DHAQ chelate modification-based perovskite solar cell and preparation method thereof

Abstract

The invention discloses a DHAQ chelate modification-based perovskite solar cell and a preparation method thereof, and the solar cell sequentially comprises an ITO conductive glass substrate layer, a nickel oxide layer NiOx, a hole transport layer MeO-4PACz, an interface modification layer DHAQ, a perovskite layer Cs0.05 (FA0. 95MA0. 05) 0. 95Pb (I0. 95Br0. 05) 3, a passivation layer PEAI, an electron transport layer [6, 6]-phenyl-C61-isomethyl butyrate, 2, 9-dimethyl-4, 7-biphenyl-1, 2, 4-triazole-1, 2, 4-triazole-1, 2, 4-triazole-1, 3-triazole-1, 3-triazole-1, 3-triazole-1, 3-triazole-1, 3- and a metal Ag electrode layer which is arranged on the substrate and comprises a 1, 10-phenanthroline hole barrier layer BCP and a metal Ag electrode layer. According to the invention, DHAQ organic chelate is introduced into the interface of the perovskite solar cell as an interface modification layer, so that multi-performance improvement is realized; the modification layer effectively passivates interface defects, optimizes energy level matching and improves carrier transmission efficiency, the morphology of the modified perovskite thin film is obviously improved, the grain size is increased, and the grain size is uniformly distributed; and meanwhile, the long-term stability of the device in a humid and hot environment is greatly improved, the cell efficiency is remarkably improved, and an effective solution is provided for developing a high-performance perovskite solar cell.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to a DHAQ chelate-modified perovskite solar cell and a preparation method thereof. Background Art

[0002] Photovoltaic technology is advancing rapidly and has become a crucial pillar of the global energy transition. To overcome the technical bottlenecks of high energy consumption and low efficiency of traditional silicon-based solar cells and achieve leapfrog development in the photovoltaic industry, new-generation photovoltaic technologies, represented by perovskite solar cells, are becoming a research focus in academia and industry. These novel photovoltaic devices not only offer significant advantages such as high theoretical efficiency and low fabrication costs, but also, due to their solution-processability, enable the realization of flexible and lightweight photovoltaic modules, presenting promising applications that are unattainable with traditional silicon-based technologies.

[0003] Perovskite solar cells, a representative example of third-generation photovoltaic technology, have achieved a dramatic improvement in photoelectric conversion efficiency from 3.8% to 27% in just over a decade thanks to their superior photoelectric performance and simple fabrication process, demonstrating enormous commercial potential. However, the technology still faces numerous challenges: non-radiative recombination caused by interface defects severely restricts effective carrier collection; device performance degradation caused by ion migration affects long-term stability; and energy level mismatches between functional layers result in significant energy losses.

[0004] Therefore, in order to solve the above problems, the present invention proposes a DHAQ chelate-modified perovskite solar cell and a preparation method thereof. Summary of the Invention

[0005] The purpose of the present invention is to provide a perovskite solar cell modified with DHAQ chelate, which achieves multiple performance improvements by using DHAQ organic chelate as an interface modification layer; it can significantly improve the interface contact performance of the device, enhance the hole extraction efficiency, and effectively suppress non-radiative recombination losses.

[0006] In order to achieve the above technical effects, the present invention is implemented by the following technical solutions: a DHAQ chelate modified perovskite solar cell, characterized in that it includes, from bottom to top, an ITO conductive glass substrate layer, a nickel oxide layer NiOx, a hole transport layer MeO-4PACz, an interface modification layer DHAQ, a perovskite layer Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05)3. Passivation layer PEAI, electron transport layer [6,6]-phenyl-C61-butyric acid isomethyl ester, 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline hole blocking layer BCP and metal Ag electrode layer

[0007] Furthermore, the preparation process of the perovskite layer is as follows:

[0008] (1) Weighing CsI, MABr, FAI, PbI2, and PbBr2 in a molar ratio of CsI:MABr:FAI:PbI2:PbBr2 = 0.05-0.1:0.05-0.1:1-2:1-2:0.05-0.1; then dissolving the weighed CsI, MABr, FAI, PbI2, and PbBr2 in a mixed solution of DMF and DMSO, and stirring at 55-65°C for 2 h to form a perovskite precursor solution with a concentration of 1.45 M;

[0009] (2) The perovskite precursor liquid is applied to form a perovskite layer, which can form a perovskite layer Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3.

[0010] Furthermore, the preparation process of the interface modification layer is as follows:

[0011] (1) Dissolve DHAQ in chlorobenzene solution and stir at 60°C for 1 h to form a DHAQ solution with a concentration of 0.2 mg / mL;

[0012] (2) taking 100 μL of the prepared DHAQ solution and mixing the DHAQ solution with 100 μL of chlorobenzene solution to form a 0.1 mg / ml DHAQ-doped DHAQ precursor solution;

[0013] (3) Applying DHAQ precursor solution to form an interface modification layer DHAQ.

[0014] Another object of the present invention is to provide a method for preparing a DHAQ chelate-modified perovskite solar cell, which comprises the following steps:

[0015] S1. Ultrasonic cleaning of the ITO glass substrate using glass cleaning solution, isopropyl alcohol solution, deionized water, and anhydrous ethanol for 13 to 17 minutes, followed by drying and cleaning with a UV ozone cleaner for 8 to 12 minutes.

[0016] S2, spin coating the hole transport layer MeO-4PACz on the cleaned ITO glass substrate, and then annealing at 100-110 ° C for 8-12 min;

[0017] S3, dynamically spin-coating the interface modification layer DHAQ on the hole transport layer MeO-4PACz at 4000 rpm for 30 seconds;

[0018] S4, dynamically spin-coating the perovskite solution on the interface modification layer DHAQ at 6000 rpm, and dynamically spin-coating 0.15 ml of chlorobenzene as an antisolvent, followed by annealing at 100-110 °C for 1 h;

[0019] S5, spin coating a passivation layer PEAI on the perovskite layer;

[0020] S6, spin coating an electron transport layer PCBM on the perovskite layer;

[0021] S7, evaporating a hole blocking layer (BCP) on the electron transport layer in a vacuum coating machine to a thickness of 5 nm;

[0022] S8. In a vacuum coating machine, a metal electrode Ag is evaporated onto the hole blocking layer to a thickness of 120 nm.

[0023] The beneficial effects of the present invention are:

[0024] The present invention significantly improves the interface contact performance of the device and enhances the hole extraction efficiency by introducing DHAQ molecules into the perovskite / hole transport layer interface, while effectively suppressing non-radiative recombination losses.

[0025] The DHAQ molecules introduced in the present invention form chemical coordination with the perovskite components through their active functional groups, passivating the uncoordinated Pb 2+ and I - defects, optimizes the energy level arrangement and promotes the efficient transport of carriers;

[0026] The DHAQ interface modification strategy adopted in the present invention improves the crystallization quality of the perovskite film, increases the grain size and improves the film uniformity, while enhancing the long-term stability of the device in a humid and hot environment, providing an effective way to prepare efficient and stable perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 The SEM images of the perovskite solar cell with or without DHAQ modification of the present invention are shown;

[0029] Figure 2 KPFM images of the perovskite solar cell with or without DHAQ modification according to the present invention;

[0030] Figure 3 UV-vis graphs of perovskite solar cells with and without DHAQ modification according to the present invention;

[0031] Figure 4 The conductivity diagram of the perovskite film with or without DHAQ modification of the present invention;

[0032] Figure 5 The forward scan and reverse scan JV curves of the perovskite solar cell with or without DHAQ modification of the present invention are shown. DETAILED DESCRIPTION

[0033] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] When the structure of the DHAQ chelate-modified perovskite solar cell according to the present invention is as follows from bottom to top:

[0036] ITO / MeO-2PACz / Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3 / PEAI / PCBM / BCP / Ag;

[0037] The preparation method comprises the following steps:

[0038] (1) Ultrasonic cleaning of the ITO glass substrate was performed using glass cleaning solution, isopropyl alcohol solution, deionized water, and anhydrous ethanol for 15 min, followed by drying and then cleaning with an ultraviolet ozone cleaner for 10 min;

[0039] (2) The hole transport layer MeO-4PACz was spin-coated on the cleaned ITO glass substrate and then annealed at 100 °C for 10 min;

[0040] (3) 1.45 M ternary perovskite precursor solution was dynamically spin-coated on the hole transport layer MeO-4PACz at 6000 rpm, and 0.15 ml of chlorobenzene was dynamically spin-coated as an antisolvent, followed by annealing at 100 °C for 1 h;

[0041] (4) Spin coating the electron transport layer PCBM on the perovskite layer;

[0042] (5) depositing a hole blocking layer (BCP) on the electron transport layer in a vacuum coating machine with a thickness of 5 nm;

[0043] (6) In a vacuum coating machine, a metal electrode Ag is evaporated onto the hole blocking layer with a thickness of 120 nm.

[0044] Example 2

[0045] When the structure of the DHAQ chelate-modified perovskite solar cell according to the present invention is as follows from bottom to top:

[0046] ITO / MeO-4PACz / DHAQ / Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3 / PEAI / PCBM+eC9-2Cl / BCP / Ag;

[0047] The preparation method comprises the following steps:

[0048] (1) Using glass cleaning fluid, isopropyl alcohol solution, deionized water, and anhydrous ethanol, the ITO glass substrate was ultrasonically cleaned for 13 to 17 minutes, and then dried and cleaned with an ultraviolet ozone cleaner for 8 to 12 minutes;

[0049] (2) spin coating the hole transport layer MeO-4PACz on the cleaned ITO glass substrate, followed by annealing at 100-110°C for 8-12 min;

[0050] (3) Dynamically spin-coating the interface modification layer DHAQ on the hole transport layer MeO-4PACz at 4000 rpm for 30 seconds;

[0051] (4) The perovskite solution was dynamically spin-coated on the interface modification layer DHAQ at 6000 rpm, and 0.15 ml of chlorobenzene was dynamically spin-coated as an antisolvent, followed by annealing at 00-110 °C for 1 h;

[0052] (5) Spin coating a passivation layer PEAI on the perovskite layer;

[0053] (6) Spin coating the electron transport layer PCBM on the perovskite layer;

[0054] (7) depositing a hole blocking layer (BCP) on the electron transport layer in a vacuum coating machine with a thickness of 5 nm;

[0055] (8) In a vacuum coating machine, a metal electrode Ag is evaporated onto the hole blocking layer with a thickness of 120 nm.

[0056] Example 3

[0057] The perovskite layer Cs in the perovskite solar cells modified with DHAQ chelating materials of different structures prepared in Examples 1 and 2 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 ) The preparation process of 3 is as follows:

[0058] (1) CsI, MABr, FAI, PbI2, and PbBr2 were weighed and dissolved in a mixed solution of DMF and DMSO at a molar ratio of CsI:MABr:FAI:PbI2:PbBr2 = 0.05-0.1:0.05-0.1:1-2:1-2:0.05-0.1, and stirred at 60°C for 2 h to form a perovskite precursor solution with a concentration of 1.45 M;

[0059] (2) The perovskite precursor liquid is applied to form a perovskite layer, which can form a perovskite layer Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3.

[0060] Example 4

[0061] The preparation process of the interface modification layer DHAQ in the perovskite solar cell modified with DHAQ chelating materials of different structures prepared in Example 2 is as follows:

[0062] (1) Dissolve DHAQ in chlorobenzene solution and stir at 60°C for 1 h to form a DHAQ solution with a concentration of 0.2 mg / mL;

[0063] (3) taking 100 μL of the prepared DHAQ solution and mixing the DHAQ solution with 100 μL of chlorobenzene solution to form a 0.1 mg / ml DHAQ-doped DHAQ precursor solution;

[0064] (4) Applying DHAQ precursor solution to form an interface modification layer DHAQ.

[0065] Example 5

[0066] The performance of the perovskite solar cells modified with DHAQ chelating materials of different structures prepared in Examples 1 and 2 was tested as follows:

[0067] By attaching Figure 1 It can be seen that the surface morphology of the perovskite solar device formed by introducing the DHAQ interface modification layer will be significantly improved, the crystals will show a more neat and orderly arrangement, the grain size will increase and the grains will be fuller, and the growth direction of the grains will be greatly improved, which can better connect the hole transport layer and the electron transport layer with the perovskite layer.

[0068] By attaching Figure 2 It can be seen that in KPFM, compared with the spectrum without DHAQ interface modification, the surface of the perovskite film after DHAQ treatment is more uniform and the roughness is significantly reduced, which is more conducive to current transmission.

[0069] By attaching Figure 3 It can be seen that in UV-vis, the addition of DHAQ enhances the properties of n-type semiconductors in the film, strengthens electron extraction, suppresses non-radiative recombination, and thus enhances the optoelectronic performance of the device.

[0070] By attaching Figure 4 It can be seen that the addition of the DHAQ modification layer greatly improves the hole mobility, indicating an increase in the carrier mobility of the device and an enhancement of the photoelectric performance of the device.

[0071] By attaching Figure 5 It can be seen that the photoelectric performance of perovskite solar devices modified with DHAQ is significantly improved, the photoelectric conversion efficiency is increased, and the photoelectron retention phenomenon is significantly suppressed.

Claims

1. A perovskite solar cell modified with DHAQ chelate, characterized in that: The solar cell comprises, from bottom to top, an ITO conductive glass substrate layer, a nickel oxide layer NiOx, a hole transport layer MeO-4PACz, an interface modification layer DHAQ, a perovskite layer Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3. Passivation layer PEAI, electron transport layer [6,6]-phenyl-C61-butyric acid isomethyl ester, 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline hole blocking layer BCP and metal Ag electrode layer.

2. A DHAQ chelate-modified perovskite solar cell according to claim 1, characterized in that: The preparation process of the perovskite layer is as follows: (1) Weighing CsI, MABr, FAI, PbI2, and PbBr2 in a molar ratio of CsI:MABr:FAI:PbI2:PbBr2 = 0.05-0.1:0.05-0.1:1-2:1-2:0.05-0.1; then dissolving the weighed CsI, MABr, FAI, PbI2, and PbBr2 in a mixed solution of DMF and DMSO, and stirring at 55-65°C for 2 h to form a perovskite precursor solution with a concentration of 1.45 M; (2) The perovskite precursor liquid is applied to form a perovskite layer, which can form a perovskite layer Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.05 )3.

3. A DHAQ chelate-modified perovskite solar cell according to claim 1, characterized in that: The preparation process of the interface modification layer is as follows: (1) Dissolve DHAQ in chlorobenzene solution and stir at 60°C for 1 h to form a DHAQ solution with a concentration of 0.2 mg / mL; (3) taking 100 μL of the prepared DHAQ solution and mixing the DHAQ solution with 100 μL of chlorobenzene solution to form a 0.1 mg / ml DHAQ-doped DHAQ precursor solution; (4) Applying DHAQ precursor solution to form an interface modification layer DHAQ.

4. A method for preparing a perovskite solar cell based on DHAQ chelate modification, characterized in that: The steps include: S1. Ultrasonic cleaning of the ITO glass substrate using glass cleaning solution, isopropyl alcohol solution, deionized water, and anhydrous ethanol for 13 to 17 minutes, followed by drying and cleaning with a UV ozone cleaner for 8 to 12 minutes. S2, spin coating the hole transport layer MeO-4PACz on the cleaned ITO glass substrate, and then annealing at 100-110°C for 8-12 min; S3, dynamically spin-coating the interface modification layer DHAQ on the hole transport layer MeO-4PACz at 4000 rpm for 30 seconds; S4, dynamically spin-coating the perovskite solution on the interface modification layer DHAQ at 6000 rpm, and dynamically spin-coating 0.15 ml of chlorobenzene as an antisolvent, followed by annealing at 100-110 °C for 1 h; S5, spin coating a passivation layer PEAI on the perovskite layer; S6, spin coating an electron transport layer PCBM on the perovskite layer; S7, evaporating a hole blocking layer (BCP) on the electron transport layer in a vacuum coating machine to a thickness of 5 nm; S8. In a vacuum coating machine, a metal electrode Ag is evaporated onto the hole blocking layer to a thickness of 120 nm.

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