A bio-modified perovskite solar cell and its fabrication method

Abstract

This invention discloses a bio-modified perovskite solar cell and its fabrication method. The method includes the following steps: preparing an electron or hole transport layer on a transparent conductive substrate; spin-coating a rare-earth-based heme solution onto the electron or hole transport layer to form a heme derivative modification layer; spin-coating a perovskite precursor solution onto the heme derivative modification layer to obtain a perovskite thin film; and spin-coating a hole or electron transport layer onto the perovskite thin film and fabricating a top electrode to obtain a perovskite solar cell. The heme derivative added to the perovskite solar cell in this invention has multiple synergistic effects. It can suppress defect-induced nonradiative recombination in the perovskite thin film, improve the carrier mobility of the device, and, more importantly, improve the utilization rate of the ultraviolet band of the solar spectrum due to the Foster resonance energy transfer effect, reduce the decomposition of the perovskite thin film under ultraviolet light, and improve the energy conversion efficiency and photothermal stability of the device.

Description

Technical Field

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

[0002] In recent years, organic-inorganic hybrid halide perovskite solar cells have developed rapidly, with their power conversion efficiency (PCE) jumping from an initial 3.9% to 25.7%. This is attributed to their excellent photoelectric properties, such as high absorption coefficient, tunable bandgap, and low-cost solution processing. However, solution-prepared perovskite films generate numerous defects at grain boundaries or surfaces, leading to significant energy loss through induced nonradiative recombination. Furthermore, the spectral response of perovskite materials is concentrated in the visible light region, failing to effectively utilize photon energy in the ultraviolet and infrared bands. Excess ultraviolet light can also cause thermal degradation and energy loss in perovskite. Therefore, passivating surface / interface defects in perovskite films and improving the photothermal stability of devices are crucial pathways to enhancing the efficiency of perovskite solar cells.

[0003] Early studies have demonstrated that, among numerous organic molecules, carboxyl-containing metalloporphyrin macrocyclic compounds can act as passivators for perovskite thin films, controlling crystallization and reducing defects, thereby improving the photoelectric performance of devices (Advanced Functional Materials, 2021, 31, 2007762). Adding Eu-monoporphyrin complexes to perovskite precursor solutions can form a two-dimensional perovskite phase, significantly improving device stability, but conversely, reducing photoelectric conversion efficiency (Advanced Science, 2019, 6, 1802040). These studies all focus on single-functional improvements and cannot simultaneously achieve defect passivation and stability enhancement in perovskite solar cells while further improving the energy conversion efficiency of perovskite devices.

[0004] This invention is influenced by the 1948... Inspired by the proposed resonant energy transfer theory model, the donor and acceptor can transfer photon energy absorbed by the donor to the acceptor through dipole-to-dipole interactions, and this energy can then be released by the latter in the form of emitted photons. Given that rare earth elements possess a unique 4f-layer electronic structure, they can absorb ultraviolet light and convert it into visible light photon energy. This visible light energy can be effectively absorbed by perovskite thin films, thus improving the ultraviolet light utilization rate and enhancing the ultraviolet stability of perovskite solar cells. This invention achieves a synergistic effect of effectively passivating defects in perovskite solar cells, enhancing photothermal stability, and improving device efficiency. Summary of the Invention

[0005] This invention provides a bio-modified perovskite solar cell and its preparation method, comprising the following steps:

[0006] Fabrication of electron or hole transport layers on transparent conductive substrates;

[0007] Rare earth-based heme solution is spin-coated onto an electron or hole transport layer to form a heme derivative modification layer;

[0008] Perovskite precursor solution was spin-coated onto heme derivative modified layer to obtain perovskite thin film layer;

[0009] A perovskite solar cell is obtained by spin-coating a hole or electron transport layer onto a heme derivative modified layer and fabricating a top electrode.

[0010] Preferably, the rare earth element in the rare earth-based heme solution is europium, samarium, cerium, terbium, or dysprosium.

[0011] Preferably, the specific steps for spin-coating a rare earth-based heme solution onto an electron or hole transport layer to form a heme derivative modified layer are as follows: the rare earth-based heme is first dissolved in chlorobenzene, and then spin-coated onto the electron or hole transport layer to form a heme derivative modified layer.

[0012] Preferably, the concentration of the rare earth-based heme solution is 0.05–0.2 mmol / L.

[0013] Preferably, the rare earth-based heme is synthesized by reacting porphyrin derivatives with rare earth ions in acetate.

[0014] Preferably, the rare earth-based heme is prepared by: dissolving a porphyrin derivative in methanol, dissolving a rare earth ion acetate in chloroform, and reacting the mixture to obtain rare earth-based heme; and dissolving the rare earth-based heme in a mixed solvent composed of chlorobenzene and acetic acid to obtain a rare earth-based heme solution.

[0015] Preferably, the ratio of chlorobenzene to acetic acid in the mixed solvent is 9:1.

[0016] Preferably, the transparent conductive substrate is one of glass substrate, quartz substrate, PET plastic substrate, PEN plastic substrate, and PI plastic substrate, and an indium tin oxide, fluorine-doped tin dioxide, or grid silver film is prepared on it as a conductive layer.

[0017] Preferably, the electron transport layer material is one or more of ZnO, TiO2, SnO2, PCBM, fullerene, and fullerene derivatives.

[0018] Preferably, the molecular structure of the perovskite thin film is ABX3, wherein A is one or more of FA, MA, and Cs, B is one or more of Pb and Sn, and X is one or more of Cl, Br, and I.

[0019] Preferably, the hole transport layer material is one or more of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly3,4-ethylenedioxythiophene / polystyrene sulfonate, nickel oxide, copper oxide, 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, cuprous thiocyanate, and molybdenum oxide.

[0020] Preferably, the top electrode is one or more of the following: Au electrode, Ag electrode, Al electrode, Cu electrode, carbon electrode, PH1000 polymer electrode, and metal oxide electrode.

[0021] This invention also provides a bio-modified perovskite solar cell. The bio-modified perovskite solar cell is prepared by the above method. The structure of the solar cell, from bottom to top, is as follows: a transparent conductive substrate, an electron transport layer, a heme derivative modification layer, a perovskite thin film layer, a hole transport layer, and a top electrode; or, a transparent conductive substrate, a hole transport layer, a heme derivative modification layer, a perovskite thin film layer, an electron transport layer, and a top electrode.

[0022] The heme derivative added to perovskite solar cells in this invention exhibits multiple synergistic effects. It can passivate defects on the surface of the perovskite thin film, effectively suppress defect-induced nonradiative recombination in perovskite solar cells, and promote carrier transport performance. The heme derivative contains rare earth ions, which can improve the utilization of the ultraviolet band of the solar spectrum, reduce the decomposition of the perovskite thin film under ultraviolet light, and enhance the energy conversion efficiency of the device. This invention realizes the application of novel natural macromolecules and their derivatives in the perovskite field, improving the device stability and energy conversion efficiency of perovskite solar cells. Attached Figure Description

[0023] Figure 1 This is a flowchart illustrating the fabrication method of bio-modified perovskite solar cells.

[0024] Figure 2 This is a schematic diagram of a bio-modified perovskite solar cell.

[0025] Figure 3 Examples of rare earth-based heme and their synthetic pathways (taking europium-based heme Eu-Hgb as an example); Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1

[0028] This embodiment provides a method for preparing a bio-modified perovskite solar cell, such as... Figure 1 As shown, the specific steps are as follows:

[0029] S110. The FTO conductive glass is continuously ultrasonically washed in deionized water, acetone, ethanol and isopropanol for 15 min, then dried under nitrogen, and treated with ultraviolet / ozone for 20-30 min. 1.0 mL of 15% SnO2 solution is taken with a pipette, and 4.6 mL of deionized water is added to dilute the SnO2 solution to 2.67% to prepare an electron transport layer precursor solution. The electron transport layer precursor solution can also be a ZnO or TiO2 solution, prepared in the same way as the SnO2 solution. The electron transport layer precursor solution is filtered and then spin-coated onto the FTO conductive glass at 4000 r / min for 30 s to form a modified electron transport layer. After annealing, it is treated with ultraviolet-ozone for 15 min, and then transferred to a glove box filled with N2.

[0030] S120. Weigh 100.00 mg of porphyrin derivative (CAS: 553-12-8, M = 562.66 g / mol) and dissolve it in 10.00 mL of methanol. Then weigh 272.957 mg of Eu(OAc)3 (M = 329.092 g / mol) and dissolve it in 100 mL of chloroform. Mix the two solutions to prepare europium heme (Eu-Hgb, M = 714.62 g / mol). Weigh 0.36 mg of Eu-Hgb and dissolve it in 10.00 mL of a mixed solvent of chlorobenzene and acetic acid (9:1) to obtain a Eu-Hgb solution with a concentration of 0.050 mmol / L. Spin-coat Eu-Hgb onto the electron transport layer using a spin-coating method with spin-coating parameters set to 4000 rpm and 30 s. Finally, anneal at 100 °C for 1 min to obtain the Eu-Hgb modified layer.

[0031] S130. Methylamine iodide (1.25 mol) and lead iodide (1.25 mol) are dissolved in a mixed solvent of N,N-dimethylformamide:dimethyl sulfoxide = 8-10:1, and stirred at 60°C for 12 hours to form a perovskite precursor solution. The perovskite precursor solution is then spin-coated onto the heme derivative modified layer to prepare a perovskite thin film. The perovskite structure of the perovskite precursor solution is MAPbI3 or MA. 0.8 FA 0.2 The specific operation method for spin coating PbI3 is as follows: accelerate to 1500 r / min at an acceleration of 5000 r / min and rotate for 10 s, then accelerate to 4000 r / min at an acceleration of 1000 r / min and rotate for another 25 s, with a total spin coating time of 30-40 s. In the last 5 s before the end of spin coating, add 300 μL of anti-solvent chlorobenzene to the perovskite film. Anneal the perovskite film with added anti-solvent chlorobenzene in a glove box at 100 °C for 10 min to form a perovskite film layer, and then cool for 5 min.

[0032] S140: Weigh 520 mg of lithium bis(trifluoromethanesulfonyl)imide and dissolve it in 1 mL of anhydrous acetonitrile to prepare a lithium bis(trifluoromethanesulfonyl)imide solution; dissolve 72.3 mg of Spiro-OMeTAD in 1 mL of chlorobenzene, then add 28.8 μL of tributyl phosphate solution and 17.5 μL of lithium bis(trifluoromethanesulfonyl)imide solution; use a pipette to pick up 75 μL of Spiro-OMeTAD precursor solution, set the rotation speed to 3000 r / min, the acceleration to 1000 r / min, and the time to 30 s, and spin-coat the hole transport material onto a perovskite film to prepare a hole transport layer. The hole transport layer is Spiro-OMeTAD, and its thickness is approximately 100 nm; under a vacuum degree <1×10 -5 Under Tor conditions, metallic Au is deposited onto the hole transport layer at a rate of 0.1–0.3 A per second to form a 100 nm Au electrode.

[0033] Example 2

[0034] This embodiment provides a method for preparing a bio-modified perovskite solar cell, which differs from Embodiment 1 in that S120 is modified as follows:

[0035] S120: Weigh 100.00 mg of porphyrin derivative (CAS: 553-12-8, M = 562.66 g / mol) and dissolve it in 10.00 mL of methanol. Then weigh 271.630 mg of Sm(OAc)3 (M = 327.492 g / mol) and dissolve it in 100 mL of chloroform. Mix the two solutions to prepare samarium-heme (Sm-Hgb, M = 713.02 g / mol). Weigh 0.36 mg of Sm-Hgb and dissolve it in 10.00 mL of a mixed solvent of chlorobenzene and acetic acid (9:1) to obtain a Sm-Hgb solution with a concentration of 0.050 mmol / L. Spin-coat the Sm-Hgb onto the electron transport layer using a spin-coating method with spin-coating parameters set to 4000 rpm and 30 s. Finally, anneal at 100 °C for 1 min to obtain the Sm-Hgb modified layer.

[0036] All other steps were the same, resulting in a Sm-Hgb modified layer with a concentration of 0.050 mmol / L.

[0037] Example 3

[0038] This embodiment provides a method for fabricating an inverted planar heterojunction perovskite solar cell, such as... Figure 1 As shown, it includes the following steps:

[0039] S110. The ITO conductive glass is continuously ultrasonically washed in deionized water, acetone, ethanol and isopropanol for 15 min, and then treated with ultraviolet / ozone for 10-20 min.

[0040] S120. A hole transport layer is prepared by continuously spin-coating a poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) solution onto ITO conductive glass at a speed of 4000 rpm for 45 s. The ITO conductive glass with the hole transport layer prepared is then annealed at 120°C for 20 min and immediately transferred to a glove box (oxygen and humidity should be less than 0.01 ppm).

[0041] S130. Weigh 100.00 mg of porphyrin derivative (CAS: 553-12-8, M = 562.66 g / mol) and dissolve it in 10.00 mL of methanol. Then weigh 272.957 mg of Eu(OAc)3 (M = 329.092 g / mol) and dissolve it in 100 mL of chloroform. Mix the two solutions to prepare europium heme (Eu-Hgb, M = 714.62 g / mol). Weigh 0.36 mg of Eu-Hgb and dissolve it in 10.00 mL of a mixed solvent of chlorobenzene and acetic acid (9:1) to obtain a Eu-Hgb solution with a concentration of 0.050 mmol / L. Spin-coat Eu-Hgb onto the hole transport layer using a spin-coating method with spin-coating parameters set to 4000 rpm and 30 s. Finally, anneal at 100 °C for 1 min to obtain the Eu-Hgb modified layer.

[0042] S140. Methylamine iodide (1.25 mol) and lead iodide (1.25 mol) are dissolved in a mixed solvent of N,N-dimethylformamide:dimethyl sulfoxide = 8-10:1, and stirred at 60°C for 12 hours to form a perovskite precursor solution. The perovskite precursor solution is then spin-coated onto the heme derivative modified layer to prepare a perovskite thin film. The perovskite structure of the perovskite precursor solution is MAPbI3 or MA. 0.8 FA 0.2 The specific spin-coating procedure for PbI3 is as follows: Accelerate from 5000 r / min to 1500 r / min and rotate for 10 seconds, then accelerate from 1000 r / min to 4000 r / min and rotate for another 25 seconds, for a total spin-coating time of 30–40 seconds. In the last 5 seconds before the end of the spin coating, add 300 μL of the anti-solvent chlorobenzene to the perovskite film; anneal the perovskite film with the added chlorobenzene in a glove box at 100°C for 10 minutes; then add PC at a concentration of 20 mg / mL. 61 BM spin-coated the perovskite thin film at 2000 rpm for 60 seconds, depositing an electron transport layer on top of the perovskite layer; the device semi-finished product was then transferred to approximately 1×10 -6 Finally, in a vacuum thermal evaporation machine with an 80-meter bar, approximately 80 nm of Ag is deposited onto the perovskite film.

[0043] Example 4

[0044] This embodiment provides a method for fabricating an inverted planar heterojunction perovskite solar cell. The difference from Embodiment 3 is that S130 is modified as follows:

[0045] S130: Weigh 100.00 mg of porphyrin derivative (CAS: 553-12-8, M = 562.66 g / mol) and dissolve it in 10.00 mL of methanol. Then weigh 263.137 mg of Ce(OAc)3 (M = 317.252 g / mol) and dissolve it in 100 mL of chloroform. Mix the two solutions to prepare cerium heme (Ce-Hgb, M = 702.78 g / mol). Weigh 0.35 mg of Ce-Hgb and dissolve it in 10.00 mL of a mixed solvent of chlorobenzene and acetic acid (9:1) to obtain a Ce-Hgb solution with a concentration of 0.050 mmol / L. Spin-coat Ce-Hgb onto the hole transport layer using a spin-coating method with spin-coating parameters set to 4000 rpm and 30 s. Finally, anneal at 100 °C for 1 min to obtain the Ce-Hgb modified layer.

[0046] All other steps were the same, resulting in a Ce-Hgb modified layer with a concentration of 0.050 mmol / L.

[0047] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a bio-modified perovskite solar cell, characterized by, It comprises the following steps: Preparation of an electron transport layer or a hole transport layer on a transparent conductive substrate; Spin coating of a rare earth-based heme solution on the electron transport layer or the hole transport layer to form a heme derivative modification layer; Spin coating of a perovskite precursor solution on the heme derivative modification layer to obtain a perovskite thin film layer; Spin coating of a hole transport layer or an electron transport layer on the perovskite thin film layer and preparation of a top electrode to obtain a perovskite solar cell.

2. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The rare earth in the rare earth-based heme solution is europium, samarium, cerium, terbium or dysprosium.

3. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The specific steps for spin coating of the rare earth-based heme solution on the electron transport layer or the hole transport layer to form the heme derivative modification layer are: first dissolving the rare earth-based heme in chlorobenzene, and then spin coating on the electron transport layer or the hole transport layer to form the heme derivative modification layer.

4. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The concentration of the rare earth-based heme solution is 0.05-0.2 mmol / L.

5. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The rare earth-based heme is synthesized by reaction of a porphine derivative and an acetate salt of a rare earth ion.

6. The preparation method of the bio-modified perovskite solar cell-based, according to claim 5, wherein, The preparation method of the rare earth-based heme is: dissolving the porphine derivative in methanol, dissolving the acetate salt of the rare earth ion in chloroform, mixing and reacting to obtain the rare earth-based heme; and dissolving the rare earth-based heme in a mixed solvent composed of chlorobenzene and acetic acid to obtain the rare earth-based heme solution.

7. The preparation method of the bio-modified perovskite solar cell-based, according to claim 6, wherein, The ratio of chlorobenzene to acetic acid in the mixed solvent composed of chlorobenzene and acetic acid is 9:

1.

8. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The transparent conductive substrate is one of a glass substrate, a quartz substrate, a PET plastic substrate, a PEN plastic substrate and a PI plastic substrate, and one of indium tin oxide, fluorine-doped tin dioxide and grid silver thin film is prepared thereon as a conductive layer; the electron transport layer material is one or more of ZnO, TiO2, SnO2, PCBM, fullerene and a fullerene derivative; the hole transport layer material is one or more of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, nickel oxide, copper oxide, 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, cuprous thiocyanate and molybdenum oxide; and the top electrode is one or more of an Au electrode, an Ag electrode, an Al electrode, a Cu electrode, a carbon electrode, a PH1000 polymer electrode and a metal oxide electrode.

9. The preparation method of the bio-modified perovskite solar cell-based, according to claim 1, wherein, The molecular structure of the perovskite thin film is ABX3, wherein A is one or more of FA, MA and Cs, B is one or more of Pb and Sn, and X is one or more of Cl, Br and I.

10. A bio-modified perovskite solar cell based on, characterized by, The solar cell is prepared by the method of any one of claims 1-9, and the structure of the solar cell from bottom to top is: a transparent conductive substrate, an electron transport layer, a heme derivative modification layer, a perovskite thin film layer, a hole transport layer and a top electrode, or a transparent conductive substrate, a hole transport layer, a heme derivative modification layer, a perovskite thin film layer, an electron transport layer and a top electrode.

Images