Colored polymer solar cell with anti-reflection resonant cavity and preparation method thereof

Abstract

The invention discloses a color polymer solar cell with an anti-reflection resonant cavity and a preparation method thereof, and relates to the technical field of solar cells, the color polymer solar cell comprises a basic cell and the anti-reflection resonant cavity on the top layer of the basic cell, the anti-reflection resonant cavity comprises a resonant cavity structure and an anti-reflection layer on the top layer of the resonant cavity structure, the resonant cavity structure comprises a metal layer, a dielectric layer and a metal layer which are arranged in sequence, and the anti-reflection layer is an MgF2 layer; a metal / medium / metal / antireflection film structure is introduced to the top of the electrode, the metal and the top metal electrode jointly form a resonant cavity, transmission light near a specific wavelength can be selectively amplified, a sharp transmission peak is formed on a transmission spectrum, and the transmission effect is further improved by introducing the antireflection film structure. The optical length of the resonant cavity can be adjusted by adjusting the thickness of the dielectric layer, so that different transmission peaks are obtained, and cells with different colors are obtained.

Description

Technical Field

[0001] This invention relates to the field of solar cell technology, specifically to a colored polymer solar cell with an anti-reflection resonant cavity and its fabrication method. Background Technology

[0002] Polymer solar cells use polymer semiconductor materials as the active layer, offering significant advantages such as simple manufacturing, high flexibility, light weight, and adjustable bandgap, making them a typical representative of third-generation photovoltaic technology. With continuous technological advancements, the application of photovoltaic technology is no longer limited to traditional photovoltaic power generation. Building-integrated photovoltaics (BIPV) perfectly integrates photovoltaic cells with buildings, opening up new scenarios for next-generation integrated photovoltaic applications. However, traditional polymer solar cells are mostly black or dark blue, offering relatively limited color options and failing to meet the diverse color requirements of BIPV and decorative applications.

[0003] Currently, methods for realizing colored polymer solar cells encompass various approaches, including the synthesis of novel active layer donor-acceptor materials, the fabrication of ultrathin metal films, and the design of multilayer back mirror structures. However, these methods are complex in their fabrication processes, often sacrificing photoelectric conversion efficiency for high transmittance, making it difficult to effectively balance the relationship between transmission and photoelectric conversion, and limiting the range of color control. An optical Fabry-Perot resonator is a structure with optical enhancement effects, consisting of two metal layers and one dielectric layer. By adjusting the thickness of the dielectric layer in the resonator, resonance enhancement of specific wavelengths of light can be achieved, thereby forming specific transmission peaks in the transmission spectrum, which can be used to adjust the cell color when applied to solar cells. However, due to the light absorption effect of the intermediate dielectric, the resonant light suffers significant loss during multiple resonance processes, resulting in a transmittance of solar cells typically below 20%. To meet the technological demands of the building-integrated photovoltaics (BIPV) market, existing technologies still require further optimization. Therefore, a colored polymer solar cell with an anti-reflection resonator and its fabrication method are needed to address the aforementioned problems. Summary of the Invention

[0004] The purpose of this invention is to provide a colored polymer solar cell with an anti-reflection resonant cavity and a method for its fabrication, so as to solve the problems existing in the prior art mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A colored polymer solar cell with an anti-reflection resonant cavity includes a base cell and an anti-reflection resonant cavity on the top layer of the base cell, wherein the anti-reflection resonant cavity includes a resonant cavity structure and an anti-reflection layer on the top layer of the resonant cavity structure;

[0007] The resonant cavity structure includes a metal layer, a dielectric layer and a metal layer arranged sequentially, and the antireflection layer is a MgF2 layer.

[0008] Preferably, the base cell is a polymer solar cell, comprising a conductive glass substrate, an electron transport layer and a polymer arranged sequentially, wherein the polymer comprises a non-fullerene active layer and a hole transport layer arranged sequentially.

[0009] Preferably, the metal layer, the dielectric layer, and the metal layer are Ag / MgF2 / Ag layers in sequence, forming a resonant cavity structure, wherein the Ag film is both the anode of the battery and the high-reflectivity metal layer of the resonant cavity structure.

[0010] Preferably, the thickness of the dielectric layer and the antireflection layer is the same, both set to 80-140 nm.

[0011] A method for fabricating a colored polymer solar cell with an anti-reflection resonant cavity includes the following steps:

[0012] S1: Fabrication of the basic polymer solar cell;

[0013] S2: Place the base cell face down in a mask with electrode shapes, and put it into a glove box vacuum evaporation system. Evacuate the chamber until the vacuum level reaches 5*10⁻⁶. -4 When the pressure is below Pa, the baffle plate blocking the top of the silver powder to be evaporated is opened, and the powder is heated and evaporated at a rate of 0.01-0.03 nm / s, thus obtaining the first Ag film on the hole transport layer.

[0014] S3: Place the basic cell obtained in S2 face down in a mask with a resonant cavity shape, put it into a glove box vacuum evaporation system, and use the same vacuum evaporation method to evaporate the MgF2 dielectric layer and the second Ag film to obtain the basic resonant cavity structure.

[0015] S4: Further deposit a layer of MgF2 to obtain an anti-reflection resonant cavity structure.

[0016] Preferably, the specific steps of S1 are as follows:

[0017] S11: After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and set it aside for use.

[0018] S12: Weigh 1.6g of zinc acetate dihydrate using an electronic balance, dissolve it in 16ml of 2-methoxyethanol, transfer 440µL ​​of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20µL using a pipette and drop it onto the surface of the ITO substrate obtained in step S11, spin coat at 4000rpm for 60s in a glove box, and heat at 200℃ for 60min on an air hot stage to obtain a ZnO film with a thickness of approximately 25nm;

[0019] S13: Prepare a PM6:Y6 solution with a total concentration of 16 mg / ml and chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step S12. Spin for 40 s, let stand for 5 min, and then place it on a glove box hot stage at 80°C for 10 min for annealing. Allow it to cool naturally to room temperature to obtain a PM6:Y6 film with a thickness of 80 nm.

[0020] S14: Place the sample obtained in step S13 face down in a mask with a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 At Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.01 nm / s, and a MoO3 film is obtained on the sample.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] 1. This invention introduces a metal / dielectric / metal / antireflection film structure at the top of the electrode, wherein the metal and the top metal electrode together form a resonant cavity. Transmitted light near a specific wavelength can be selectively amplified, forming a sharp transmission peak on the transmission spectrum. The introduction of the antireflection film structure further enhances the transmission effect. In addition, by adjusting the thickness of the dielectric layer, the optical length of the resonant cavity can be adjusted, thereby obtaining different transmission peaks and batteries of different colors.

[0023] 2. The anti-reflection resonant cavity structure proposed in this invention can generate transmitted light with a narrow transmission spectrum. The remaining light outside the resonant transmitted light can still be reflected back into the battery and absorbed a second time. Therefore, this structure can achieve both high efficiency and high transmittance. Moreover, the anti-reflection resonant cavity structure is prepared by vapor deposition, which is a simple process. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the structure of the colored polymer solar cell of the present invention.

[0025] Figure 2The transmission spectra of polymer solar cells with resonant cavity (AMA) and anti-reflection resonant cavity (AMAM) provided by this invention are shown at different MgF2 material thicknesses.

[0026] Wherein: (a) is the transmission spectrum data of the polymer solar cell with MgF2 at 80 nm in the AMA structure resonant cavity in Example 1;

[0027] (b) is the transmission spectrum data of the polymer solar cell with two MgF2 layers of 80nm in the AMAM structure antireflection resonant cavity in Example 2;

[0028] (c) is the transmission spectrum data of the polymer solar cell with MgF2 at 100 nm in the AMA structure resonant cavity in Example 3;

[0029] (d) is the transmission spectrum data of the polymer solar cell with two MgF2 layers of 100nm in the AMAM structure antireflection resonant cavity in Example 4;

[0030] (e) shows the transmission spectrum data of the polymer solar cell with MgF2 at 120 nm in the AMA structure resonant cavity in Example 5;

[0031] (f) is the transmission spectrum data of the polymer solar cell with two MgF2 layers of 120nm in the AMAM structure antireflection resonant cavity in Example 6;

[0032] (g) is the transmission spectrum data of the polymer solar cell with MgF2 at 140 nm in the AMA structure resonant cavity in Example 7;

[0033] (h) is the transmission spectrum data of the polymer solar cell with two MgF2 layers of 140nm in the AMAM structure antireflection resonant cavity in Example 8.

[0034] Figure 3 These are the IPCE spectra of polymer solar cells with resonant cavity (AMA) and anti-reflection resonant cavity (AMAM) provided by the present invention at different MgF2 material thicknesses.

[0035] Figure 4 The integral current values ​​J of the IPCE spectrum of polymer solar cells with resonant cavity (AMA) and anti-reflection resonant cavity (AMAM) provided by this invention are obtained under different MgF2 material thicknesses.

[0036] Figure 5 These are the JV characteristic curves of polymer solar cells with resonant cavity (AMA) and anti-reflection resonant cavity (AMAM) provided by the present invention under different MgF2 material thicknesses.

[0037] Figure 6The coordinates of the CIE1931 chromaticity diagram obtained by calculation of the transmitted light from the anti-reflection resonant cavity (AMAM) provided by this invention;

[0038] Where: Point A is the CIE1931 color coordinate of the transmitted light of the polymer solar cell with two 80nm MgF2 layers in the AMAM structure anti-reflection resonant cavity of Example 2;

[0039] Point B represents the CIE1931 color coordinates of the transmitted light from the polymer solar cell with two 100nm MgF2 layers in the AMAM structure antireflection resonant cavity of Example 4.

[0040] Point C represents the CIE1931 color coordinates of the transmitted light from the polymer solar cell with two MgF2 layers of 120nm in the AMAM structure antireflection resonant cavity of Example 6.

[0041] Point D represents the CIE1931 color coordinates of the transmitted light from the polymer solar cell with two MgF2 layers of 140nm in the AMAM structure antireflection resonant cavity of Example 8.

[0042] In the figure: 1. Conductive glass substrate (ITO); 2. Electron transport layer (ZnO); 3. Non-fullerene active layer (PM6:Y6); 4. Hole transport layer (MoO3); 51. Metal layer (Ag); 52. Dielectric layer (MgF2); 53. Metal layer (Ag); 54. Antireflective layer (MgF2). Detailed Implementation

[0043] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is further described below in conjunction with specific implementation methods.

[0044] Please see Figure 1-6 The present invention provides the following technical solutions:

[0045] This invention uses a polymer solar cell as a substrate and fabricates an antireflective resonant cavity on the top layer. The polymer solar cell consists of a conductive glass substrate 1, an electron transport layer 2, a polymer:non-fullerene active layer 3, a hole transport layer 4, and an antireflective resonant cavity. The antireflective resonant cavity structure is metal, dielectric, metal, and antireflective film (Ag / MgF2 / Ag / MgF2). The first three layers (Ag / MgF2 / Ag) constitute the basic resonant cavity structure, and the fourth layer, MgF2, is the antireflective film. The first Ag film serves as both the anode of the solar cell and the high-reflectivity metal layer of the resonant cavity. The space between the two Ag films forms the basic resonant cavity structure. After light is transmitted through the cell, it enters the resonant cavity and resonates within the dielectric. Therefore, the intermediate dielectric layer uses MgF2 material with an extinction coefficient close to 0 and an extremely low refractive index (1.39). The resonance condition must satisfy the following formula:

[0046]

[0047] In the formula above, φ represents the phase difference caused by the reflection of light at the upper and lower Ag interfaces; m is a positive integer representing the order of the resonant cavity mode; n and d represent the refractive index and thickness of the intermediate dielectric layer, respectively. It is evident that the resonant wavelength of the resonant cavity is extremely sensitive to the optical parameters and thickness of the dielectric. Therefore, by controlling the characteristics of the intermediate dielectric layer, different transmission peaks can be achieved, thereby flexibly adjusting the color of the polymer solar cell.

[0048] This invention proposes to introduce a top-layer antireflection film MgF2 at the top of the resonant cavity. When the film thickness is one-quarter of the wavelength of the incident light in the film, the optical path difference of the reflected light at the two interfaces is λ / 2 (i.e., the phase difference is π), which will form an interference destructive condition, thereby significantly reducing the reflectivity and further improving the transmission peak performance of the resonant cavity.

[0049] Example 1

[0050] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0051] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0052] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml and chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in the glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, place for 5 min, and then place on the glove box hot stage at 80 °C for 10 min for annealing. Allow it to cool naturally to room temperature to obtain a PM6:Y6 film with a thickness of 80 nm.

[0053] (4) Place the sample obtained in step (3) face down in the mask of the specific electrode pattern of the vacuum evaporation system. When the cavity pressure is lower than 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.01nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0054] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0055] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern. When the cavity pressure is below 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.1 nm / s, and an 80 nm thick MgF2 film is obtained on (5).

[0056] (7) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0057] The above steps completed the fabrication of a polymer solar cell with an AMA resonant cavity structure of 80 nm thick MgF2.

[0058] Example 2

[0059] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0060] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0061] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml and chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in the glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, place for 5 min, and then place on the glove box hot stage at 80 °C for 10 min for annealing. Allow it to cool naturally to room temperature to obtain a PM6:Y6 film with a thickness of 80 nm.

[0062] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.03nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0063] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0064] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern, and re-evacuate the vacuum. When the cavity pressure is lower than 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.1 nm / s, and an 80 nm thick MgF2 film is obtained on (5).

[0065] (7) Open the baffle plate on top of the silver powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0066] (8) Open the baffle plate on top of the MgF2 powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.3nm / s, and an 80nm thick MgF2 anti-reflection layer film is obtained on (7).

[0067] The above steps completed the fabrication of a polymer solar cell with an AMAM resonant cavity structure of 80 nm thick MgF2.

[0068] Example 3

[0069] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0070] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0071] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml and chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in the glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, place for 5 min, and then place on the glove box hot stage at 80 °C for 10 min for annealing. Allow it to cool naturally to room temperature to obtain a PM6:Y6 film with a thickness of 80 nm.

[0072] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.02nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0073] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0074] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern. When the cavity pressure is below 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.3 nm / s, and a 100 nm thick MgF2 film is obtained on (5).

[0075] (7) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0076] The above steps completed the fabrication of a polymer solar cell with an AMA resonant cavity structure of 100 nm thick MgF2.

[0077] Example 4

[0078] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0079] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0080] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml, using chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, let stand for 5 min, and then place it on a glove box hot plate at 80°C for 10 min for annealing. After naturally cooling to room temperature, a PM6:Y6 film with a thickness of 80 nm is obtained.

[0081] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.03nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0082] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0083] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern, and re-evacuate the vacuum. When the cavity pressure is lower than 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.1 nm / s, and a 100 nm thick MgF2 film is obtained on (5).

[0084] (7) Open the baffle plate on top of the silver powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0085] (8) Open the baffle plate blocking the top of the MgF2 powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.1nm / s, and a 100nm thick MgF2 antireflection layer film is obtained on (7).

[0086] The above steps completed the fabrication of a polymer solar cell with an AMAM resonant cavity structure of 100 nm thick MgF2.

[0087] Example 5

[0088] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0089] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0090] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml, using chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, let stand for 5 min, and then place it on a glove box hot plate at 80°C for 10 min for annealing. After naturally cooling to room temperature, a PM6:Y6 film with a thickness of 80 nm is obtained.

[0091] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.02nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0092] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0093] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern. When the cavity pressure is below 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.3 nm / s, and a 120 nm thick MgF2 film is obtained on (5).

[0094] (7) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0095] The above steps completed the fabrication of a polymer solar cell with an AMA resonant cavity structure of 120 nm thick MgF2.

[0096] Example 6

[0097] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0098] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0099] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml, using chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, let stand for 5 min, and then place it on a glove box hot plate at 80°C for 10 min for annealing. After naturally cooling to room temperature, a PM6:Y6 film with a thickness of 80 nm is obtained.

[0100] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.03nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0101] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0102] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern, and re-evacuate the vacuum. When the cavity pressure is lower than 5 × 10⁻⁶, -4When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.2nm / s, and a 120nm thick MgF2 film is obtained on (5).

[0103] (7) Open the baffle plate on top of the silver powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.03nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0104] (8) Open the baffle plate blocking the top of the MgF2 powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.1nm / s, and a 120nm thick MgF2 anti-reflection layer film is obtained on (7).

[0105] The above steps completed the fabrication of a polymer solar cell with an AMAM resonant cavity structure of 120 nm thick MgF2.

[0106] Example 7

[0107] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0108] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0109] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml, using chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, let stand for 5 min, and then place it on a glove box hot plate at 80°C for 10 min for annealing. After naturally cooling to room temperature, a PM6:Y6 film with a thickness of 80 nm is obtained.

[0110] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.03nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0111] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.03nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0112] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern. When the cavity pressure is below 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.3 nm / s, and a MgF2 film with a thickness of 140 nm is obtained on (5).

[0113] (7) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0114] The above steps completed the fabrication of a polymer solar cell with an AMA resonant cavity structure of 140 nm thick MgF2.

[0115] Example 8

[0116] (1) After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and then use it.

[0117] (2) Weigh 1.6 g of zinc acetate dihydrate using an electronic balance, dissolve it in 16 ml of 2-methoxyethanol, transfer 440 μL of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20 μL using a pipette and drop it onto the surface of the ITO substrate obtained in step (1), rotate the spin coater at 4000 rpm for 60 s in a glove box, and heat it at 200 °C for 60 min on a hot stage in air to obtain a ZnO film with a thickness of about 25 nm.

[0118] (3) Prepare a PM6:Y6 solution (1:1.2) with a total concentration of 16 mg / ml, using chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step (2). Spin for 40 s, let stand for 5 min, and then place it on a glove box hot plate at 80°C for 10 min for annealing. After naturally cooling to room temperature, a PM6:Y6 film with a thickness of 80 nm is obtained.

[0119] (4) Place the sample obtained in step (3) face down in a mask of a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 When Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.01nm / s, and a 10nm thick MoO3 film is obtained on (3).

[0120] (5) Open the baffle at the top of the silver powder to be evaporated, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.01nm / s, and a 35nm thick Ag electrode is obtained on (4).

[0121] (6) Transfer the sample obtained in step (5) downwards into a mask with a resonant cavity pattern, and re-evacuate the vacuum. When the cavity pressure is lower than 5 × 10⁻⁶, -4 When Pa, the baffle plate blocking the top of the MgF2 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.1 nm / s, and a MgF2 film with a thickness of 140 nm is obtained on (5).

[0122] (7) Open the baffle plate on top of the silver powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.02nm / s, and a 35nm thick Ag mirror is obtained on (6).

[0123] (8) Open the baffle plate on top of the MgF2 powder to be evaporated again, turn on the evaporation source to heat and evaporate, the evaporation rate is 0.3nm / s, and a 140nm thick MgF2 anti-reflection layer film is obtained on (7).

[0124] The above steps completed the fabrication of a polymer solar cell with an AMAM resonant cavity structure of 140 nm thick MgF2.

[0125] The performance parameters of polymer solar cells with resonant cavity (Ag / MgF2 / Ag, hereinafter referred to as AMA structure) and anti-reflection resonant cavity (Ag / MgF2 / Ag / MgF2, hereinafter referred to as AMAM structure) involved in this invention at different MgF2 material thicknesses (80nm, 100nm, 120nm and 140nm), including short-circuit current (Jsc), open-circuit voltage (Voc), fill factor (FF), power conversion efficiency (PCE), peak transmittance (AVT) and peak light utilization (LUEtop), are detailed in the table below:

[0126]

[0127] These photoelectric performance parameters are based on AM 1.5G simulated sunlight (100mW / cm²). 2The results were measured under irradiation. In this invention, the thickness of the first MgF2 layer was set to 80nm, 100nm, 120nm to 140nm respectively; to enhance the transmission effect of the resonant light transmission peak, the thickness of the second antireflective film MgF2 was kept consistent with that of the first layer. As can be seen from the data in the table, the antireflective resonant cavity structure provided by this invention enables polymer solar cells to achieve a high transmission peak of 42.6%, at which point the photoelectric conversion efficiency of the cell can reach as high as 13.45%, and the peak light utilization rate can reach 5.73%. These figures are leading in the relevant field. Therefore, this invention proposes a technical solution to improve the transmittance of polymer solar cells through an antireflective resonant cavity. This solution improves transmittance while having minimal impact on the light absorption of the cell, ensuring the photoelectric conversion efficiency of the cell. Furthermore, by adjusting the thickness of the intermediate dielectric layer, the output of different transmission peaks can be controlled, thereby adjusting the color of the polymer solar cell.

[0128] like Figure 2 As shown in the transmission spectra at different MgF2 material thicknesses, it can be seen that the transmission peak redshifts with the increase of MgF2 thickness, and the transmission peak of the AMAM antireflection resonant cavity structure battery is significantly improved compared with the AMA structure after the addition of the antireflection layer.

[0129] like Figure 3 As shown, the transmission peak of the resonant cavity directly causes the photoelectric conversion loss, and a significant decrease is observed at the corresponding transmission peak position in the IPCE spectrum. With the increase of thickness, the IPCE concave peak gradually red-shifts in the spectrum, where the structures (a)-(h) are the same as... Figure 2 .

[0130] like Figure 4 As shown, it can be seen that, for the same MgF2 thickness, the integral current of the AMAM structure is slightly lower than that of the AMA structure. This is because the antireflection film enhances the transmission peak, resulting in a decrease in absorbable light at the corresponding peak. This value is consistent with... Figure 2 The peak values ​​of the transmission spectrum in the image are consistent.

[0131] like Figure 5 As shown, the photocurrent density Jsc and Figure 3 The trends of the maximum integral current Jmax are basically consistent. Furthermore, the differences in the maximum integral current Jmax among different devices are minimal. Although each transmission peak causes a slight decrease in light absorption, the light loss is relatively small due to the extremely narrow transmission peaks, thus effectively ensuring the photoelectric conversion efficiency of the battery. It is worth mentioning that both the AMA resonant cavity and the AMAM anti-reflection resonant cavity are additional structures added to the top electrode, having no significant impact on the battery's energy levels and transport, thereby keeping the open-circuit voltage and fill factor essentially unchanged.

[0132] like Figure 6As shown in the figure, the chromaticity coordinates exhibit a clockwise color change with different MgF2 thicknesses, transitioning from blue to green, and then to yellow and red. The colors in the chromaticity diagram further verify the effectiveness of the resonant cavity in spectral control. By adjusting the thickness of the MgF2 material, different colored batteries can be achieved.

[0133] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A colored polymer solar cell with an anti-reflection resonant cavity, characterized in that, The resonant cavity includes a base cell and an anti-reflection resonant cavity on the top layer of the base cell. The anti-reflection resonant cavity includes a resonant cavity structure and an anti-reflection layer (54) on the top layer of the resonant cavity structure. The resonant cavity structure includes a metal layer (51), a dielectric layer (52) and a metal layer (53) arranged sequentially, and the anti-reflection layer (54) is a MgF2 layer.

2. A colored polymer solar cell with an anti-reflection resonant cavity according to claim 1, characterized in that: The base cell is a polymer solar cell, comprising a conductive glass substrate (1), an electron transport layer (2), and a polymer arranged sequentially, wherein the polymer comprises a non-fullerene active layer (3) and a hole transport layer (4) arranged sequentially.

3. A colored polymer solar cell with an anti-reflection resonant cavity according to claim 1, characterized in that: The metal layer (51), dielectric layer (52) and metal layer (53) are Ag / MgF2 / Ag layers in sequence, forming a resonant cavity structure. The Ag film is both the anode of the battery and the high-reflectivity metal layer of the resonant cavity structure.

4. A colored polymer solar cell with an anti-reflection resonant cavity according to claim 2, characterized in that: The dielectric layer (52) and the antireflective layer (54) have the same thickness, both set to 80-140 nm.

5. A method for fabricating a color polymer solar cell with an anti-reflection resonant cavity according to any one of claims 1-4, characterized in that, Includes the following steps: S1: Fabrication of the basic polymer solar cell; S2: Place the base cell face down in a mask with electrode shapes, and put it into a glove box vacuum evaporation system. Evacuate the chamber until the vacuum level reaches 5*10⁻⁶. -4 When the pressure is below Pa, the baffle plate blocking the top of the silver powder to be evaporated is opened, and the powder is heated and evaporated at a rate of 0.01-0.03 nm / s, thus obtaining the first Ag film on the hole transport layer. S3: Place the basic cell obtained in S2 face down in a mask with a resonant cavity shape, put it into a glove box vacuum evaporation system, and use the same vacuum evaporation method to evaporate the MgF2 dielectric layer and the second Ag film to obtain the basic resonant cavity structure. S4: Further deposit a layer of MgF2 to obtain an anti-reflection resonant cavity structure.

6. The method for fabricating a color polymer solar cell with an anti-reflection resonant cavity according to claim 5, characterized in that, The specific steps of S1 are as follows: S11: After cleaning the ITO electrode with the etched pattern with detergent, rinse it with water and place it on a polytetrafluoroethylene cleaning rack. Then, put it into beakers of deionized water, ethanol and isopropanol in sequence, sonicate each for 15 minutes, blow it dry with a nitrogen gun, treat it with ultraviolet ozone and set it aside for use. S12: Weigh 1.6g of zinc acetate dihydrate using an electronic balance, dissolve it in 16ml of 2-methoxyethanol, transfer 440µL ​​of ethanolamine to the above solution using a pipette, stir at room temperature for 24 hours, age for 48 hours, extract 20µL using a pipette and drop it onto the surface of the ITO substrate obtained in step S11, spin coat at 4000rpm for 60s in a glove box, and heat at 200℃ for 60min on an air hot stage to obtain a ZnO film with a thickness of approximately 25nm; S13: Prepare a PM6:Y6 solution with a total concentration of 16 mg / ml and chloroform as the solvent. Using a dynamic spin coating method, when the spin coater speed reaches 4000 rpm in a glove box, use a pipette to extract 20 μL and drop it onto the ITO / ZnO surface obtained in step S12. Spin for 40 s, let stand for 5 min, and then place it on a glove box hot stage at 80°C for 10 min for annealing. Allow it to cool naturally to room temperature to obtain a PM6:Y6 film with a thickness of 80 nm. S14: Place the sample obtained in step S13 face down in a mask with a specific electrode pattern in the vacuum evaporation system. When the chamber pressure is below 5 × 10⁻⁶... -4 At Pa, the baffle plate blocking the top of the MoO3 powder to be evaporated is opened, the evaporation source is turned on to heat and evaporate, the evaporation rate is 0.01 nm / s, and a MoO3 film is obtained on the sample.

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