer solar cell is obtained.

[0060] The terbium nanoclusters-doped flexible semi-transparent polymer solar cell prepared in this invention has a flexible substrate and high transparency compared with common solar cell devices, and can be fabricated on a large area. The performance parameters of the semi-transparent organic solar cell are shown in Table 1. The conversion efficiency of the terbium nanoclusters-doped flexible semi-transparent polymer solar cell reaches 5.37%, while the average transmittance remains at 40.55%, and the light utilization rate reaches 2.2%.

[0061] Example 8: Fabrication of Samarium Nanoparticle-Doped Flexible Semi-Transparent Polymer Solar Cells (1) Weigh an appropriate amount of samarium nanoparticle powder and ZnO and put them into a glass bottle. Add methanol as a solvent. The mass ratio of samarium nanoparticles to ZnO is 1:19. Prepare a blended solution with a concentration of 1 mg / mL.

[0062] (2) Weigh the donor material PM6 and acceptor material Y6 of the polymer solar cell and put them into a glass bottle. Add chlorobenzene as a solvent. The mass ratio of PM6 to Y6 is 1:1.2. Prepare a blend solution with a concentration of 16 mg / mL. Heat and stir the blend solution at 45°C for 5-7 hours.

[0063] (3) Prepare an aqueous solution of 1 mg / L AgNO3 and mix it with transparent conductive ink at a ratio of 1:9. Weigh rare earth samarium nanoparticles and add them to the mixed AgNO3 transparent conductive ink. Stir thoroughly at room temperature for 2 hours to prepare a samarium nanoparticle-doped conductive ink solution with a concentration of 0.75 mg / mL.

[0064] (4) The flexible transparent PET film coated with ITO was cleaned in an isopropanol solution using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment for 5-10 minutes to improve the adhesion of the substrate material.

[0065] (5) Place the cleaned flexible transparent PET film from step (4) on the substrate of the coating machine, start the scraper to coat a layer of the samarium nano-aggregate doped ZnO mixed solution prepared in step (1) as an electron transport layer, with a scraping speed of 40 mm / s. After the coating is completed, place it on the heating table and anneal at 120 ℃ for 20 min.

[0066] (6) Add 1% by volume of 1,8-diiodooctane (DIO) as an additive to the donor-acceptor blend solution prepared in step (2), continue stirring the blend solution for 30 minutes, and then coat the donor-acceptor blend solution onto the electron transport layer prepared in step (5) at a coating speed of 30 mm / s. After coating, anneal at 100 °C for 15 minutes on a heating stage.

[0067] (7) A mixed solution of PEDOT:PSS and molybdenum trioxide (mass ratio of PEDOT:PSS and molybdenum trioxide is 9:1) is coated onto the active layer film prepared in step (6) as a hole transport layer at a coating speed of 40 mm / s.

[0068] (8) The samarium nano-aggregate doped conductive ink prepared in step (3) is scraped onto the surface of the hole transport layer prepared in step (7) as a transparent electrode. The scraping speed is 45 mm / s, and the samarium nano-aggregate doped flexible scraped polymer solar cell is obtained.

[0069] The samarium nano-aggregate-doped flexible semi-transparent polymer solar cell prepared in this invention has a flexible substrate and high transparency compared with common solar cell devices, and can be fabricated on a large area. The performance parameters of the semi-transparent organic solar cell are shown in Table 1. Finally, the conversion efficiency of the samarium nano-aggregate-doped flexible semi-transparent polymer solar cell reached 5.71%, while the average transmittance remained at 40.03% and the light utilization rate reached 2.3%.

[0070] Example 9: Europium-terbium-samarium nanoaggregates synergistic flexible semi-transparent polymer solar cells (1) Weigh europium nanoaggregate powder, terbium nanoaggregate, samarium nanoaggregate powder and ZnO in a mass ratio of 1:1:1:57 and put them into a glass bottle. Add methanol as a solvent to prepare a blended solution with a concentration of 1 mg / mL.

[0071] (2) Weigh the donor material PM6 and acceptor material Y6 of the polymer solar cell and put them into a glass bottle. Add chlorobenzene as a solvent. The mass ratio of PM6 to Y6 is 1:1.2. Prepare a blend solution with a concentration of 16 mg / mL. Heat and stir the blend solution at 45°C for 5-7 hours.

[0072] (3) Prepare an aqueous solution of 1 mg / L AgNO3 and mix it with transparent conductive ink in a ratio of 1:9. Weigh rare earth europium, terbium and samarium nanoaggregates and add them to the mixed AgNO3 transparent conductive ink in a ratio of 1:1:1. Stir thoroughly at room temperature for 2 hours to prepare a light energy conversion type high conductivity transparent electrode solution with a concentration of 0.75 mg / mL.

[0073] (4) The flexible transparent PET film coated with ITO was cleaned in an isopropanol solution using an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment for 5-10 minutes to improve the adhesion of the substrate material.

[0074] (5) Place the cleaned flexible transparent PET film from step (4) on the substrate of the coating machine, start the scraper to coat a layer of europium, terbium, and samarium nano-aggregates co-doped ZnO mixed solution prepared in step (1) as an electron transport layer, with a coating speed of 40 mm / s. After the coating is completed, place it on the heating table and anneal at 120°C for 20 min.

[0075] (6) Add 1% by volume of 1,8-diiodooctane (DIO) as an additive to the donor-acceptor blend solution prepared in step (2), continue stirring the blend solution for 30 minutes, and then coat the donor-acceptor blend solution onto the electron transport layer prepared in step (5) at a coating speed of 30 mm / s. After coating, anneal at 100°C for 15 minutes on a heating stage.

[0076] (7) A mixed solution of PEDOT:PSS and molybdenum trioxide (mass ratio of PEDOT:PSS and molybdenum trioxide is 9:1) is coated onto the active layer film prepared in step (6) as a hole transport layer at a coating speed of 40 mm / s.

[0077] (8) The europium terbium samarium nano-aggregate co-doped conductive ink prepared in step (3) is scraped onto the surface of the hole transport layer prepared in step (7) as a transparent electrode. The scraping speed is 45 mm / s, and europium terbium samarium nano-aggregate co-doped flexible scraped polymer solar cell is obtained.

[0078] The europium-samarium nanocluster co-doped flexible semi-transparent polymer solar cell prepared in this invention further improves the photoelectric conversion efficiency and light utilization rate compared to devices doped with single rare-earth nanoclusters, while maintaining high transparency. The performance parameters of the semi-transparent organic solar cell are shown in Table 1. Ultimately, the europium-terbium-samarium nanocluster co-doped flexible semi-transparent polymer solar cell achieves a photoelectric conversion efficiency of 6.09%, an average transmittance of 39.27%, and a light utilization rate of 2.4%. Compared to undoped devices and individually doped devices, both photoelectric conversion efficiency and light utilization rate are significantly improved. Furthermore, the calculated color rendering index (CRI) of this device is 90.3, exceeding the basic requirement of 80 for architectural lighting.

[0079] Table 1

[0080] It should be understood that those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing a polymer solar cell with synergistic enhancement of europium, terbium, and samarium nanoclusters, characterized in that, Polymer solar cells were fabricated by simultaneously doping rare-earth europium nanoclusters, rare-earth terbium nanoclusters, and rare-earth samarium nanoclusters into the ZnO electron transport layer and transparent electrode.

2. The preparation method according to claim 1, characterized in that, Preparation method of ZnO electron transport layer blend solution: rare earth europium nanopolymer powder, rare earth terbium nanopolymer powder, rare earth samarium nanopolymer powder and ZnO are mixed in a mass ratio of 1:1:1:57, and methanol is added as solvent to prepare a blend solution with a concentration of 1 mg / mL.

3. The preparation method according to claim 2, characterized in that, The preparation method of the rare earth europium nanopolymers, rare earth terbium nanopolymers, or rare earth samarium nanopolymers is as follows: Amphiphilic block polymers PS-b-PAA, europium chloride / terbium / samarium chloride, Phen, and aacac are taken in a molar ratio of 1:1:1:

3. DMF is added as the reaction solvent, and the mixture is placed in an oil bath at 60°C and reacted continuously for 6 hours to obtain a mixed solution of terbium nanopolymers. The reaction solution is washed with ethanol, centrifuged to remove the supernatant, and dried in a vacuum drying oven at 45°C for 8 hours to obtain rare earth europium / terbium / samarium nanopolymer powder.

4. The preparation method according to claim 3, characterized in that, Preparation of transparent electrode solution: Prepare a 1 mg / L AgNO3 aqueous solution and mix it with transparent conductive ink in a 1:9 ratio. Weigh rare earth europium, terbium, and samarium nanoaggregates and add them to the mixed AgNO3 transparent conductive ink in a ratio of (1-3):(1-3):(1-3). Stir thoroughly at room temperature for 2 hours to prepare a light energy conversion type highly conductive transparent electrode solution with a concentration of 0.75 mg / mL.

5. The preparation method according to claim 3, characterized in that, Specifically, the following steps are included: 1) The flexible conductive transparent substrate material was placed in an isopropanol solution and cleaned with an ultrasonic cleaner. After ultrasonic cleaning, the substrate was dried with a nitrogen gun and placed in an oxygen plasma cleaner for ultraviolet ozone treatment. 2) A layer of europium-terbium-samarium nanopolymer co-doped ZnO electron transport layer blend solution is coated onto a flexible conductive transparent film to obtain the electron transport layer, followed by annealing. 3) Coat the electron transport layer obtained in step 2) with an active layer solution composed of donor and acceptor polymers to obtain the active layer, and anneal it; after annealing, continue to coat the active layer with a hole transport layer. 4) Coat a layer of the transparent electrode solution onto the surface of the hole transport layer to complete the fabrication of europium, terbium, and samarium nanoclusters co-doped flexible semi-transparent polymer solar cells.

6. The preparation method according to claim 5, characterized in that, The flexible conductive transparent substrate material is a PET film or a PEN film coated with ITO.

7. The preparation method according to claim 4, characterized in that, The conductive ink is silver nanowires or a mixture of silver nanowires and a conductive polymer solution.

8. The preparation method according to claim 5, characterized in that, The hole transport layer is a solution formed from a PEDOT:PSS conductive polymer solution or other metal oxides.

9. The preparation method according to claim 5, characterized in that, The coating speed is 5-90 mm / s, and the annealing temperature is 70-120℃.

10. A polymer solar cell with synergistic enhancement of europium, terbium, and samarium nanoclusters prepared by any one of the methods described in claims 1-9.

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