Method for improving light stability of perovskite solar cell
By introducing inorganic p-type semiconductor materials into perovskite solar cells, the contact between iodine ions and hole transport layer is hindered, and the problem of irreversible decomposition of perovskite materials under light conditions is solved, and the photostability of perovskite solar cells is significantly improved.
Patent Information
- Application Number
- CN202311634824.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-30
- Publication Date
- 2025-05-30
AI Technical Summary
Perovskite solar cells are prone to irreversible decomposition of perovskite materials under light conditions, resulting in a decline in performance, and the prior art is difficult to effectively solve this problem.
Inorganic p-type semiconductor material is introduced between the hole transport layer and the perovskite absorption layer of the perovskite solar cell, which hinders the direct contact between the iodine ions and the hole transport layer, inhibits the redox reaction, and seals the iodine atoms in the perovskite body.
Effectively prevent the migration of iodine atoms to the hole transport layer, prevent the irreversible decomposition of perovskite materials, significantly improve the light stability of perovskite solar cells, and avoid the problem of ultraviolet light instability in the traditional organic interface layer.
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Figure CN120076671A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a method for improving the light stability of perovskite solar cells. Background Art
[0002] An important challenge faced by perovskite solar cells in applications is that perovskite materials are prone to decomposition under the influence of the external environment. Perovskite materials will decompose under continuous light, high humidity, oxygen environment, and high heat environment, resulting in a decline in the performance of perovskite solar cells. Among them, the stability of oxygen and humidity can be solved by encapsulation. However, for solar cells, light is the essence of photovoltaic power generation. Therefore, light stability is a problem that must be solved during the application process of perovskite solar cells.
[0003] For perovskite solar cells, whether it is an n-i-p or p-i-n cell structure, high-efficiency perovskite solar cells all need to use a hole transport layer for carrier separation and transport. The latest research found that under light illumination, photo-generated holes will oxidize iodide ions in the perovskite material into iodine atoms, and then the iodine atoms combine with each other to form iodine molecules, causing the perovskite material to decompose. However, if there is no hole layer in the perovskite material, this reaction is a reversible reaction, that is, under dark conditions, iodine atoms will be reduced to iodide ions and react again to form perovskite materials. However, when there is a hole layer, due to the energy level difference between the perovskite layer and the hole transport layer, iodine molecules are easily migrated into the hole transport layer, resulting in irreversible decomposition of the perovskite absorption layer, making the perovskite solar cell unable to work stably under light illumination. On the other hand, due to the existence of a large number of dangling bonds and some defect sites such as oxygen vacancies on the surface of the hole transport layer, the existence of these defects is also likely to cause the perovskite material to decompose at the interface, reducing the stability of the perovskite solar cell. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a method for improving the light stability of perovskite solar cells by introducing an inorganic p-type semiconductor material between the hole transport layer and the perovskite absorption layer of the perovskite solar cell. On the one hand, it hinders the direct contact between iodide ions and the hole transport layer and inhibits the redox reaction. On the other hand, it can seal iodine atoms in the perovskite matrix to achieve the purpose of inhibiting the irreversible decomposition of the perovskite material caused by the migration of iodine atoms generated by light illumination in the perovskite absorption layer to the hole transport layer. Since an inorganic substance is used as the blocking layer, the problem of ultraviolet light instability of the traditional organic interface layer itself can be effectively avoided.
[0005] The present invention is implemented as follows. A method for improving the light stability of a perovskite solar cell is provided. The perovskite solar cell includes a perovskite layer and a hole transport layer. The method is as follows: A p-type semiconductor layer is disposed between the perovskite layer and the hole transport layer. The material for preparing the p-type semiconductor layer includes at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide.
[0006] The p-type semiconductor layer of the present invention effectively hinders the migration of iodine atoms inside the perovskite material caused by light to the hole transport layer, and also further hinders the interfacial reaction with the perovskite layer caused by surface defects of the hole transport layer, thereby enhancing the stability of the interfacial layer itself, and further greatly improving the full-spectrum light stability of the perovskite solar cell. The method of the present invention greatly promotes the commercialization of perovskite solar cells.
[0007] Further, the method includes: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
[0008] Further, the method includes: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
[0009] Further, the method includes: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
[0010] Further, the method includes: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
[0011] The present invention is implemented as follows. A method for preparing a perovskite solar cell is provided. The perovskite solar cell sequentially includes a substrate, a conductive layer, an electron transport layer, a perovskite layer, a p-type semiconductor layer, a hole transport layer, and an electrode layer from bottom to top. The material for preparing the p-type semiconductor layer includes at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The preparation method includes the following steps: Step 1: Prepare an electron transport layer on the substrate with the conductive layer by chemical bath deposition, and then prepare a perovskite layer on the electron transport layer by slot die coating; Step 2: Prepare a p-type semiconductor layer on the perovskite layer by physical vapor deposition or spin coating method; Step 3: Prepare a hole transport layer on the p-type semiconductor layer by slot die coating method, and then prepare an electrode layer on the hole transport layer by coating method. After completion of assembly, a perovskite solar cell is obtained.
[0012] The present invention is realized as follows. A preparation method of a perovskite solar cell is provided. The perovskite solar cell sequentially includes a substrate, a conductive layer, a hole transport layer, a p-type semiconductor layer, a perovskite layer, an electron transport layer, and an electrode layer from bottom to top. The material for preparing the p-type semiconductor layer includes at least one compound of cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The preparation method includes the following steps: Step A: Prepare a hole transport layer on the substrate with a conductive layer already prepared by slot die coating method; Step B: Prepare a p-type semiconductor layer on the hole transport layer by physical vapor deposition or spin coating method; Step C: Prepare a perovskite layer on the p-type semiconductor layer by slot die coating method, and then sequentially prepare an electron transport layer and an electrode layer on the prepared perovskite layer by physical vapor deposition method. After completion of assembly, a perovskite solar cell is obtained.
[0013] Further, in Step B, an annealing treatment is further included for the p-type semiconductor layer before preparing the perovskite layer.
[0014] Compared with the prior art, the method for improving the light stability of the perovskite solar cell in the present invention sets a p-type semiconductor layer between the perovskite layer and the hole transport layer. The material for preparing the p-type semiconductor layer includes at least one compound of cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. On the one hand, the inorganic p-type semiconductor material is used to block the migration of iodine atoms in the perovskite layer to the hole transport layer, improving the stability of the perovskite. On the other hand, the p-type semiconductor material is used to passivate the defects in the hole transport layer, inhibiting the reaction between the surface defects in the hole transport layer and the iodide ions in the perovskite, further improving the stability of the perovskite. In addition, since the inorganic material does not have the characteristic of external light instability, the use of the inorganic material can effectively solve the problem of ultraviolet light instability of the traditional organic interface layer. The present invention provides an effective method for improving the light stability of the perovskite solar cell, which is of great significance for promoting the commercial application of low-cost perovskite solar cells. Description of the Drawings
[0015] Figure 1 It is a schematic internal structure diagram of a perovskite solar cell of the present invention; Figure 2 It is a schematic internal structure diagram of another perovskite solar cell of the present invention; Figure 3 Schematic diagram for comparing the light aging test curves of the perovskite solar cell (with an MnS interface layer) prepared in Example 1 of the present invention and the perovskite solar cell without a p-type semiconductor layer (without an interface layer); Figure 4 Schematic diagram for comparing the light aging test curves of the perovskite solar cell (with a ZnTe interface layer) prepared in Example 2 of the present invention and the perovskite solar cell without a p-type semiconductor layer (without an interface layer). Detailed implementation manners
[0016] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0017] In a preferred embodiment of the method for improving the light stability of a perovskite solar cell of the present invention, the perovskite solar cell includes a perovskite layer and a hole transport layer, and the method is as follows: a p-type semiconductor layer is provided between the perovskite layer and the hole transport layer, and the material for preparing the p-type semiconductor layer includes at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide.
[0018] The method includes: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
[0019] The method includes: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
[0020] The method includes: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
[0021] The method includes: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
[0022] Please refer to Figure 1As shown, the present invention also discloses a preparation method of a perovskite solar cell. The perovskite solar cell sequentially includes a substrate 1, a conductive layer 2, an electron transport layer 3, a perovskite layer 4, a p-type semiconductor layer 5, a hole transport layer 6, and an electrode layer 7 from bottom to top. The perovskite solar cell uses an n-i-p structure. The material for preparing the p-type semiconductor layer includes at least one compound of cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The preparation method includes the following steps: Step 1: Prepare the electron transport layer 3 on the substrate 1 with the conductive layer 2 already prepared by a chemical bath method, and then prepare the perovskite layer 4 on the electron transport layer 3 by a slot-die coating method.
[0023] Step 2: Prepare the p-type semiconductor layer 5 on the perovskite layer 4 by physical vapor deposition or spin coating.
[0024] Step 3: Prepare the hole transport layer 6 on the p-type semiconductor layer 5 by a slot-die coating method, and then prepare the electrode layer 7 on the hole transport layer 6 by a coating method. After completion of the assembly, the perovskite solar cell is obtained.
[0025] Please refer to Figure 2 As shown, the present invention also discloses a preparation method of a perovskite solar cell. The perovskite solar cell sequentially includes a substrate 1, a conductive layer 2, a hole transport layer 6, a p-type semiconductor layer 5, a perovskite layer 4, an electron transport layer 3, and an electrode layer 7 from bottom to top. The material for preparing the p-type semiconductor layer includes at least one compound of cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The perovskite solar cell uses a p-i-n structure. The preparation method includes the following steps: Step A: Prepare the hole transport layer 6 on the substrate 1 with the conductive layer 2 already prepared by a slot-die coating method.
[0026] Step B: Prepare the p-type semiconductor layer 5 on the hole transport layer 6 by physical vapor deposition or spin coating.
[0027] Step C: Prepare the perovskite layer 4 on the p-type semiconductor layer 5 by a slot-die coating method, and then sequentially prepare the electron transport layer 3 and the electrode layer 7 on the perovskite layer 4 by physical vapor deposition. After completion of the assembly, the perovskite solar cell is obtained.
[0028] In step B, an annealing treatment is further included for the p-type semiconductor layer 5 before preparing the perovskite layer 4.
[0029] The method for improving the light stability of the perovskite solar cell according to the present invention is further described below through specific examples. Example 1
[0030] The first embodiment of the preparation method of the perovskite solar cell of the present invention includes the following steps: Step 11: Use glass with FTO prepared as the conductive layer 2 as the substrate 1, and use a cleaning agent, deionized water, acetone, and isopropanol to ultrasonically clean it, blow dry it with nitrogen, and then use a UV ozone cleaning machine to treat it for 20 minutes.
[0031] Step 12: Prepare the electron transport layer 3. First, prepare 2% by mass of tin dioxide SnO 2 The SnO2 precursor solution was then coated on the FTO conductive glass by a doctor blade method. Subsequently, the substrate 1 was heated at 150°C for 30 min and then cooled naturally to obtain a dense SnO 2 The layer serves as an electron transport layer 3.
[0032] Step 13: Preparation of perovskite layer 4. 0.05 (FA 0.83 MA 0.17 ) 0.95 pb(I 0.83 Br 0.17 ) 3 The required element ratio is a certain ratio of CsI, FAI, MAI, and PbI. 2 , pbBr 2 The precursor solution of the perovskite layer is prepared by dissolving it in a mixed solvent of DMSO and DMF. Then the precursor solution is coated on the SnO 2 Subsequently, the substrate 1 coated with the perovskite precursor solution was placed on a heating platform and heat treated at 150°C for 10 min to obtain Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 pb(I 0.83 Br 0.17 ) 3 Perovskite layer 4.
[0033] Step 14: Preparation of the MnS p-type semiconductor layer 5. First, MnS powder is placed in an evaporation crucible, and then MnS is deposited on the perovskite layer 4 at a rate of 0.1 nm / s, with the thickness controlled within 10 nm, to obtain the MnS p-type semiconductor layer 5.
[0034] Step 15, preparation of hole transport layer 6. 72.3 mg of Spiro-OMeTAD, 17.5 uL of acetonitrile solution of lithium bis(trifluoromethanesulfonyl)imide with a concentration of 520 mg / mL, and 28.8 uL of TBp were added to 1 mL of chlorobenzene solvent to prepare a spiro-OMeTAD mixed solution, which was then scraped onto the surface of the p-type semiconductor layer of MnS and dried to obtain a hole transport layer 6.
[0035] Step 16: Thermally evaporate the electrode layer 7. Using a thermal evaporation coating machine, under a vacuum of 1.0×10 -4 Pa, thermally evaporate 200 nm of silver onto the hole transport layer 6 to form the metal electrode layer 7. After encapsulation, the preparation of the perovskite solar cell is completed.
[0036] Figure 3 Shows the perovskite solar cell (with a MnS interface layer) using MnS as the p-type semiconductor layer in this embodiment. After being irradiated under standard illumination conditions for 1000 hours, the decay of the perovskite solar cell efficiency is shown. It can be seen that for the perovskite solar cell without a p-type semiconductor layer (without an interface layer), after 800 hours of standard illumination, the perovskite solar cell efficiency has decayed to 47% of the initial efficiency. While for the perovskite solar cell with a MnS interface layer, the efficiency still remains at 89% of the original, and the light stability has been greatly improved. Example 2
[0037] The second embodiment of the preparation method of the perovskite solar cell of the present invention includes the following steps: Step 21: Use the glass with the prepared FTO as the conductive layer 2 as the substrate 1, and ultrasonically clean it with a cleaning agent, deionized water, acetone, and isopropanol. After drying with nitrogen, then treat it with an ultraviolet ozone cleaning machine for 20 min.
[0038] Step 22: Preparation of the hole transport layer 6. In this example, NiO is used as the hole transport layer 6. First, disperse NiOx nanoparticles in deionized water (20 mg / mL), and obtain the NiOx nanoparticle dispersion after ultrasonic treatment in an ultrasonic instrument for 24 h. Then, spin-coat the NiOx nanoparticle solution on the FTO glass by the coating method, and then anneal at 120 °C for 30 min to obtain the NiOx hole transport layer 6.
[0039] Step 23: Preparation of the p-type semiconductor layer 5 of ZnTe. First, place the ZnTe powder in an evaporation crucible, and then deposit ZnTe on the NiOx hole transport layer 6 at a rate of 0.1 nm / s, with the thickness controlled within 10 nm to obtain the p-type semiconductor layer 5 of ZnTe.
[0040] Step 24: Preparation of the perovskite layer 4. According to the required elemental ratio of Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 pb(I 0.83 Br 0.17 ) 3 Take a certain proportion of CsI, FAI, MAI, pbI 2 , pbBr 2Dissolved in a mixed solvent of DMSO and DMF, a precursor solution of the perovskite layer was prepared. Then, the precursor solution was coated on the p-type semiconductor layer 5 of ZnTe by a coating method. Subsequently, the substrate 1 coated with the perovskite precursor solution was placed on a heating table and heat-treated at 150 °C for 10 min to obtain Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 pb(I 0.83 Br 0.17 ) 3 perovskite layer 4.
[0041] Step 25: Preparation of the electron transport layer 3. The fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (pCBM) was deposited on the perovskite layer 4 by thermal evaporation as the electron transport layer 3.
[0042] Step 26: Thermal evaporation of the electrode layer 7. Using a thermal evaporation coating machine, 200 nm of silver was thermally evaporated onto the electron transport layer 3 under a vacuum of 1.0×10 -4 Pa to form the metal electrode layer 7. After encapsulation, the preparation of the perovskite solar cell was completed.
[0043] Figure 4 Shows the perovskite solar cell (containing the ZnTe interface layer) using ZnTe as the p-type semiconductor layer in this embodiment. After being irradiated under standard illumination conditions for 1000 hours, the decay of the perovskite solar cell efficiency is shown. It can be seen that for the perovskite solar cell without the p-type semiconductor layer (without the interface layer), after being irradiated under standard illumination for 800 hours, the perovskite solar cell efficiency has decayed to 47% of the initial efficiency. While the perovskite solar cell efficiency with the ZnTe interface layer still remains at 87% of the original, and the light stability has been greatly improved.
[0044] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
Claims
1. A method for improving the light stability of perovskite solar cells, the perovskite solar cells comprising a perovskite layer and a hole transport layer, characterized in that, the method lies in: arranging a p-type semiconductor layer between the perovskite layer and the hole transport layer, and the material for preparing the p-type semiconductor layer comprises at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide.
2. The method for improving the light stability of perovskite solar cells according to claim 1, characterized in that, the method comprises: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
3. The method for improving the light stability of perovskite solar cells according to claim 1, characterized in that, the method comprises: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared perovskite layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a hole transport layer on the p-type semiconductor layer.
4. The method for improving the light stability of perovskite solar cells according to claim 1, characterized in that, the method comprises: depositing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by physical vapor deposition to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
5. The method for improving the light stability of perovskite solar cells according to claim 1, characterized in that, the method comprises: coating a coating solution containing at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide on the surface of the prepared hole transport layer by spin coating, and drying to obtain a p-type semiconductor layer; and then preparing a perovskite layer on the p-type semiconductor layer.
6. A method for preparing a perovskite solar cell, characterized in that, the perovskite solar cell sequentially comprises a substrate, a conductive layer, an electron transport layer, a perovskite layer, a p-type semiconductor layer, a hole transport layer, and an electrode layer from bottom to top. The material for preparing the p-type semiconductor layer comprises at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The preparation method comprises the following steps: Step 1: Prepare an electron transport layer on the substrate with a prepared conductive layer by chemical bath deposition, and then prepare a perovskite layer on the electron transport layer by slot die coating; Step 2: Prepare a p-type semiconductor layer on the perovskite layer by physical vapor deposition or spin coating; Step 3: Prepare a hole transport layer on the p-type semiconductor layer by slot die coating, and then prepare an electrode layer on the hole transport layer by coating, and obtain a perovskite solar cell after assembly.
7. A method for preparing a perovskite solar cell, characterized in that, the perovskite solar cell sequentially comprises a substrate, a conductive layer, a hole transport layer, a p-type semiconductor layer, a perovskite layer, an electron transport layer, and an electrode layer from bottom to top. The material for preparing the p-type semiconductor layer comprises at least one compound among cadmium telluride, zinc telluride, antimony sulfide, and manganese sulfide. The preparation method comprises the following steps: Step A: Prepare a hole transport layer on a substrate with a conductive layer already prepared by the slot coating method; Step B: Prepare a p-type semiconductor layer on the hole transport layer by physical vapor deposition or spin coating; Step C: Prepare a perovskite layer on the p-type semiconductor layer by the slot coating method, and then sequentially prepare an electron transport layer and an electrode layer on the perovskite layer by physical vapor deposition. After completion of the assembly, a perovskite solar cell is obtained.
8. The method for preparing a perovskite solar cell according to claim 7, wherein, in Step B, it further includes annealing the p-type semiconductor layer before preparing the perovskite layer.