A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive

Abstract

The present invention discloses a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. 1,3,5-tribromobenzene (TBB) is used as a novel solid additive with high volatility and low cost. The method utilizes a continuous deposition method in combination with thermal annealing to regulate the morphology of the photoactive layer thin film of the cell. Introduction of the TBB additive into the acceptor L8-BO further promotes the self-assembly of the L8-BO, thereby facilitating the formation of a photoactive layer morphology with finer phase separation and higher crystallinity. This effectively improves the charge injection efficiency of the cell, enables faster and more balanced carrier transport, and suppresses carrier recombination. The prepared organic solar cell has a device structure of Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag. Compared to the efficiency of a control cell (17.2%) (average efficiency 16.7%), the synergistic effect of the additive and the continuous deposition method enables the efficiency of the D18-Cl / L8-BO (TBB+TA) cell to reach 18.5% (average efficiency 18.1%), effectively improving the cell efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of solar cell photoactive layer films, and in particular to a method for constructing an organic solar cell photoactive layer film using a solid additive. Background Art

[0002] Solar cells are devices that directly convert light energy into electrical energy through the photoelectric or photochemical effects. As long as they are exposed to light, they can instantly output voltage and current. In physics, this is known as solar photovoltaics (PV). Thin-film solar cells based on the photoelectric effect are the mainstream, while wet-type solar cells based on the photochemical effect are still in their infancy. Solar cells can be divided into two categories based on their crystal state: crystalline thin-film solar cells and amorphous thin-film solar cells. The former is further divided into single-crystalline and polycrystalline types. Based on the material, they can be divided into silicon thin-film solar cells, compound semiconductor thin-film solar cells, and organic film solar cells. Compound semiconductor thin-film solar cells are further divided into amorphous, Group IIIV, Group IIVI, and zinc phosphide types. Based on the materials used, solar cells can be further divided into silicon solar cells, multi-component compound thin-film solar cells, polymer multilayer modified electrode solar cells, nanocrystalline solar cells, organic solar cells, and plastic solar cells. Silicon solar cells are currently the most mature and dominate in applications. Organic solar cells (OSCs) have attracted widespread attention due to their high flexibility, lightweight, and large-area fabrication capabilities. However, organic solar cells still face the problems of insufficient battery performance and high production costs. How to prepare organic solar cell devices with higher efficiency and lower cost remains a research focus. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive with higher cell efficiency and lower production cost.

[0004] To achieve the above-mentioned object, the technical solution adopted by the present invention is as follows: A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0005] (1) ITO substrate pretreatment:

[0006] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol in sequence to obtain an ultrasonically cleaned ITO substrate;

[0007] 1.2) Drying: The ultrasonically cleaned ITO substrate prepared in step 1.1) is then placed in a UV-ozone cleaning chamber for treatment, removed, and stored in isopropyl alcohol to obtain a wetted ITO substrate. This pretreatment of the ITO substrate can make the ITO surface more wettable and also adjust its hydrophobicity and work function, facilitating spin coating of the photoactive layer solution.

[0008] (2) Preparation of hole transport layer PEDOT:PSS:

[0009] 2.1) Before use, PEDOT:PSS was filtered using a PVDF water filter and then spin-coated onto the soaked ITO substrate to obtain a PEDOT:PSS-coated ITO substrate.

[0010] 2.2) Anneal the PEDOT:PSS-coated ITO substrate at 140-160°C for 15-25 min, then transfer it to a glove box and cool it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0011] (3) Configure the donor and recipient in the glove box:

[0012] 3.1) In a glove box, prepare a 10-20 mg / mL TBB solution in chloroform.

[0013] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) with the concentration of the L8-BO solution controlled between 7.5 and 9 mg / mL to obtain an acceptor solution;

[0014] 3.3) Add the polymer donor D18-Cl solid to chloroform, controlling the D18-Cl solution concentration to 6-7 mg / mL to obtain a donor solution.

[0015] 3.4) Stirring the receptor solution and donor solution at a constant temperature of 40-60°C to obtain a pretreated receptor solution and a pretreated donor solution;

[0016] (4) Spin coating:

[0017] 4.1) Spin-coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Then, spin-coat the pretreated acceptor solution to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0018] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 70-85°C for 4-6 minutes to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0019] 4.3) Spin-coat the PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN.

[0020] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 90~110 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0021] Furthermore, in the step 1.1), the ITO substrate is ultrasonically cleaned for 10 to 20 minutes using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol in sequence to obtain an ultrasonically cleaned ITO substrate.

[0022] Furthermore, in step 1.2), the ultrasonically cleaned ITO substrate prepared in step 1.1) is quickly dried with high-pressure nitrogen, then placed in a UV-ozone cleaning chamber for 20-30 minutes, taken out, and stored in isopropyl alcohol to obtain a wetted ITO substrate.

[0023] Furthermore, before use in step 2.1), the PEDOT:PSS is first filtered with a PVDF water filter with a pore size of 0.45 μm and a diameter of 13 mm, and then spin-coated on the soaked ITO substrate at a rate of 4000-5000 rpm / 20 seconds to obtain an ITO substrate coated with PEDOT:PSS.

[0024] Furthermore, in step 2.2), the ITO substrate coated with PEDOT:PSS is annealed at 150-160° C. for 20-25 min, and then transferred to a glove box and cooled to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS.

[0025] Furthermore, in step 3.1), a 15-20 mg / mL TBB solution is prepared in a glove box, and the solvent of the TBB solution is chloroform.

[0026] Furthermore, in step (4), the spin coating rate of the pre-treated donor solution is 4000-5500 rpm / 30 seconds, the spin coating rate of the pre-treated acceptor solution is 3500-4500 rpm / 30 seconds, and the spin coating rate of the PDIN solution is 4500-5500 rpm / 20 seconds.

[0027] Furthermore, in step 4.2), the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO is annealed at 75-85° C. for 5-6 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0028] Furthermore, the solvent of the PDIN solution in step (4) is methanol, the concentration of PDIN in the PDIN solution is 2.0 mg / mL, and 0.3 vol% of acetic acid is added at the same time.

[0029] Furthermore, in step (5), Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN is thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber is controlled to be maintained below 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100~110 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0030] The present invention discloses a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. The method effectively regulates the phase separation and molecular crystallinity of the active layer through a continuous deposition method assisted by a highly volatile solid additive, thereby regulating the morphology of the photoactive layer of the organic solar cell to form a photoactive layer morphology with finer phase separation and higher crystallinity, effectively improving the charge injection efficiency of the cell, obtaining faster and more balanced carrier transport, suppressing carrier recombination, and thereby improving cell efficiency.

[0031] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive, using 1,3,5-tribromobenzene (abbreviated as TBB) as a new solid additive with high volatility and low cost, and combining it with thermal annealing. Annealing (abbreviated as TA) was used to control the morphology of the cell's photoactive layer film by continuous deposition, and a high-efficiency organic solar cell with a structure of Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag was prepared. The changes in the vertical phase separation and molecular crystallinity of the cell's photoactive layer were revealed. After the additive TBB was introduced into the acceptor L8-BO, the self-assembly of L8-BO was further promoted, thereby helping to form a photoactive layer morphology with finer phase separation and higher crystallinity. The charge injection efficiency of the cell was effectively improved, the carrier transport was faster and more balanced, and the carrier recombination was suppressed. Compared with the efficiency of the control cell of 17.2%, the synergistic effect of the additive and the continuous deposition method made the efficiency of the D18-Cl / L8-BO (TBB+TA) cell reach 18.5%, which is the current open circuit voltage ( V OC ) is one of the highest efficiencies of binary organic solar cells with a voltage drop of over 900 mV; in addition, the efficiencies of 20 devices were also counted, and the results showed that the average efficiency of the devices increased from 16.7% to 18.1%.

[0032] The outstanding advantages of the present invention are: (1) a simpler and more effective method is used to facilitate the preparation of high-efficiency organic solar cells. The device preparation method is simple and practical, the solid additive is highly volatile and inexpensive (100 yuan for 100 g), and annealing is performed at 75°C for 5 minutes (liquid additives are generally annealed at 100°C for 10 minutes); (2) 1,3,5-tribromobenzene (abbreviated as TBB) is used as a new solid additive with high volatility and low cost (note: it has not been used in organic solar cells), and combined with thermal annealing (abbreviated as TA), the morphology of the cell photoactive layer film is controlled by a continuous deposition method, thereby significantly improving the device efficiency.

[0033] Figures in the specification

[0034] Figure 1 It is a schematic diagram of vertical phase separation and molecular crystallization of the photoactive layer of the battery of the present invention.

[0035] Figure 2 It is a chemical structure and analysis result diagram of the composition of the present invention; Figure 2Middle: (a) Chemical structures of the polymer donor D18-Cl, the non-fullerene acceptor L8-BO, and the solid additive 1,3,5-tribromobenzene (abbreviated as TBB); (b) Energy level diagram of D18-Cl and L8-BO; (c) Absorption spectra of the untreated pure film and the mixed film prepared by sequential deposition; (d) Photoluminescence spectrum.

[0036] Figure 3 1 is a graph showing test results of the present invention; Figure 3 Middle: (a) Short-circuit current density-open-circuit voltage ( JV ) characteristic curve; (b) external quantum efficiency (EQE) spectrum; (c) transient photocurrent test (TPC) spectrum; (d) transient photovoltage test (TPV) spectrum; (e) charge carrier density and delay time spectra of Control, TBB and TBB+TA devices composed of D18-Cl / L8-BO; the solid lines in the figure are the fitting of the experimental data. The charge injection efficiency of the TBB+TA device is effectively improved, the carrier transport is faster and more balanced, and the carrier recombination is suppressed.

[0037] Figure 4 Graph showing the dark current experimental results of the Control, TBB, and TBB+TA devices composed of D18-Cl / L8-BO according to the present invention.

[0038] Figure 5 These are AFM height images and AFM phase images of the active layers of the Control, TBB, and TBB+TA devices composed of D18-Cl / L8-BO according to the present invention, obtained using an atomic force microscope (AFM).

[0039] Figure 6 These are Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS) and Transmission Electron Microscope (TEM) images of the active layers of the Control, TBB, and TBB+TA devices composed of D18-Cl / L8-BO. DETAILED DESCRIPTION

[0040] The following examples may help those skilled in the art to more fully understand the present invention, but shall not limit the present invention in any way.

[0041] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. The parameters in the glove box are controlled to be: oxygen content <10 ppm; water content <0.1 ppm.

[0042] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. The PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany) used was purchased from Xi'an Biolight Optoelectronics Technology Co., Ltd.

[0043] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. The cleaning solution used in step 1.1) of the following embodiment is a detergent aqueous solution, but the cleaning solution is not limited to a detergent aqueous solution. Cleansers similar to detergent aqueous solutions can also be used.

[0044] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell with a solid additive. Figure 5 and Figure 6 It is a commonly used spectrum to characterize the morphology of the active layer. Figure 5 、 Figure 6 The test results show that the photoactive layer of the TBB+TA device composed of D18-Cl / L8-BO prepared by the present invention has a finer phase separation and higher crystallinity. It can also be seen that compared with the efficiency of the control cell of 17.2%, the synergistic effect of the additive and the continuous deposition method makes the efficiency of the D18-Cl / L8-BO (TBB+TA) cell reach 18.5%, which is the highest open circuit voltage ( V OC ) exceeds 900 mV, achieving one of the highest efficiencies for binary organic solar cells.

[0045] The present invention discloses a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive. The statistical results of 20 devices show that the average device efficiency increased from 16.7% to 18.1%. Specifically, under AM 1.5G simulation conditions, the parameters of the control group, TBB, and TBB+TA OSCs, irradiance (100 mW cm -2 ), the average value and standard deviation (in brackets) are from 20 independent devices. The experimental results are shown in Table 1 below:

[0046] Table 1

[0047]

[0048] The analysis parameters of the forward bias portion of the dark current were fitted using the diode equation. The results are shown in Table 2 below:

[0049] Table 2

[0050]

[0051] Example 1

[0052] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0053] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0054] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 10 min each to obtain an ultrasonically cleaned ITO substrate;

[0055] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 20 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0056] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0057] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4000 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0058] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 140°C for 15 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0059] (3) Configure the donor and recipient in the glove box:

[0060] 3.1) In a glove box, prepare a 10 mg / mL TBB solution in chloroform. Stir the TBB solution (chloroform) at room temperature for 20 min before use.

[0061] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) at a concentration of 7.5 mg / mL to obtain an acceptor solution;

[0062] 3.3) Add the polymer donor D18-Cl solid to the chloroform solution, controlling the D18-Cl solution concentration to 6 mg / mL, to obtain a donor solution.

[0063] 3.4) Stirring the receptor solution and donor solution at 40°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0064] (4) Spin coating:

[0065] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 5000 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Then, using a pipette, spin coat the pretreated acceptor solution at 3500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0066] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 70°C for 4 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0067] 4.3) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at a rate of 5000 rpm for 20 seconds to obtain a Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN solution. The PDIN concentration in the methanol solution is 2.0 mg / mL, and 0.3 vol% acetic acid is added. After completing the above steps, use a blade to scrape off a small portion of the ends of the ITO to facilitate the thermal evaporation of the Ag electrode.

[0068] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0069] Example 2

[0070] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0071] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0072] 1.1) Ultrasonic cleaning an ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 20 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0073] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0074] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0075] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 5000 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0076] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 160°C for 25 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0077] (3) Configure the donor and recipient in the glove box:

[0078] 3.1) In a glove box, prepare a 20 mg / mL TBB solution (chloroform). Stir the TBB solution at room temperature for 20 min before use.

[0079] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) at a concentration of 9 mg / mL to obtain an acceptor solution;

[0080] 3.3) Add the polymer donor D18-Cl solid to the chloroform solution, controlling the D18-Cl solution concentration to 7 mg / mL, to obtain a donor solution;

[0081] 3.4) Stirring the receptor solution and the donor solution at 60°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0082] (4) Spin coating:

[0083] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 5000 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Then, using a pipette, spin coat the pretreated acceptor solution at 3800 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0084] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 85°C for 6 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0085] 4.3) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ends of the ITO to facilitate the thermal evaporation of the Ag electrode.

[0086] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0087] Example 3

[0088] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0089] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0090] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0091] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0092] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0093] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4500 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0094] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0095] (3) Configure the donor and recipient in the glove box:

[0096] 3.1) In a glove box, prepare a 15 mg / mL TBB solution (chloroform). Stir the TBB solution at room temperature for 20 min before use.

[0097] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) at a concentration of 8.5 mg / mL to obtain an acceptor solution;

[0098] 3.3) Add the polymer donor D18-Cl solid to the chloroform solution, controlling the D18-Cl solution concentration to 6.5 mg / mL to obtain a donor solution.

[0099] 3.4) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0100] (4) Spin coating:

[0101] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Next, spin coat the pretreated acceptor solution at 4000 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0102] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 75°C for 5 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0103] 4.3) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ITO ends to facilitate the thermal evaporation of the Ag electrodes.

[0104] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0105] Example 4

[0106] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0107] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0108] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0109] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0110] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0111] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4300 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0112] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0113] (3) Configure the donor and recipient in the glove box:

[0114] 3.1) In a glove box, prepare a 15 mg / mL TBB solution (chloroform). Stir the TBB solution at room temperature for 20 min before use.

[0115] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) at a concentration of 8.5 mg / mL to obtain an acceptor solution;

[0116] 3.3) Add the polymer donor D18-Cl solid to the chloroform solution, controlling the D18-Cl solution concentration to 6.5 mg / mL to obtain a donor solution.

[0117] 3.4) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0118] (4) Spin coating:

[0119] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Next, spin coat the pretreated acceptor solution at 4300 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0120] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 75°C for 5 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0121] 4.3) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 4500 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ITO ends to facilitate thermal evaporation of the Ag electrode.

[0122] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0123] Example 5

[0124] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0125] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0126] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0127] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0128] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0129] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4500 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0130] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0131] (3) Configure the donor and recipient in the glove box:

[0132] 3.1) In a glove box, prepare a 15 mg / mL TBB solution (chloroform). Stir the TBB solution at room temperature for 20 min before use.

[0133] 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) at a concentration of 8.5 mg / mL to obtain an acceptor solution;

[0134] 3.3) Add the polymer donor D18-Cl solid to the chloroform solution, controlling the D18-Cl solution concentration to 6.5 mg / mL to obtain a donor solution.

[0135] 3.4) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0136] (4) Spin coating:

[0137] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Next, spin coat the pretreated acceptor solution at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0138] 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 75°C for 5 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO;

[0139] 4.3) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ITO ends to facilitate the thermal evaporation of the Ag electrodes.

[0140] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0141] Comparative Example 1

[0142] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0143] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0144] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0145] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0146] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0147] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4500 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0148] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0149] (3) Configure the donor and recipient in the glove box:

[0150] 3.1) Add the non-fullerene acceptor L8-BO solid to chloroform, controlling the concentration of the L8-BO solution to 8.5 mg / mL, to obtain an acceptor solution.

[0151] 3.2) Add the polymer donor D18-Cl solid to chloroform, controlling the D18-Cl solution concentration to 6.5 mg / mL, to obtain a donor solution.

[0152] 3.3) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0153] (4) Spin coating:

[0154] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Then, using a pipette, spin coat the pretreated acceptor solution at 3500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0155] 4.2) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at a rate of 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ends of the ITO to facilitate the thermal evaporation of the Ag electrode.

[0156] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0157] Comparative Example 2

[0158] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0159] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0160] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0161] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0162] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0163] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4500 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0164] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0165] (3) Configure the donor and recipient in the glove box:

[0166] 3.1) Add the non-fullerene acceptor L8-BO solid to chloroform, controlling the concentration of the L8-BO solution to 8.5 mg / mL, to obtain an acceptor solution.

[0167] 3.2) Add the polymer donor D18-Cl solid to chloroform, controlling the D18-Cl solution concentration to 6.5 mg / mL, to obtain a donor solution.

[0168] 3.3) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0169] (4) Spin coating:

[0170] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Next, spin coat the pretreated acceptor solution at 4000 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0171] 4.2) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at a rate of 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ends of the ITO to facilitate the thermal evaporation of the Ag electrode.

[0172] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0173] Comparative Example 3

[0174] A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive comprises the following steps:

[0175] (1) ITO (1.5 cm × 1.5 cm, sheet resistance = 15 Ω square -1 ) Substrate pretreatment:

[0176] 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol for 15 minutes each to obtain an ultrasonically cleaned ITO substrate;

[0177] 1.2) Rapidly dry the ultrasonically cleaned ITO substrate prepared in step 1.1) with high-pressure nitrogen, then place it in a UV-ozone cleaning chamber for 30 minutes to further wet the ITO surface. Remove the substrate and store it in isopropyl alcohol to obtain a wetted ITO substrate.

[0178] (2) Preparation of hole transport layer PEDOT:PSS (CLEVIOSTM P VP AI 4083, Heraeus, Germany):

[0179] 2.1) Before use, PEDOT:PSS was filtered through a 0.45 μm pore size, 13 mm diameter PVDF (polyvinylidene fluoride) water filter and then spin-coated onto the soaked ITO substrate at 4500 rpm / 20 seconds to obtain a PEDOT:PSS-coated ITO substrate.

[0180] 2.2) Annealing the PEDOT:PSS-coated ITO substrate at 150°C for 20 min, then transferring it to a glove box and cooling it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate.

[0181] (3) Configure the donor and recipient in the glove box:

[0182] 3.1) Add the non-fullerene acceptor L8-BO solid to chloroform, controlling the concentration of the L8-BO solution to 8.5 mg / mL, to obtain an acceptor solution.

[0183] 3.2) Add the polymer donor D18-Cl solid to chloroform, controlling the D18-Cl solution concentration to 6.5 mg / mL, to obtain a donor solution.

[0184] 3.3) Stirring the receptor solution and donor solution at 45°C for 2 hours to obtain a pretreated receptor solution and a pretreated donor solution;

[0185] (4) Spin coating:

[0186] 4.1) Using a pipette, spin coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Next, spin coat the pretreated acceptor solution at 4500 rpm for 30 seconds, 15 μL at a time, to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

[0187] 4.2) Using a pipette, spin-coat the electron transport layer PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at a rate of 5000 rpm for 20 seconds to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. The PDIN concentration in the methanol solution was 2.0 mg / mL, and 0.3 vol% acetic acid was added. After completing the above steps, use a blade to scrape off a small portion of the ends of the ITO to facilitate the thermal evaporation of the Ag electrode.

[0188] (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

[0189] The test results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0190] Table 1

[0191]

[0192] The above test results show that the method of the present invention for constructing a photoactive layer thin film of an organic solar cell using a solid additive can effectively regulate the phase separation and molecular crystallinity of the active layer through a continuous deposition method assisted by a highly volatile solid additive, thereby regulating the morphology of the photoactive layer of the organic solar cell, forming a photoactive layer morphology with finer phase separation and higher crystallinity, effectively improving the charge injection efficiency of the battery, obtaining faster and more balanced carrier transport, suppressing carrier recombination, and thereby improving battery efficiency.

[0193] The present invention provides a method for constructing a photoactive layer thin film of an organic solar cell using a solid additive, using 1,3,5-tribromobenzene (abbreviated as TBB) as a new solid additive with high volatility and low cost, and combining it with thermal annealing. Annealing (abbreviated as TA) was used to control the morphology of the cell's photoactive layer film by continuous deposition, and a high-efficiency organic solar cell with a structure of Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag was prepared. The changes in the vertical phase separation and molecular crystallinity of the cell's photoactive layer were revealed. After the additive TBB was introduced into the acceptor L8-BO, the self-assembly of L8-BO was further promoted, thereby helping to form a photoactive layer morphology with finer phase separation and higher crystallinity. The charge injection efficiency of the cell was effectively improved, the carrier transport was faster and more balanced, and the carrier recombination was suppressed. Compared with the efficiency of the control cell of 17.2%, the synergistic effect of the additive and the continuous deposition method made the efficiency of the D18-Cl / L8-BO (TBB+TA) cell reach 18.5%, which is the current open circuit voltage ( V OC ) is one of the highest efficiencies of binary organic solar cells with a voltage of over 900 mV; in addition, the efficiencies of 20 devices were statistically analyzed, and the results showed that the average efficiency of the devices increased from 16.7% to 18.1%. The outstanding advantages of the present invention are: (1) a simpler and more effective method is used to help prepare high-efficiency organic solar cells. The device preparation method is simple and practical, the solid additive has high volatility and low price (100 yuan for 100 g), and annealing is performed at 75°C for 5 minutes (liquid additives are generally annealed at 100°C for 10 minutes); (2) 1,3,5-tribromobenzene (abbreviated as TBB) is used as a new solid additive with high volatility and low cost (Note: it has not been used in organic solar cells), and combined with thermal annealing (TA), the morphology of the cell photoactive layer film is controlled by continuous deposition, which greatly improves the device efficiency.

[0194] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for constructing a photoactive layer thin film of an organic solar cell using a solid additive, characterized in that: The following steps are involved: (1) ITO substrate pretreatment: 1.1) Ultrasonic cleaning the ITO substrate using a detergent solution, deionized water, acetone, deionized water, and isopropyl alcohol in sequence to obtain an ultrasonically cleaned ITO substrate; 1.2) Drying: The ultrasonically cleaned ITO substrate prepared in step 1.1) is then placed in a UV-ozone cleaning chamber for treatment, removed, and stored in isopropyl alcohol to obtain a wetted ITO substrate; (2) Preparation of hole transport layer PEDOT:PSS: 2.1) Before use, PEDOT:PSS was filtered using a PVDF water filter and then spin-coated onto the soaked ITO substrate to obtain a PEDOT:PSS-coated ITO substrate. 2.2) Anneal the PEDOT:PSS-coated ITO substrate at 140-160°C for 15-25 min, then transfer it to a glove box and cool it to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS substrate. (3) Configure the donor and recipient in the glove box: 3.1) In a glove box, prepare a 10-20 mg / mL TBB solution in chloroform. 3.2) Add the non-fullerene acceptor L8-BO solid to the TBB solution prepared in step 3.1) with the concentration of the L8-BO solution controlled between 7.5 and 9 mg / mL to obtain an acceptor solution; 3.3) Add the polymer donor D18-Cl solid to chloroform, controlling the D18-Cl solution concentration to 6-7 mg / mL to obtain a donor solution. 3.4) Stirring the receptor solution and donor solution at a constant temperature of 40-60°C to obtain a pretreated receptor solution and a pretreated donor solution; (4) Spin coating: 4.1) Spin-coat the pretreated donor solution onto the cooled Glass / ITO / PEDOT:PSS to obtain Glass / ITO / PEDOT:PSS / D18-Cl. Then, spin-coat the pretreated acceptor solution to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO. 4.2) Annealing the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO at 70-85°C for 4-6 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO; 4.3) Spin-coat the PDIN solution onto the annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO to obtain Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN. (5) Thermal evaporation: Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN were thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber was controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 90~110 nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

2. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In the step 1.1), the ITO substrate is ultrasonically cleaned for 10 to 20 minutes using a cleaning solution, deionized water, acetone, deionized water, and isopropyl alcohol in sequence to obtain an ultrasonically cleaned ITO substrate.

3. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In step 1.2), the ultrasonically cleaned ITO substrate prepared in step 1.1) is quickly dried with high-pressure nitrogen, then placed in a UV-ozone cleaning chamber for 20-30 minutes, taken out, and stored in isopropyl alcohol to obtain a wetted ITO substrate.

4. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: Before use in step 2.1), the PEDOT:PSS was first filtered using a PVDF water filter with a pore size of 0.45 μm and a diameter of 13 mm, and then spin-coated on the soaked ITO substrate at a rate of 4000-5000 rpm / 20 seconds to obtain an ITO substrate coated with PEDOT:PSS.

5. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In step 2.2), the PEDOT:PSS-coated ITO substrate is annealed at 150-160° C. for 20-25 min, and then transferred to a glove box and cooled to room temperature to obtain a cooled Glass / ITO / PEDOT:PSS.

6. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In step 3.1), a 15-20 mg / mL TBB solution was prepared in a glove box, wherein the solvent of the TBB solution was chloroform.

7. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In the step (4), the spin coating rate of the pre-treated donor solution is 4000-5500 rpm / 30 seconds, the spin coating rate of the pre-treated acceptor solution is 3500-4500 rpm / 30 seconds, and the spin coating rate of the PDIN solution is 4500-5500 rpm / 20 seconds.

8. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In step 4.2), the Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO is annealed at 75-85°C for 5-6 min to obtain annealed Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO.

9. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: The solvent of the PDIN solution in step (4) is methanol, the concentration of PDIN in the PDIN solution is 2.0 mg / mL, and 0.3 vol% acetic acid is added at the same time.

10. The method for constructing a photoactive layer thin film of an organic solar cell using a solid additive according to claim 1, characterized in that: In step (5), Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN is thermally evaporated in a vacuum evaporation chamber, and the pressure of the chamber is controlled to be less than 2×10 -4 Pa level, the thickness of the silver electrode was controlled at 100~110nm, and the forward device structure obtained was Glass / ITO / PEDOT:PSS / D18-Cl / L8-BO / PDIN / Ag.

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