Halogenated triphenylethylene modified inverted perovskite solar cell and preparation method thereof

Abstract

The invention discloses a halogenated triphenylethylene modified inverted perovskite solar cell and a preparation method thereof, and relates to the technical field of solar cells, and the inverted perovskite solar cell structurally comprises a substrate, an anode, a hole transport layer, a perovskite light absorption layer, an interface modification layer, an electron transport layer and a cathode from bottom to top. Wherein the interface modification layer is made of triphenylethylene and / or halogenated triphenylethylene, and the perovskite light absorption layer is made of an organic-inorganic hybrid halogen perovskite material. The interface modification layer of triphenylethylene and / or halogenated triphenylethylene is introduced to the surface of the perovskite light absorption layer, the performance and the stability are improved by utilizing halogen coordination passivation defects and blocking water and oxygen migration of the interface modification layer, and the interface behavior is adaptively adjusted under dynamic illumination by means of the photochromic characteristic, so that the ultraviolet tolerance and the light response capability are enhanced.

Description

Technical Field

[0001] This invention belongs to the field of solar cell technology, specifically relating to a halotriphenylene-modified inverse perovskite solar cell and its preparation method. Background Technology

[0002] Organic-inorganic hybrid halide perovskite materials are based on the ABX3 type perovskite structure, which consists of a central A cation (usually methylammonium (MA)). + ), formamide (FA) + ) or Cs + ) and divalent metals (B) such as Pb 2+ Occupying the octahedral cage, and the halide ions (usually I) located in the corners. or Br Defined as follows. It has excellent photoelectric properties; however, it still faces the following problems: (1) The composition evolution is complex and halide phase separation is easy to occur, resulting in poor phase stability of perovskite thin films; (2) The defect density is large. Positively charged metal cations and negatively charged halide anions can not only act as non-radiative recombination centers to affect carrier transport, but also provide a path for the penetration of water or oxygen molecules, resulting in severe non-radiative recombination at the perovskite / transport layer interface and a large photovoltage loss.

[0003] To address the aforementioned issues, current methods primarily employ precursor doping and post-treatment strategies to modulate the microstructure of perovskite films and the interfacial electrical properties of the perovskite / transport layer. These methods can improve the quality, stability, and carrier transport characteristics of perovskite films to some extent. However, these methods lack dynamic adaptability because most of the passivation effect depends on chemical reactions, and the functional groups of the passivation molecules interact with the uncoordinated Pb on the perovskite surface / bulk phase. 2+ The passivation molecules reduce surface defects in thin films by forming coordination bonds, or by forming hydrogen bonds or electrostatic attraction with halide ions. However, the role of passivation molecules in photoresponse compensation is neglected, and their ability to adapt to external stimuli (such as light) is lacking. Summary of the Invention

[0004] To address the aforementioned problems in the prior art, this invention provides a halotriphenylene-modified inverse perovskite solar cell and its preparation method. The technical problem to be solved by this invention is achieved through the following technical solution: This invention provides a halotriphenylene-modified inverse perovskite solar cell, comprising: a substrate, an anode, a hole transport layer, a perovskite light-absorbing layer, an interface modification layer, an electron transport layer, and a cathode, which are stacked sequentially from bottom to top. The interface modification layer is made of at least one of triphenylene and halotriphenylene. The perovskite light-absorbing layer is made of an organic-inorganic hybrid haloperovskite material.

[0005] This invention also provides a method for preparing a halotriphenylene-modified inverse perovskite solar cell, applicable to the halotriphenylene-modified inverse perovskite solar cell described in any of the above embodiments, comprising: Step 1: Pre-treat the substrate, wherein the substrate includes a substrate and an anode located on the surface of the substrate; Step 2: Prepare a hole transport layer on the surface of the anode; Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, wherein the material of the perovskite light-absorbing layer is an organic-inorganic hybrid halide perovskite material; Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, wherein the material of the interface modification layer includes at least one of triphenylene and halotriphenylene; Step 5: Prepare an electron transport layer on the surface of the interface modification layer; Step 6: Prepare a cathode on the surface of the electron transport layer or prepare a cathode buffer layer on the surface of the electron transport layer and then prepare the cathode on the surface of the cathode buffer layer.

[0006] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention relates to a triphenylene halotriphenylene-modified inverted perovskite solar cell. By introducing photochromic materials, represented by triphenylene and its halo derivatives, as an interface modification layer at the light-absorbing layer surface of the perovskite solar cell, the photoelectric performance and operational stability of the cell are effectively improved. This material, on the one hand, utilizes its halogen functional groups to interact with uncoordinated ions (such as Pb²⁺) on the perovskite surface. + I - The formation of strong coordination bonds significantly reduces the surface defect state density and suppresses nonradiative recombination, thereby improving the open-circuit voltage and fill factor. Simultaneously, its physical barrier effect inhibits water and oxygen intrusion and halide ion migration, slowing down phase separation and performance degradation. Furthermore, the photochromic units in the material undergo reversible photocyclization under dynamic illumination, altering their molecular configuration and electronic structure. This allows for selective absorption of ultraviolet or high-energy blue light, mitigating light damage to the perovskite lattice. Through dynamic control of interfacial charge transport behavior, the battery adaptively adjusts light absorption and carrier extraction efficiency under different illumination conditions. This interface modification strategy achieves synergy between passivation, encapsulation, and photoresponse functions, significantly enhancing the long-term light stability of the device while improving its photovoltaic performance.

[0007] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described in detail below with reference to the accompanying drawings. Attached Figure Description

[0008] Figure 1 This is a schematic diagram of the structure of a halotriphenylene-modified inverse perovskite solar cell provided in an embodiment of the present invention; Figure 2 This is a schematic diagram of another halotriphenylene-modified inverse perovskite solar cell provided in an embodiment of the present invention; Figure 3 This is a schematic diagram of a method for preparing a halotriphenylene-modified inverse perovskite solar cell according to an embodiment of the present invention; Figure 4 This is a process flow diagram of the fabrication of a halotriphenylene-modified inverse perovskite solar cell provided in an embodiment of the present invention; Figure 5 These are the JV curve measurement results of the inverted perovskite solar cell provided in the embodiments of the present invention; Figure 6 These are the stability test results of the inverted perovskite solar cell provided in the embodiments of the present invention. Detailed Implementation

[0009] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following, in conjunction with the accompanying drawings and specific embodiments, provides a detailed description of a halotriphenylene-modified inverse perovskite solar cell and its preparation method according to the present invention.

[0010] The foregoing and other technical contents, features, and effects of the present invention will be clearly presented in the following detailed description of specific embodiments in conjunction with the accompanying drawings. Through the description of the specific embodiments, a more in-depth and concrete understanding can be gained of the technical means and effects adopted by the present invention to achieve its intended purpose. However, the accompanying drawings are for reference and illustration only and are not intended to limit the technical solutions of the present invention.

[0011] In a first aspect, embodiments of the present invention provide a halotriphenylene-modified inverse perovskite solar cell, please refer to... Figure 1 , Figure 1 This is a schematic diagram of the structure of a halotriphenylene-modified inversion perovskite solar cell provided in an embodiment of the present invention, as shown below. Figure 1 As shown, the halotriphenylene-modified inverted perovskite solar cell of this embodiment includes: a substrate, an anode, a hole transport layer, a perovskite light-absorbing layer, an interface modification layer, an electron transport layer, and a cathode, which are stacked sequentially from bottom to top.

[0012] In this embodiment, the substrate is a transparent conductive substrate, and its material can be a large-area silicon wafer, glass, flexible metal foil, or flexible plastic. The flexible metal foil can be stainless steel, molybdenum, titanium, aluminum, or copper, etc., and the flexible plastic can be polyimide (PI), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN).

[0013] In this embodiment, an anode is provided on the surface of the substrate to form a substrate sheet. The anode serves as the bottom electrode and is matched with the hole transport layer for collecting holes. For example, the substrate sheet can be transparent conductive glass (ITO / FTO).

[0014] In this embodiment, the hole transport layer material includes MeO-2PACz, Me-4PACz, Spiro-MeOTAD, PMMA, and NiO. x At least one of the following. The hole transport layer helps charge transport in solar cells, improving the cell's conversion efficiency.

[0015] The perovskite light-absorbing layer is the core layer of a perovskite solar cell, and its main function is to absorb sunlight and convert light energy into electrical energy. In this embodiment, the material of the perovskite light-absorbing layer is an organic-inorganic hybrid halogen perovskite material, and the thickness of the perovskite light-absorbing layer is 100-300 nm. The organic-inorganic hybrid halogen perovskite material is a cesium-methylammonium-methylammonium mixed halogen lead-based perovskite, which can be written with the general formula ABX3, where A is FA, CS, and MA, B is Pb, and X is I and Br.

[0016] For example, the material of the perovskite light-absorbing layer can be Cs 0.15 FA 0.65 MA 0.20 Pb(I 0.80 Br 0.20 3. Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 )3 or (Cs 0.15 FA 0.60 MA 0.25 )Pb(I 0.9 Br 0.1 3.

[0017] In this embodiment, the material of the interface modification layer includes at least one of tristyrene and halotristyrene. The thickness of the interface modification layer is 300-500 nm.

[0018] The molecular structural formula of triphenylene is: ; The molecular structural formula of halotriphenylene is: ; Among them, R1, R2 and R3 have the same element, which is H, F, Cl or Br.

[0019] In this embodiment, to enable the perovskite solar cell to dynamically respond to changes in illumination during operation, a photochromic material, namely triphenylene and its halogenated derivatives, is used at the interface of the perovskite light-absorbing layer of the perovskite solar cell. Triphenylene and its halogenated derivatives form a three-dimensional propeller-like twisted configuration with a central ethylene double bond and three benzene rings. Under illumination, the central double bond and the adjacent benzene rings can undergo a photocyclization reaction, changing the molecular structure from an open-ring state (colorless) to a closed-ring state (colored). This effectively absorbs ultraviolet light or high-energy blue light, reduces the damage of ultraviolet light to the perovskite lattice, improves charge extraction efficiency, and enhances the stability of the cell under long-term illumination.

[0020] Furthermore, the hydrogen atoms on the benzene ring in triphenylene can be replaced by various functional groups (especially halogen atoms) to form halotriphenylene. Halotriphenylene can react with uncoordinated ions on the perovskite surface (such as Pb²⁺). + I - This process forms strong coordination bonds, reduces the defect state density on the perovskite surface, lowers carrier nonradiative recombination losses, and improves open-circuit voltage and fill factor. Simultaneously, this interface modification layer physically blocks water and oxygen, inhibits the migration of halide ions along grain boundaries, suppresses phase separation, enhances overall stability, and slows performance degradation.

[0021] In this embodiment, the material of the electron transport layer includes PC. 61 At least one of BM, TiO2, and ZnO. An electron transport layer can enhance the separation of electrons and holes, thereby effectively improving the conversion efficiency of solar cells.

[0022] In this embodiment, the cathode material includes at least one of Ag and Cu.

[0023] Please see Figure 2 , Figure 2 This is a schematic diagram of another halotriphenylene-modified inverse perovskite solar cell provided in an embodiment of the present invention. Compared to Figure 1 The halotriphenylene-modified inverse perovskite solar cell shown is, for example... Figure 2The halotriphenylene-modified inverse perovskite solar cell shown also includes a cathode buffer layer located between the electron transport layer and the cathode to improve the cell's conversion efficiency. The cathode buffer layer can be a single layer or a two-layer structure, the specific number of layers being selected based on the cell's performance. In this embodiment, the cathode buffer layer includes a first buffer layer and a second buffer layer stacked from bottom to top; that is, the first buffer layer is located on the upper surface of the electron transport layer, the second buffer layer is located on the upper surface of the first buffer layer, and the cathode is located on the upper surface of the second buffer layer. The material of the first buffer layer is C. 60 The material of the second buffer layer is BCP.

[0024] The present invention relates to a triphenylene halide-modified inverted perovskite solar cell, which uses triphenylene and its halide derivatives as interface modification materials. Triphenylene is a functional molecule containing a photochromic framework and linked to halide ions. Based on coordination, hydrogen bonding, and other interactions, this molecule can passivate the perovskite film, thereby inhibiting surface / interface charge recombination and ion migration in organic-inorganic halide hybrid perovskites. Simultaneously, it optimizes interface energy level matching and improves the thermal stability of the inverted organic-inorganic hybrid halide perovskite solar cell. Furthermore, the photochromic unit undergoes a configurational change upon dynamic light irradiation, resulting in reversible changes in molecular dipole moment, light absorption wavelength, and refractive index. This reversible effect influences charge transport behavior at the interface.

[0025] The halotriphenylene-modified inverse perovskite solar cell of the present invention can adjust the light absorption and carrier extraction efficiency under different illumination conditions. At the same time, the interface modification material can improve the grain size and crystallinity of the perovskite thin film, thereby improving the photovoltaic performance and stability of the device.

[0026] Secondly, embodiments of the present invention provide a method for preparing a halotriphenylene-modified inverted perovskite solar cell, applicable to the halotriphenylene-modified inverted perovskite solar cell provided in the first aspect.

[0027] Please see Figure 3 , Figure 3 This is a schematic diagram illustrating a method for preparing a halotriphenylene-modified inverse perovskite solar cell according to an embodiment of the present invention. Figure 3 As shown, the preparation method of the halotriphenylene-modified inverse perovskite solar cell in this embodiment includes the following steps: Step 1: Pre-treat the substrate, wherein the substrate includes a substrate and an anode located on the surface of the substrate.

[0028] Specifically, step 1 includes: Step 1.1: Select a substrate with a transparent conductive oxide thin film electrode; Step 1.2: The substrate is ultrasonically cleaned sequentially with cleaning agent, deionized water and anhydrous ethanol, and finally dried with a nitrogen gun; Step 1.3: Pre-treat the substrate in an ultraviolet ozone environment.

[0029] For example, a transparent conductive glass substrate with fluorine-doped tin oxide (FTO) can be selected as the substrate.

[0030] Step 2: Prepare a hole transport layer on the surface of the anode.

[0031] Specifically, step 2 includes: Step 2.1: Spin-coat the prepared hole transport material precursor solution onto the substrate; wherein the spin-coating speed is 2000~4000 r / min and the spin-coating time is 20~50 s; Step 2.2: Place the entire substrate on a hot plate for annealing at a temperature of 100 °C for 10 min to form a hole transport layer; Step 2.3: Clean the surface of the substrate using a poor solvent for hole transport materials to reduce the anchored hole transport materials and obtain a hole transport layer.

[0032] Alternatively, the hole transport layer can be made of MeO-2PACz, Me-4PACz, Spiro-MeOTAD, PMMA, or NiO. x .

[0033] Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, wherein the material of the perovskite light-absorbing layer is an organic-inorganic hybrid halogen perovskite material.

[0034] Specifically, step 3 includes: Step 3.1: Using a one-step spin coating method, spin coat the perovskite precursor solution onto the surface of the hole transport layer. The spin coating conditions are as follows: first spin coat at a speed of 500~2000 r / min for 3~10 s, then increase the speed to 2000~6000 r / min for 20~40 s. Step 3.2: Anneal the spin-coated substrate in air at a temperature of 100-200 ℃ for 5-30 min to form a perovskite light-absorbing layer.

[0035] In this embodiment, the organic-inorganic hybrid halogen perovskite material is a cesium carbamate carbamate mixed halogen lead-based perovskite.

[0036] For example, the material of the perovskite light-absorbing layer can be Cs 0.15 FA 0.65 MA 0.20 Pb(I 0.80 Br0.20 3. Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 )3 or (Cs 0.15 FA 0.60 MA 0.25 )Pb(I 0.9 Br 0.1 3.

[0037] Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, wherein the material of the interface modification layer includes at least one of triphenylene and halotriphenylene.

[0038] Triphenylene can be represented as TP, and halotriphenylene can be represented as TP-R, where R includes R1, R2, and R3. R1, R2, and R3 have the same element, which is H, F, Cl, or Br.

[0039] Specifically, step 4 includes: Step 4.1: Dissolve the material of the interface modification layer in isopropanol or ethanol solution to obtain the interface modification material precursor solution; In this embodiment, triphenylene and / or halotriphenylene are dissolved in isopropanol or ethanol solution to obtain a mixed solution; then the mixture is stirred at room temperature to obtain a clear interface modification material precursor solution.

[0040] Step 4.2: Spin-coat the interface modification material precursor solution onto the surface of the perovskite light-absorbing layer to form an interface modification layer.

[0041] In this embodiment, the spin-coated substrate is annealed in air at a temperature of 100°C for 5 to 30 minutes to form an interface modification layer.

[0042] Step 5: Prepare an electron transport layer on the surface of the interface modification layer.

[0043] Specifically, step 5 includes: Step 5.1: Spin-coat the prepared electron transport material precursor solution onto the interface modification layer; wherein the spin-coating speed is 1000~3000 r / min and the spin-coating time is 20~40 s.

[0044] Step 5.2: Anneal the entire substrate on a hot plate under a nitrogen atmosphere to form an electron transport layer. The annealing temperature is 50~200 ℃, and the annealing time is 3~10 min.

[0045] Step 6: Prepare a cathode on the surface of the electron transport layer or prepare a cathode buffer layer on the surface of the electron transport layer and then prepare a cathode on the surface of the cathode buffer layer.

[0046] Specifically, the preparation of a cathode on the surface of the electron transport layer includes depositing a 50–200 nm metal electrode on the surface of the electron transport layer to complete the preparation of an inverted perovskite solar cell.

[0047] The cathode buffer layer has two layers, and the material of the first buffer layer is C. 60 Taking BCP as an example, the second buffer layer is made of a material that, after preparing a cathode buffer layer on the surface of the electron transport layer, prepares a cathode on the surface of the cathode buffer layer. Specifically, this includes depositing 10–40 nm C on the electron transport layer. 60 Cathode buffer layer; in C 60 A 5–10 nm BCP is deposited on the cathode buffer layer to complete the preparation of the cathode buffer layer; a 50–200 nm metal electrode is evaporated on the surface of the cathode buffer layer to complete the preparation of the inverted perovskite solar cell.

[0048] In this embodiment, the cathode buffer layer is used to improve the conversion efficiency of the cell and can be selectively fabricated. The fabrication process of the halotriphenylene-modified inverse perovskite solar cell, taking the fabrication of the cathode buffer layer as an example, is as follows: Figure 4 As shown, Figure 4 This is a process flow diagram of the fabrication process of a halotriphenylene-modified inverse perovskite solar cell provided in an embodiment of the present invention.

[0049] For details regarding the preparation method of the halotriphenylene-modified inverted perovskite solar cell and its corresponding beneficial effects, please refer to the relevant content on the halotriphenylene-modified inverted perovskite solar cell provided in the first aspect, which will not be repeated here.

[0050] Furthermore, the preparation method of the halotriphenylene-modified inverse perovskite solar cell of the present invention will be illustrated by way of specific embodiments.

[0051] Example 1 Fabrication of halotriphenylene-modified inverse perovskite solar cells: ITO / NiO x / Cs 0.15 FA 0.65 MA 0.20 Pb(I 0.80 Br 0.20 )3 / TP-F / PC 61 BM / C 60 / BCP / Ag, the preparation method includes the following steps: Step 1: Pre-process the substrate, specifically including: Step 1.1: Select an ITO transparent conductive glass substrate as the substrate. Step 1.2: The substrate was ultrasonically cleaned for 15 minutes in sequence with cleaning agent, deionized water and anhydrous ethanol, and finally dried with nitrogen gun; Step 1.3: Pre-treat the substrate in an ultraviolet ozone environment for 15 min.

[0052] Step 2: Prepare a hole transport layer on the surface of the anode, specifically including: Step 2.1: Take 10 mg of NiO x Dissolve in 1 mL of a mixture of water and hydrogen peroxide (9:1), and stir at room temperature for 1 hour until dissolved to obtain NiO. x Precursor solution. Then, spin-coating NiO. x The precursor solution is on the substrate; the spin coating speed is 3000 r / min and the spin coating time is 30 s; Step 2.2: Place the entire substrate on a hot plate for annealing to obtain 20 nm NiO. x Hole transport layer; wherein the hot stage temperature is 100 ℃ and annealing is performed for 10 min.

[0053] Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, specifically including: Step 3.1: Dissolve 145.3 mg, 29.1 mg, 479.4 mg, 50.7 mg, 95.4 mg, and 10 mg of FAI, MABr2, PbI2, CsI, PbBr2, and Pb(SCN)2 in 1.0 mL of DMF:NMP (4:1), and then stir at room temperature for 3 hours to fully dissolve the perovskite light-absorbing material to obtain a pale yellow perovskite precursor solution. Use a one-step spin coating method to spin coat the perovskite precursor solution onto the surface of the hole transport layer. The spin coating conditions are as follows: first spin coat at a speed of 500~2000 r / min for 3~10 s, and then increase the speed to 2000~6000 r / min for 20~40 s. Step 3.2: Anneal the spin-coated substrate in air at a temperature of 100-200 ℃ for 5-30 min to form a perovskite light-absorbing layer.

[0054] Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, specifically including: Step 4.1: Dissolve TP-F in isopropanol or ethanol to obtain a mixed solution; stir the mixture at room temperature to obtain a clear precursor solution. Spin-coat the precursor solution of the interface modification material onto the surface of the perovskite light-absorbing layer at a spin-coating speed of 2000~6000 r / min for 30~50 s to form an interface modification layer.

[0055] Step 4.2: Anneal the spin-coated substrate in air at a temperature of 100 ℃ for 5~30 min to form an interface modification layer.

[0056] Step 5: Prepare an electron transport layer on the surface of the interface modification layer, specifically including: Step 5.1: Take 10 mg of PC 61 BM was dissolved in 1 mL of chlorobenzene and stirred at room temperature for 6 hours to ensure complete dissolution, yielding black PC. 61 BM precursor solution; Prepared PC 61 The BM precursor solution was spin-coated onto the interface modification layer at a spin speed of 3000 r / min and a spin time of 30 s. Step 5.2: Place the entire substrate in a glove box and anneal it on a hot plate at 60 °C for 5 minutes to form a 20 nm electron transport layer film.

[0057] Step 6: After preparing a cathode buffer layer on the surface of the electron transport layer, prepare a cathode on the surface of the cathode buffer layer.

[0058] Step 6.1: Deposit 30 nm C on the electron transport layer using a vacuum evaporation machine. 60 As the first buffer layer, the growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s; Step 6.2: Use a vacuum evaporation machine to deposit C 60 A 6 nm BCP was deposited on top as a second buffer layer, with a growth pressure of 1E-4 Pa, a power of 100 W, and a growth rate of 0.5 Å / s. Step 6.3: Vacuum evaporation is used to deposit 100 nm Ag as the cathode on the second buffer layer. The growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s.

[0059] Example 2 Fabrication of halotriphenylene-modified inverse perovskite solar cells: ITO / / NiO x / Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 )3 / TP-Cl / PC 61 BM / C 60 / BCP / Cu, the preparation method includes the following steps: Step 1: Pre-process the substrate, specifically including: Step 1.1: Select an ITO transparent conductive glass substrate as the substrate. Step 1.2: The substrate was ultrasonically cleaned for 15 minutes in sequence with cleaning agent, deionized water and anhydrous ethanol, and finally dried with nitrogen gun; Step 1.3: Pre-treat the substrate in an ultraviolet ozone environment for 15 min.

[0060] Step 2: Prepare a hole transport layer on the surface of the anode, specifically including: Step 2.1: Take 10 mg of NiO x Dissolve in 1 mL of a mixture of water and hydrogen peroxide (9:1), and stir at room temperature for 1 hour until dissolved to obtain NiO. x Precursor solution. Then, spin-coating NiO. x The precursor solution is on the substrate; the spin coating speed is 3000 r / min and the spin coating time is 30 s; Step 2.2: Place the entire substrate on a hot plate for annealing to obtain 20 nm NiO. x Hole transport layer; wherein the hot stage temperature is 100 ℃ and annealing is performed for 10 min.

[0061] Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, specifically including: Step 3.1: Dissolve 177.3 mg, 23.5 mg, 494.9 mg, 16.9 mg, 83.1 mg, and 10 mg of FAI, MABr2, PbI2, CsI, PbBr2, and Pb(SCN)2 in 1.0 mL of DMF:NMP (4:1), and then stir at room temperature for 3 hours to fully dissolve the perovskite light-absorbing material to obtain a pale yellow perovskite precursor solution. Use a one-step spin-coating method to spin-coat the perovskite precursor solution onto the surface of the hole transport layer. The spin-coating conditions are as follows: first spin-coat at a speed of 500~2000 r / min for 3~10 s, and then increase the speed to 2000~6000 r / min for 20~40 s. Step 3.2: Anneal the spin-coated substrate in air at a temperature of 100-200 ℃ for 5-30 min to form a perovskite light-absorbing layer.

[0062] Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, specifically including: Step 4.1: Dissolve TP-Cl in isopropanol or ethanol to obtain a mixed solution; stir the mixture at room temperature to obtain a clear precursor solution. Spin-coat the precursor solution of the interface modification material onto the surface of the perovskite light-absorbing layer at a spin-coating speed of 2000~6000 r / min for 30~50 s to form an interface modification layer.

[0063] Step 4.2: Anneal the spin-coated substrate in air at a temperature of 100 ℃ for 5~30 min to form an interface modification layer.

[0064] Step 5: Prepare an electron transport layer on the surface of the interface modification layer, specifically including: Step 5.1: Take 10 mg of PC 61 BM was dissolved in 1 mL of chlorobenzene and stirred at room temperature for 6 hours to ensure complete dissolution, yielding black PC. 61 BM precursor solution; Prepared PC 61 The BM precursor solution was spin-coated onto the interface modification layer at a spin speed of 3000 r / min and a spin time of 30 s. Step 5.2: Place the entire substrate in a glove box and anneal it on a hot plate at 60 °C for 5 minutes to form a 20 nm electron transport layer film.

[0065] Step 6: After preparing a cathode buffer layer on the surface of the electron transport layer, prepare a cathode on the surface of the cathode buffer layer.

[0066] Step 6.1: Deposit 30 nm C on the electron transport layer using a vacuum evaporation machine. 60 As the first buffer layer, the growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s; Step 6.2: Use a vacuum evaporation machine to deposit C 60 A 6 nm BCP was deposited on top as a second buffer layer, with a growth pressure of 1E-4 Pa, a power of 100 W, and a growth rate of 0.5 Å / s. Step 6.3: Vacuum evaporation is used to deposit 100 nm Cu as the cathode on the second buffer layer. The growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s.

[0067] Example 3 Fabrication of halotriphenylene-modified inverse perovskite solar cells: ITO / / NiO x / (Cs 0.15 FA 0.60 MA 0.25 )Pb(I 0.9 Br 0.1 )3 / TP-Br / PC 61 BM / C 60 / BCP / Ag, the preparation method includes the following steps: Step 1: Pre-process the substrate, specifically including: Step 1.1: Select an ITO transparent conductive glass substrate as the substrate. Step 1.2: The substrate was ultrasonically cleaned for 15 minutes in sequence with cleaning agent, deionized water and anhydrous ethanol, and finally dried with nitrogen gun; Step 1.3: Pre-treat the substrate in an ultraviolet ozone environment for 15 min.

[0068] Step 2: Prepare a hole transport layer on the surface of the anode, specifically including: Step 2.1: Take 10 mg of NiO x Dissolve in 1 mL of a mixture of water and hydrogen peroxide (9:1), and stir at room temperature for 1 hour until dissolved to obtain NiO. x Precursor solution. Then, spin-coating NiO. x The precursor solution is on the substrate; the spin coating speed is 3000 r / min and the spin coating time is 30 s; Step 2.2: Place the entire substrate on a hot plate for annealing to obtain 20 nm NiO. x Hole transport layer; wherein the hot stage temperature is 100 ℃ and annealing is performed for 10 min.

[0069] Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, specifically including: Step 3.1: Dissolve 134.9 mg, 36.4 mg, 584.3 mg, 50.7 mg, 11.9 mg, and 10 mg of FAI, MABr2, PbI2, CsI, PbBr2, and Pb(SCN)2 in 1.0 mL of DMF:NMP (4:1), and then stir at room temperature for 3 hours to fully dissolve the perovskite light-absorbing material to obtain a pale yellow perovskite precursor solution. Use a one-step spin-coating method to spin-coat the perovskite precursor solution onto the surface of the hole transport layer. The spin-coating conditions are as follows: first spin-coat at a speed of 500~2000 r / min for 3~10 s, and then increase the speed to 2000~6000 r / min for 20~40 s. Step 3.2: Anneal the spin-coated substrate in air at a temperature of 100-200 ℃ for 5-30 min to form a perovskite light-absorbing layer.

[0070] Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, specifically including: Step 4.1: Dissolve TP-Br in isopropanol or ethanol to obtain a mixed solution; stir the mixture at room temperature to obtain a clear precursor solution. Spin-coat the precursor solution of the interface modification material onto the surface of the perovskite light-absorbing layer at a spin-coating speed of 2000~6000 r / min for 30~50 s to form an interface modification layer.

[0071] Step 4.2: Anneal the spin-coated substrate in air at a temperature of 100 ℃ for 5~30 min to form an interface modification layer.

[0072] Step 5: Prepare an electron transport layer on the surface of the interface modification layer, specifically including: Step 5.1: Take 10 mg of PC 61 BM was dissolved in 1 mL of chlorobenzene and stirred at room temperature for 6 hours to ensure complete dissolution, yielding black PC. 61 BM precursor solution; Prepared PC 61 The BM precursor solution was spin-coated onto the interface modification layer at a spin speed of 3000 r / min and a spin time of 30 s. Step 5.2: Place the entire substrate in a glove box and anneal it on a hot plate at 60 °C for 5 minutes to form a 20 nm electron transport layer film.

[0073] Step 6: After preparing a cathode buffer layer on the surface of the electron transport layer, prepare a cathode on the surface of the cathode buffer layer.

[0074] Step 6.1: Deposit 30 nm C on the electron transport layer using a vacuum evaporation machine. 60 As the first buffer layer, the growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s; Step 6.2: Use a vacuum evaporation machine to deposit C 60 A 6 nm BCP was deposited on top as a second buffer layer, with a growth pressure of 1E-4 Pa, a power of 100 W, and a growth rate of 0.5 Å / s. Step 6.3: Vacuum evaporation is used to deposit 100 nm Ag as the cathode on the second buffer layer. The growth pressure is 1E-4 Pa, the power is 100 W, and the growth rate is 0.5 Å / s.

[0075] Furthermore, the inverted organic-inorganic hybrid perovskite solar cells prepared in Examples 1, 2, and 3 above were subjected to optical and electrical tests, and their performance was compared with that of conventional inverted perovskite solar cells. The conventional inverted perovskite solar cells, from bottom to top, are: ITO / NiOx / Cs0.15FA0.65MA0.20Pb(I0.80Br0.20)3 / PC61BM / C60 / BCP / Ag.

[0076] The effective area of ​​the inverted perovskite solar cells prepared in the above embodiments is 7 mm². 2The electrical performance and defect state density of the perovskite solar cells prepared in Examples 1, 2 and 3 were tested under the AM 1.5G solar spectrum.

[0077] Please see Figure 5 , Figure 5 This is the JV curve measurement result of the inverted perovskite solar cell provided in the embodiment of the present invention. Figure 5 As shown, the open-circuit voltage (V) of the unmodified device (traditional device) OC = 1.16 V, fill factor (FF) = 78.35%, short-circuit current density (J) SC =20.93 mA / cm 2 The device's power conversion efficiency (PCE) is 19.02%. Example 1 shows a solar cell based on TP-F interface modification, with a device V... OC = 1.20 V, fill factor (FF) = 79.59%, short-circuit current density (J) SC =21.95 mA / cm 2 The device's power conversion efficiency (PCE) is 20.97%; the solar cell based on TP-Cl interface modification prepared in Example 2 has a V... OC =1.20 V, fill factor (FF) =77.95%, short-circuit current density (J) SC =21.98mA / cm 2 The device's power conversion efficiency (PCE) is 20.56%; the solar cell based on TP-Br interface modification prepared in Example 3 has a V... OC =1.20 V, fill factor (FF) =79.34%, short-circuit current density (J) SC =21.12mA / cm 2 The device achieved a power conversion efficiency (PCE) of 20.11%. This demonstrates that adding styrene derivative interface modification materials to perovskite solar cells improves the open-circuit voltage and fill factor, ultimately resulting in a high-performance inverted perovskite solar cell.

[0078] Please see Figure 6 , Figure 6 These are the stability test results of the inverted perovskite solar cell provided in the embodiments of the present invention. From... Figure 6 As can be seen, the perovskite solar cells prepared using TP-F, TP-Cl and TP-Br still maintained their original efficiencies of 88%, 91.5% and 93% after 500 h, respectively, while the PCE of the undoped reference device rapidly decreased to 67% of the initial efficiency.

[0079] Organic-inorganic hybrid halide perovskites possess outstanding performance advantages, such as high absorption coefficient, tunable bandgap, long carrier diffusion length, and low manufacturing cost. High-quality perovskite thin films are crucial for realizing efficient PSC devices. To enable materials to dynamically respond to illumination during operation, photochromic properties through photoinduced conversion are necessary, effectively passivating grain boundaries or surface defects. This is beneficial for achieving higher photoelectric conversion efficiency and excellent stability in inverted organic-inorganic hybrid perovskite solar cells. The fabrication of perovskite solar cells using tristyrene and its derivatives as interface modification materials not only precisely controls the crystallization process of the perovskite layer, promoting crystal orientation and reducing defect formation and phase separation, but also significantly improves the stability and lifespan of the cells; this facilitates the commercial large-scale production of perovskite solar cells. Perovskite thin films and solar cells prepared based on the method of this invention have great potential in crystalline silicon-perovskite and perovskite-perovskite tandem solar cells.

[0080] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations are intended to cover non-exclusive inclusion, such that an article or device comprising a list of elements includes not only those elements but also other elements not expressly listed. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the article or device comprising said element. Terms such as "connected" or "linked" are not limited to physical or mechanical connections but can include electrical connections, whether direct or indirect. The orientations or positional relationships indicated by terms such as "upper," "lower," "left," and "right" are based on the orientations or positional relationships shown in the accompanying drawings and are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the invention.

[0081] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0082] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A halotriphenylene-modified inverse perovskite solar cell, characterized in that, include: The substrate, anode, hole transport layer, perovskite light-absorbing layer, interface modification layer, electron transport layer, and cathode are stacked sequentially from bottom to top. The interface modification layer is made of at least one of tristyrene and halotristyrene. The perovskite light-absorbing layer is made of an organic-inorganic hybrid haloperovskite material.

2. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, The thickness of the interface modification layer is 300-500 nm.

3. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, The molecular structural formula of the triphenylene is: ； The molecular structural formula of the halotriphenylene is: ； Among them, R1, R2 and R3 have the same element, which is H, F, Cl or Br.

4. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, The thickness of the perovskite light-absorbing layer is 100-300 nm; the organic-inorganic hybrid halogen perovskite material is a cesium carbamate carbamate mixed halogen lead-based perovskite.

5. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, The substrate material includes silicon wafers, glass, flexible metal foil, or flexible plastic.

6. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, The hole transport layer is made of materials including MeO-2PACz, Me-4PACz, Spiro-MeOTAD, PMMA, and NiO. x At least one of them; The electron transport layer is made of PC. 61 At least one of BM, TiO2 and ZnO.

7. The halotriphenylene-modified inverse perovskite solar cell according to claim 1, characterized in that, It also includes a cathode buffer layer, which is located between the electron transport layer and the cathode.

8. The halotriphenylene-modified inverse perovskite solar cell according to claim 7, characterized in that, The cathode buffer layer includes a first buffer layer and a second buffer layer stacked from bottom to top, wherein the material of the first buffer layer is C. 60 The material of the second buffer layer is BCP.

9. A method for preparing a halotriphenylene-modified inverse perovskite solar cell, characterized in that, The halotriphenylene-modified inverse perovskite solar cell according to any one of claims 1-8 comprises: Step 1: Pre-treat the substrate, wherein the substrate includes a substrate and an anode located on the surface of the substrate; Step 2: Prepare a hole transport layer on the surface of the anode; Step 3: Prepare a perovskite light-absorbing layer on the surface of the hole transport layer, wherein the material of the perovskite light-absorbing layer is an organic-inorganic hybrid halide perovskite material; Step 4: Prepare an interface modification layer on the surface of the perovskite light-absorbing layer, wherein the material of the interface modification layer includes at least one of triphenylene and halotriphenylene; Step 5: Prepare an electron transport layer on the surface of the interface modification layer; Step 6: Prepare a cathode on the surface of the electron transport layer or prepare a cathode buffer layer on the surface of the electron transport layer and then prepare the cathode on the surface of the cathode buffer layer.

10. The method for preparing the halotriphenylene-modified inverse perovskite solar cell according to claim 9, characterized in that, Step 4 includes: Step 4.1: Dissolve the material of the interface modification layer in isopropanol or ethanol solution to obtain an interface modification material precursor solution. Step 4.2: Spin-coat the interface modification material precursor solution onto the surface of the perovskite light-absorbing layer to form the interface modification layer.

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