A process for the preparation of P - type EDTA-N materials and their use in trans-inorganic perovskite solar cells

Abstract

A type of P ‑ Preparation method of n-type EDTA-N material and its application in inverse inorganic perovskite solar cells. Common n-type EDTA is modified to P... ‑ Type EDTA-N material, as NiO x The modification layer is applied in inverted inorganic perovskite solar cells, forming a layer composed of P ‑ To P + The field-enhancing structure solves the problem of NiO in inverted inorganic perovskite solar cells. x The problem of energy level mismatch and electron-hole extraction imbalance between the EDTA-N layer and perovskite light-absorbing materials is addressed. The preparation method of the EDTA-N layer is as follows: an EDTA-N solution is prepared using an ion exchange method, and the prepared EDTA-N solution is spin-coated onto NiO. x NiO on thin film x The interfacial layer between the PI and perovskite. The semiconductor properties of the EDTA-N material of this invention are P... ‑ The type is simple to prepare and is used in NiO. x The interaction between inorganic perovskite and NiO can be improved. x This addresses the mismatch in valence band energy levels, enhances the ability to extract holes, achieves carrier extraction balance, and improves the open-circuit voltage and photoelectric conversion efficiency of inverted inorganic perovskite solar cells.

Description

Technical Field

[0001] This invention belongs to the field of new energy, specifically relating to a P - Preparation method of EDTA-N material and its application in inverted inorganic perovskite solar cells. Background Technology

[0002] Inorganic perovskites have attracted widespread attention and rapid development due to their excellent thermal stability and great potential in high-efficiency tandem solar cells. Although the photoelectric conversion efficiency (PCE) of positive-structure inorganic perovskite solar cells (IPSCs) has exceeded 21%, inverse-structure inorganic perovskite solar cells are more suitable for tandem cells due to their advantages such as less parasitic absorption of light by charge transport materials, low hysteresis, and lower fabrication temperature. However, the efficiency of inverse-structure IPSCs is still significantly lower than that of positive-structure IPSCs. One reason for this is the higher open-circuit voltage (Vo) of inverse-structure IPSCs. OC The loss is larger than that of positive structure IPSCs. OC The main reasons for the loss include the following two points: First, the nonradiative recombination of charge carriers caused by trapped states, including defects in the polycrystalline perovskite film and at the interface between the perovskite and the transport layer. The defect state density at the interface is much greater than that in the film. For inverse inorganic perovskite solar cells, hole transport layers such as NiO are commonly used. x The surface contains many high valence states, such as Ni. 3+ Ni 2+ Defects such as these are also present. Secondly, the mismatch in energy level positions between the inorganic perovskite and the carrier transport layers (hole transport layer and electron transport layer) leads to suboptimal carrier extraction, which can also cause V... OC The loss of NiO has led many researchers to focus on passivating it. x Defects of NiO x Energy level arrangement between it and perovskite.

[0003] EDTA is a strong chelating agent with a strong chelating effect on metals. Zhang et al. introduced EDTA and its derivatives EDTA-Na and EDTA-K into ZnO (Small 2023,19,2205604) and used this doped ZnO as an intermediate layer between SnO2 and CsPbI2Br inorganic perovskite. This strategy simultaneously passivates defects in ZnO and perovskite films, lowers the Fermi level of ZnO, modulates the interfacial energy level arrangement, releases interfacial stress, improves interfacial contact, alleviates nonradiative recombination of charges at the interface, and promotes electron transport. Yang et al. introduced EDTA into the electron transport layer SnO2 of a positive-structure perovskite solar cell (Nature Communications, 2018, 9:3239). The SnO2 composite with EDTA showed a better match with the conduction band energy level of the perovskite, and the electron mobility increased threefold. Ultimately, the positive-structure device achieved a photoelectric conversion efficiency of 21.60% (certified 21.52%). Furthermore, the low-temperature prepared SnO2 was applied to a flexible device, achieving an efficiency of 18.28%. This demonstrates that EDTA has a strong chelating effect and can be used to passivate defects at the interface between charge transport materials and perovskites. However, there are no reports of EDTA being used in inverted devices. This may be because pure EDTA is almost insoluble in ethanol and common organic solvents.

[0004] In summary, existing NiO-based technologies can be categorized as follows: x The shortcomings of inverse inorganic perovskite solar cells with hole transport layers and EDTA: 1) NiO x The surface has a large number of defects and NiO x The contact between the perovskite absorber layer and the solar cell needs improvement, as it leads to easy nonradiative recombination of charge carriers, thus suppressing the efficiency of inverse inorganic perovskite solar cells. 2) NiO x The energy level positions between the valence band and inorganic perovskite are not well matched, resulting in a large energy level barrier, which is not conducive to the effective extraction and rapid transport of holes. 3) Although EDTA can effectively passivate related defects in metal oxides and perovskites, its poor solubility in common organic solvents limits its application in inverted devices. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned shortcomings of the prior art and provide a P - Preparation method of EDTA-N material and its application in inverted inorganic perovskite solar cells.

[0006] To achieve the objectives of this invention, we propose using methylamine groups to replace some of the carboxyl groups on EDTA to form EDTA-N materials. EDTA-N materials formed in ethanol solvent exhibit P... -Its semiconductor properties allow it to be compatible with NiO. x Formed by P - To P + The field-enhancing structure forms a gradient energy level arrangement, which enhances the hole extraction capability and can achieve a higher open-circuit voltage (V). OC The -NH2CH3 and -COOH groups on EDTA-N can passivate NiO. x Ni in higher valence states 3+ Ni 2+ Defects were addressed by improving interfacial contact and reducing charge recombination, thereby increasing the battery's Vt. OC .

[0007] The technical solution of this invention:

[0008] A P - A method for preparing type EDTA-N materials, the method comprising:

[0009] (1) Regarding the preparation of EDTA-N solution;

[0010] (1-1) Weigh an appropriate amount of EDTA powder using a balance, disperse it in an appropriate amount of ethanol, and heat and stir at 40-80℃ for 1-2 hours in air.

[0011] (1-2) Add an appropriate amount of methylamine liquid to the dispersion obtained in step (1-1) and continue stirring for 1-2 hours to obtain P. - Type EDTA-N;

[0012] (2) Preparation of EDTA-N modified layer;

[0013] The EDTA-N modified layer was applied to NiO using a spin-coating method. x The hole transport layer was prepared by spin-coating the EDTA-N solution prepared in step (1) onto NiO at a rotation speed of 4000-6000 rpm. x The annealing process is carried out at a temperature of 80-120℃ for 20-40 seconds and a time of 5-15 minutes.

[0014] Furthermore, in this invention, NiO x The hole transport layer was obtained as follows: the FTO surface was ultrasonically cleaned with deionized water and isopropanol, then dried with nitrogen gas, and finally subjected to ultraviolet ozone for 15-30 minutes; the prepared NiO was then taken. x Nanoparticles were dispersed in deionized water at a concentration of 20-25 mg / mL; FTO was placed in a spin coater, and NiO was then coated onto the surface. xThe nanoparticle dispersion was uniformly spin-coated onto the FTO surface at a speed of 1500-2500 rpm for 20-40 s, and then annealed in ambient air at 120-140℃ for 20-40 min to obtain NiO. x Hole transport layer.

[0015] This invention also provides P - Application of EDTA-N material in inverted inorganic perovskite solar cells.

[0016] Furthermore, the P - The application of EDTA-N material in inverted inorganic perovskite solar cells is achieved through the following steps:

[0017] 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide were dissolved in 1 mL of N,N-dimethylformamide (DMF) solvent and heated and stirred until completely dissolved to obtain a CsPbI3 perovskite solution.

[0018] The obtained CsPbI3 perovskite solution was coated on the surface of an EDTA-N film. After rotating at 1800-2200 rpm for 20-40 seconds, it was removed and annealed in air at 180-190℃ for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0019] 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0020] PC obtained 61 BM solution was spin-coated onto a CsPbI3 perovskite film at 2000 rpm for 20-40 s to obtain PC. 61 BM electron transport layer;

[0021] Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0022] The obtained BCP solution was spin-coated onto PC. 61 The BM surface is rotated at a speed of 4000-6000 rpm for 20-40 seconds to obtain a buffer layer;

[0023] An 80-100 nm thick metal electrode Ag was deposited using a thermal evaporation method.

[0024] Trans-inorganic perovskite solar cells were obtained.

[0025] This invention relates to an inorganic perovskite solar cell with a PIN structure. The inorganic perovskite is CsPbI3 with a bandgap of 1.68 eV. The inorganic perovskite solar cell comprises, in sequence: a transparent conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode. This invention's inorganic perovskite solar cell also incorporates NiO obtained by the above method. x Thin films and in NiO x Preparation of P on thin films - Type EDTA-N modified layer.

[0026] The transparent conductive substrate is FTO conductive glass. The perovskite light-absorbing layer is a perovskite thin film with a thickness of 450-500 nm. The hole transport layer material is NiO. x The electron transport layer material is PC. 61 BM. The buffer layer material is BCP. The electrode is a silver electrode with a thickness of 80-100 nm deposited by vacuum evaporation.

[0027] The method for preparing the perovskite solar cell of the present invention is as follows:

[0028] (1) Preparation of NiO on FTO conductive glass x (1) Electron transport layer; (2) Perovskite light-absorbing layer is prepared by spin coating on hole transport layer in air; (3) Electron transport layer is prepared by spin coating on perovskite light-absorbing layer; (4) Buffer layer is deposited after electron transport layer; (5) Metal electrode is deposited on buffer layer.

[0029] The advantages and positive effects of this invention are:

[0030] This invention forms EDTA-N material by replacing some of the carboxyl groups on EDTA with methylamine groups. EDTA-N is highly soluble in ethanol. Furthermore, this invention also achieves P-type EDTA-N material. - Type semiconductor, and used as an interface layer in NiO x The PI interface with perovskite successfully formed a P-type interface. - To P + The field-enhancing structure also effectively passivates NiO. x The improved wettability, which addresses the defects of perovskite, enhances the interfacial contact between perovskite and P-type materials, thereby improving the crystallinity of the perovskite film and increasing the V-value of the battery. OC And FF, thus obtaining more efficient inverse inorganic perovskite solar cells, in addition, P - The EDTA-N type can also be used as an intermediate layer at the PI interface in inverted inorganic perovskite and silicon tandem solar cells. Attached Figure Description

[0031] Figure 1 The specific embodiments of the present invention are based on P - A schematic diagram of the structure of EDTA-N material applied to inverted inorganic perovskite solar cells;

[0032] Figure 2 This is a current-voltage characteristic curve of an inverting inorganic perovskite solar cell based on EDTA-N with a concentration of 0.25 mg / mL as the intermediate layer of the PI interface, according to a specific embodiment of the present invention.

[0033] Figure 3 This is a current-voltage characteristic curve of an inverting inorganic perovskite solar cell based on EDTA-N with a concentration of 0.5 mg / mL as the intermediate layer of the PI interface, according to a specific embodiment of the present invention.

[0034] Figure 4 This is a current-voltage characteristic curve of an inverting inorganic perovskite solar cell based on a 1 mg / mL concentration of EDTA-N as the intermediate layer of the PI interface, according to a specific embodiment of the present invention.

[0035] Figure 5 This is a current-voltage characteristic curve of an inverting inorganic perovskite solar cell based on 0.5 mg / mL EDTA-N annealed at 80 °C as an intermediate layer of the PI interface, according to a specific embodiment of the present invention.

[0036] Figure 6 This is a current-voltage characteristic curve of an inverting inorganic perovskite solar cell based on 0.5 mg / mL EDTA-N annealed at 120 °C as an intermediate layer of the PI interface, according to a specific embodiment of the present invention.

[0037] Figure 7 The comparative embodiments of the present invention are based on P-free - The current-voltage characteristic curve of an inverse inorganic perovskite solar cell made of EDTA-N material;

[0038] Figure 8 This is a current-voltage characteristic curve of an inverse inorganic perovskite solar cell based on 1 mg / mL EDTA-N as the hole transport layer in the comparative embodiment of the present invention. Detailed Implementation

[0039] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0040] According to the appendix Figure 1 The structure shown includes, from bottom to top, a transparent conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode.

[0041] Example 1:

[0042] The present invention provides a P - The preparation method of type EDTA-N material and its application in inverted inorganic perovskite solar cells include the following steps:

[0043] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 20 minutes.

[0044] 2. Take the prepared NiO x Nanoparticles were dispersed in deionized water at a concentration of 20 mg / mL;

[0045] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 2000 rpm for 30 s, and then annealed in ambient air at 130 °C for 30 min to obtain NiO. x Hole transport layer;

[0046] 4. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 60°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1 hour. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0047] 5. Take the 0.25 mg / mL EDTA-N solution obtained in step 4 and spin-coat it onto the NiO obtained in step 3. x The hole transport layer surface was rotated at 5000 rpm for 30 seconds, then removed and annealed at 100°C for 10 minutes to obtain an EDTA-N film.

[0048] 6. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0049] 7. Spin-coat the perovskite solution obtained in step 6 onto the surface of the EDTA-N film obtained in step 5. After spinning at 2000 rpm for 30 seconds, remove the film and anneal it in air at 185°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0050] 8. Take 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0051] 9. Take the PC obtained in step 8. 61 The BM solution was spin-coated onto the perovskite film obtained in step 7 at a speed of 2000 rpm for 30 seconds to obtain PC. 61 BM electron transport layer;

[0052] 10. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0053] 11. Take the BCP solution from step 10 and spin-coat it onto the PC from step 9. 61 The BM surface is rotated at 5000 rpm for 30 seconds to obtain a buffer layer;

[0054] 12. Deposit an 80-100 nm thick metal electrode Ag using a thermal evaporation method.

[0055] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 2 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.199V and a short-circuit current density of 19.96mA / cm². 2 The fill factor is 83.47%, and the efficiency is 19.98%.

[0056] Example 2:

[0057] The present invention provides a P - The preparation method of type EDTA-N material and its application in inverted inorganic perovskite solar cells include the following steps:

[0058] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 20 minutes.

[0059] 2. Take the prepared NiO x Nanoparticles were dispersed in deionized water at a concentration of 20 mg / mL;

[0060] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 2000 rpm for 30 s, and then annealed in ambient air at 130 °C for 30 min to obtain NiO. x Hole transport layer;

[0061] 4. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 60°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1 hour. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0062] 5. Take the 0.5 mg / mL EDTA-N solution obtained in step 4 and spin-coat it onto the NiO obtained in step 3. xThe hole transport layer surface was rotated at 5000 rpm for 30 seconds, then removed and annealed at 100°C for 10 minutes to obtain an EDTA-N film.

[0063] 6. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0064] 7. Spin-coat the perovskite solution obtained in step 6 onto the surface of the EDTA-N film obtained in step 5. After spinning at 2000 rpm for 30 seconds, remove the film and anneal it in air at 185°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0065] 8. Take 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0066] 9. Take the PC obtained in step 8. 61 The BM solution was spin-coated onto the perovskite film obtained in step 7 at a speed of 2000 rpm for 30 seconds to obtain PC. 61 BM electron transport layer;

[0067] 10. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0068] 11. Take the BCP solution from step 10 and spin-coat it onto the PC from step 9. 61 The BM surface is rotated at 5000 rpm for 30 seconds to obtain a buffer layer;

[0069] 12. Deposit an 80-100 nm thick metal electrode Ag using a thermal evaporation method.

[0070] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 3 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.234V and a short-circuit current density of 19.97mA / cm². 2 The fill factor is 83.97%, and the efficiency is 20.71%.

[0071] Example 3:

[0072] The present invention provides a P - The preparation method of type EDTA-N material and its application in inverted inorganic perovskite solar cells include the following steps:

[0073] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 20 minutes.

[0074] 2. Take the prepared NiO x Nanoparticles were dispersed in deionized water at a concentration of 20 mg / mL;

[0075] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 2000 rpm for 30 s, and then annealed in ambient air at 130 °C for 30 min to obtain NiO. x Hole transport layer;

[0076] 4. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 60°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1 hour. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0077] 5. Take the 1 mg / mL EDTA-N solution obtained in step 4 and spin-coat it onto the NiO obtained in step 3. x The hole transport layer surface was rotated at 5000 rpm for 30 seconds, then removed and annealed at 100°C for 10 minutes to obtain an EDTA-N film.

[0078] 6. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0079] 7. Spin-coat the perovskite solution obtained in step 6 onto the surface of the EDTA-N film obtained in step 5. After spinning at 2000 rpm for 30 seconds, remove the film and anneal it in air at 185°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0080] 8. Take 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0081] 9. Take the PC obtained in step 8. 61 The BM solution was spin-coated onto the perovskite film obtained in step 7 at a speed of 2000 rpm for 30 seconds to obtain PC. 61 BM electron transport layer;

[0082] 10. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0083] 11. Take the BCP solution from step 10 and spin-coat it onto the PC from step 9. 61 The BM surface is rotated at 5000 rpm for 30 seconds to obtain a buffer layer;

[0084] 12. Deposit an 80-100 nm thick metal electrode Ag using a thermal evaporation method.

[0085] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 4 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.203V and a short-circuit current density of 19.93mA / cm². 2 The fill factor is 84.66%, and the efficiency is 20.30%.

[0086] Example 4:

[0087] This invention provides a P - The preparation method of type EDTA-N material and its application in inverted inorganic perovskite solar cells include the following steps:

[0088] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 15 minutes.

[0089] 2. Take the prepared NiO x Nanoparticles were dispersed in deionized water at a concentration of 20 mg / mL;

[0090] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 1500 rpm for 20-40 s, and then annealed in ambient air at 120 °C for 40 min to obtain NiO. x Hole transport layer;

[0091] 4. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 40°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1-2 hours. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0092] 5. Take the 0.5 mg / mL EDTA-N solution obtained in step 4 and spin-coat it onto the NiO obtained in step 3. x The hole transport layer surface was rotated at 4000 rpm for 20 seconds, then removed and annealed at 80°C for 15 minutes to obtain an EDTA-N film.

[0093] 6. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0094] 7. Spin-coat the perovskite solution obtained in step 6 onto the surface of the EDTA-N film obtained in step 5. After spinning at 1800 rpm for 20 seconds, remove the film and anneal it in air at 180°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0095] 8. Take 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0096] 9. Take the PC obtained in step 8. 61 The BM solution was spin-coated onto the perovskite film obtained in step 7 at a speed of 2000 rpm for 20 seconds to obtain PC. 61 BM electron transport layer;

[0097] 10. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0098] 11. Take the BCP solution from step 10 and spin-coat it onto the PC from step 9. 61 The BM surface is rotated at 4000 rpm for 20-40 seconds to obtain a buffer layer;

[0099] 12. Deposit an 80-100 nm thick metal electrode Ag using a thermal evaporation method.

[0100] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 5 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.193V and a short-circuit current density of 20.09mA / cm². 2 The fill factor is 83.58%, and the efficiency is 20.03%.

[0101] Example 5:

[0102] The present invention provides a P - The preparation method of type EDTA-N material and its application in inverted inorganic perovskite solar cells include the following steps:

[0103] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 30 minutes.

[0104] 2. Take the prepared NiOx Nanoparticles were dispersed in deionized water at a concentration of 25 mg / mL;

[0105] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 2500 rpm for 20-40 s, and then annealed in ambient air at 140 °C for 20 min to obtain NiO. x Hole transport layer;

[0106] 4. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 80°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1-2 hours. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0107] 5. Take the 0.5 mg / mL EDTA-N solution obtained in step 4 and spin-coat it onto the NiO obtained in step 3. x The hole transport layer surface was rotated at 6000 rpm for 40 seconds, then removed and annealed at 120°C for 5 minutes to obtain an EDTA-N film.

[0108] 6. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0109] 7. Spin-coat the perovskite solution obtained in step 6 onto the surface of the EDTA-N film obtained in step 5. After spinning at 2200 rpm for 40 seconds, remove the film and anneal it in air at 190°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0110] 8. Take 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0111] 9. Take the PC obtained in step 8. 61 The BM solution was spin-coated onto the perovskite film obtained in step 7 at a speed of 2000 rpm for 40 s to obtain PC. 61 BM electron transport layer;

[0112] 10. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0113] 11. Take the BCP solution from step 10 and spin-coat it onto the PC from step 9. 61 The BM surface is rotated at 6000 rpm for 20-40 seconds to obtain a buffer layer;

[0114] 12. Deposit an 80-100 nm thick metal electrode Ag using a thermal evaporation method.

[0115] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 6 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.217V and a short-circuit current density of 19.63mA / cm². 2 The fill factor is 84.42%, and the efficiency is 20.18%.

[0116] Comparative Example 1:

[0117] Based on no P - The application of inverse inorganic perovskite solar cells using EDTA-N materials includes the following steps:

[0118] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 20 minutes.

[0119] 2. Take the prepared NiO x Nanoparticles were dispersed in deionized water at a concentration of 20 mg / mL;

[0120] 3. Place FTO in a spin coater and coat NiO. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at 2000 rpm for 30 s, and then annealed in ambient air at 130 °C for 30 min to obtain NiO. x Hole transport layer;

[0121] 4. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0122] 5. Spin-coat the perovskite solution obtained in step 4 onto the NiO obtained in step 3. x The hole transport layer surface was rotated at 2000 rpm for 30 seconds, then removed and annealed in air at 185°C for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0123] 6. Add 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0124] 7. Take the PC obtained in step 6. 61 The BM solution was spin-coated onto the perovskite film obtained in step 5 at a speed of 2000 rpm for 30 seconds to obtain PC.61 BM electron transport layer;

[0125] 8. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0126] 9. Take the BCP solution from step 8 and spin-coat it onto the PC from step 7. 61 The BM surface is rotated at 5000 rpm for 30 seconds to obtain a buffer layer;

[0127] 10. Deposit 80-100 nm thick Ag metal electrodes using thermal evaporation.

[0128] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 5 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.194V and a short-circuit current density of 19.78mA / cm². 2 The fill factor is 80.31%, and the efficiency is 18.97%.

[0129] Comparative Example 2:

[0130] 1. The FTO area is 2cm×2cm. The surface treatment sequence is: ultrasonic cleaning with deionized water and isopropanol, then drying with nitrogen, and finally UV ozone treatment of the substrate for 20 minutes.

[0131] 2. Disperse EDTA powder in an appropriate amount of ethanol, heat and stir at 60°C for 1-2 hours, add an appropriate amount of methylamine liquid, and continue stirring for 1 hour. Then dilute with pure ethanol in equal proportions to obtain EDTA-N solutions of different concentrations.

[0132] 3. Take the 1 mg / mL EDTA-N solution obtained in step 2 and spin-coat it onto the FTO obtained in step 1. Spin-coat it at 5000 rpm for 30 seconds, remove it, and anneal it at 100°C for 10 minutes to obtain an EDTA-N film as a hole transport layer.

[0133] 4. Dissolve 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heat and stir until completely dissolved to obtain a CsPbI3 perovskite solution;

[0134] 5. Take the perovskite solution obtained in step 4 and spin-coat it onto the surface of the EDTA-N hole transport layer obtained in step 3. After spinning at 2000 rpm for 30 seconds, remove it and anneal at 70°C for 30-40 seconds, then anneal at 185°C in air for 5-10 minutes to obtain a CsPbI3 perovskite film.

[0135] 6. Add 20mg PC 61 BM was dissolved in 1 mL of chlorobenzene solvent;

[0136] 7. Take the PC obtained in step 6. 61 The BM solution was spin-coated onto the perovskite film obtained in step 5 at a speed of 2000 rpm for 30 seconds to obtain PC. 61 BM electron transport layer;

[0137] 8. Dissolve 6 mg of BCP in 12 mL of isopropanol solvent and stir until completely dissolved;

[0138] 9. Take the BCP solution from step 8 and spin-coat it onto the PC from step 7. 61 The BM surface is rotated at 5000 rpm for 30 seconds to obtain a buffer layer;

[0139] 10. Deposit 80-100 nm thick Ag metal electrodes using thermal evaporation.

[0140] Experimental Results: Performance testing of solar cells was conducted, such as... Figure 6 As shown, at AM1.5, 100mW / cm 2 Under standard light intensity irradiation, the solar cell prepared in this embodiment exhibits an open-circuit voltage of 1.136V and a short-circuit current density of 18.73mA / cm². 2 The fill factor is 80.37%, and the efficiency is 17.10%.

[0141] In summary, the present invention provides a P - The preparation method of type EDTA-N material and its application in trans-inorganic perovskite solar cells are described. EDTA-N is formed by replacing some of the carboxyl groups on EDTA with methylamine. EDTA-N is a P... - A type of semiconductor material that is well soluble in ethanol, NiO can be used in inverse inorganic perovskite solar cells. x At the PI interface with perovskite, a structure composed of P... - To P + The field-enhancing structure improves the hole extraction capability and enhances hole transport, thereby increasing the fill factor (FF) of the battery; this invention can also passivate NiO using EDTA-N. x Surface defects improve the contact between the perovskite and the p-type substrate, enhance crystal quality, and reduce nonradiative recombination of charge carriers, thereby increasing the open-circuit voltage (V). OC This will enable the production of more efficient trans-inorganic perovskite solar cells.

[0142] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An inorganic perovskite solar cell, characterized in that, The inorganic perovskite solar cell has a PIN structure, and the inorganic perovskite is CsPbI3 with a band gap of 1.68 eV. The inorganic perovskite solar cell structure comprises, in sequence: a transparent conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode; The inorganic perovskite solar cell has NiO x Thin films and in NiO x P prepared on thin film - Type EDTA-N modified layer; EDTA-N is a material formed by replacing some of the carboxyl groups on EDTA with methylamine groups; The P mentioned - The preparation method of the type EDTA-N modified layer is as follows: (1) Weigh an appropriate amount of EDTA powder using a balance, disperse it in an appropriate amount of ethanol, and heat and stir at 40-80℃ for 1-2 h in air. (2) Add an appropriate amount of methylamine liquid to the dispersion obtained in step (1) and continue stirring for 1-2 h to obtain P. - Type EDTA-N; (3) Spin coating method is used on NiO x P prepared on thin film - Type EDTA-N modified layer; spin coating method with a rotation speed of 4000-6000 rpm, a time of 20-40 s, an annealing temperature of 80-120℃, and an annealing time of 5-15 min.

2. The inorganic perovskite solar cell as described in claim 1, characterized in that, The transparent conductive substrate of the inorganic perovskite solar cell is FTO conductive glass; The hole transport layer of the inorganic perovskite solar cell is NiO. x ; The inorganic perovskite light-absorbing layer of the inorganic perovskite solar cell is a CsPbI3 inorganic perovskite thin film with a thickness of 450-500 nm. The electron transport layer material of the inorganic perovskite solar cell is PC. 61 BM; The buffer layer material of the inorganic perovskite solar cell is BCP; The electrodes of the perovskite solar cell are silver electrodes deposited at 80-100 nm using a vacuum evaporation method.

3. The inorganic perovskite solar cell as described in claim 2, characterized in that, NiO x The hole transport layer was obtained as follows: the FTO surface was ultrasonically cleaned with deionized water and isopropanol, then dried with nitrogen gas, and finally subjected to ultraviolet ozone for 15-30 min; the prepared NiO was then taken. x Nanoparticles were dispersed in deionized water at a concentration of 20-25 mg / mL; FTO was placed in a spin coater, and NiO was then coated onto the surface. x The nanoparticle dispersion was uniformly spin-coated onto the FTO surface at a speed of 1500-2500 rpm for 20-40 s, and then annealed in ambient air at 120-140℃ for 20-40 min to obtain NiO. x Hole transport layer.

4. The inorganic perovskite solar cell as described in claim 2, characterized in that, CsPbI3 perovskite films were obtained by dissolving 181.87 mg of cesium iodide, 121.1 mg of dimethylammonium iodide, and 322.7 mg of lead iodide in 1 mL of N,N-dimethylformamide (DMF) solvent, heating and stirring until completely dissolved to obtain a CsPbI3 perovskite solution. A CsPbI3 perovskite solution was spin-coated onto the surface of an EDTA-N film. After spinning at 1800-2200 rpm for 20-40 s, the film was removed and annealed in air at 180-190℃ for 5-10 min to obtain a CsPbI3 perovskite film.

5. The inorganic perovskite solar cell as described in claim 2, characterized in that, The electron transport layer was obtained by: adding 20 mg of PC 61 BM was dissolved in 1 mL of chlorobenzene solvent; PC was then added. 61 BM solution was spin-coated onto a CsPbI3 perovskite film at 2000 rpm for 20-40 s to obtain PC. 61 BM electron transport layer.

6. The inorganic perovskite solar cell as described in claim 2, characterized in that, The buffer layer was obtained by dissolving 6 mg BCP in 12 mL of isopropanol solvent and stirring until completely dissolved; Spin-coating BCP solution onto PC 61 The surface of the BM electron transport layer is rotated at a speed of 4000-6000 rpm for 20-40 s to obtain the BCP buffer layer.

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