An interface modification material, an interface modification ink, an interface modification layer, a method for preparing the same, products and applications.
By using an interface modification material composed of bulk amines and bulk organic acids, an interface modification ink is prepared and an interface modification layer is formed on the surface of the photoactive layer. This solves the problem of concentration sensitivity in perovskite solar cells, improves photoelectric conversion efficiency and stability, and is suitable for the commercial production of perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANGTZE DELTA REGION INST OF UNIV OF ELECTRONICS SCI & TECH OF CHINE (HUZHOU)
- Filing Date
- 2023-11-29
- Publication Date
- 2026-06-30
Smart Images
Figure CN117603059B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of perovskite solar cell materials technology, specifically to an interface modification material, an interface modification ink, an interface modification layer, its preparation method, products, and applications. Background Technology
[0002] Developing clean energy technologies and increasing the utilization of clean energy is an inevitable trend. Among various clean energy sources, solar cells have received high attention and vigorous development due to their ease of acquisition and clean, pollution-free characteristics. Among various new types of solar cells, perovskite solar cells have rapidly become a research hotspot due to their high photoelectric conversion efficiency and low manufacturing cost. Perovskite solar cells utilize perovskite-type organometal halide semiconductors as light-absorbing materials and belong to the third generation of solar cells. Due to the special solvent processing technology, perovskites have a large number of defect sites at the interface, thus requiring interface defect passivation to improve device efficiency and stability.
[0003] In existing technologies, the reagents used for interface passivation in perovskite solar cells can only function within a limited concentration range. Low-concentration reagents cannot cover all interface defect sites, while high-concentration reagents can affect carrier transport or even penetrate into the perovskite active layer, thus significantly reducing device current. The thickness difference caused by varying concentrations is often only a few nanometers. However, large-scale industrial production cannot control coating thickness at the nanometer level, making it impossible to effectively passivate interface defects.
[0004] Therefore, developing an interface modification material that is insensitive to concentration range, preparing an interface modification ink, and then preparing an interface modification layer for application in perovskite solar cells is of great significance for the commercialization of perovskite solar cells. Summary of the Invention
[0005] To address the technical problem of perovskite solar cells being sensitive to the concentration of interface modification ink, this invention provides an interface modification material, an interface modification ink, an interface modification layer, its preparation method, products, and applications.
[0006] In a first aspect, the present invention provides an interface modification material comprising a bulky amine and a bulky organic acid, wherein the bulky amine is one or more of propylamine, butylamine, hexamethylenediamine, benzylamine, and phenylethylamine, and the bulky organic acid is one or more of benzylphosphonic acid, triphenylamine ethylphosphonic acid, N-phosphonate ethylcarbazole, MeO-2PACz, and Me-4PACz.
[0007] MeO-2PACz is [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, and Me-4PACz is [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid.
[0008] Furthermore, the bulk amine is phenylethylamine, and the bulk organic acid is MeO-2PACz; the molar ratio of MeO-2PACz to phenylethylamine is 1:1-2.
[0009] Secondly, the present invention provides an interface-modified ink, comprising a solvent and an interface-modifying material, wherein the solvent is one or more selected from isopropanol, ethanol, toluene, chlorobenzene, trifluoroethanol, and chloroform.
[0010] Furthermore, the solvent is a mixed solution of toluene and isopropanol in a volume ratio of 4:1.
[0011] Furthermore, the mass concentration of the interface modification ink is 2-16 mg / mL.
[0012] Furthermore, the mass concentration of the interface modification ink is 2-8 mg / mL.
[0013] Thirdly, the present invention provides an interface modification layer mainly formed by interface modification ink.
[0014] Fourthly, the present invention provides a method for preparing an interface modification layer, wherein an interface modification ink is dropped onto the surface of a photoactive layer, and the layer is left to stand, spin-coated, and annealed to obtain the interface modification layer; wherein the standing time is 0-20s, the annealing temperature is 80-150℃, and the annealing time is 1-20min.
[0015] Furthermore, the standing time was 10 seconds, the annealing temperature was 100°C, and the annealing time was 5 minutes.
[0016] Fifthly, the present invention provides a perovskite solar cell, comprising, from top to bottom, a substrate, a transparent electrode, a hole transport layer, a photoactive layer, an interface modification layer, an electron transport layer, a metal electrode layer, and an interface modification layer.
[0017] Furthermore, the photoactive layer is a perovskite material.
[0018] Furthermore, the perovskite material can be a two-dimensional all-inorganic perovskite material, a two-dimensional organic-inorganic hybrid perovskite material, a three-dimensional all-inorganic perovskite material, or a three-dimensional organic-inorganic hybrid perovskite material.
[0019] Furthermore, perovskite materials are three-dimensional organic-inorganic hybrid perovskite materials.
[0020] Furthermore, the film formation method for perovskite materials is either a one-step or a two-step process.
[0021] Furthermore, the perovskite material is formed in a one-step process.
[0022] Furthermore, the perovskite material also includes a buffer layer between the electron transport layer and the metal electrode. The buffer layer is BCP or zirconium acetylacetonate; the substrate is glass, quartz, PET or PEN; the transparent electrode is indium tin oxide or fluorine-doped tin oxide; the hole transport layer is nickel oxide, PTAA, PEDOT:PSS or Poly-TPD; the electron transport layer is zinc oxide, PCBM or C60; and the metal electrode is silver, gold, aluminum, magnesium or copper.
[0023] Among them, BCP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, PET is polyethylene terephthalate, PEN is polyethylene naphthalate, PTAA is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], PEDOT:PSS is poly(3,4-ethylenedioxythiophene / polystyrene sulfonate), Poly-TPD is poly[bis(4-phenyl)(4-butylphenyl)amine], and PCBM is isomethyl [6,6]-phenyl-C61-butyrate.
[0024] In a sixth aspect, the present invention provides an application of the above-mentioned interface modification material, interface modification ink or interface modification layer in the preparation of perovskite solar cells.
[0025] Seventhly, the present invention provides a method for preparing a perovskite solar cell, the specific steps of which are as follows:
[0026] (1) The transparent conductive glass with striped ITO etched on the surface was cleaned by ultrasonic oscillation for 15 min with cleaning agent, deionized water, acetone and isopropanol in sequence, dried with nitrogen gas, and then treated with ultraviolet ozone for 20 min. A layer of NiO was then spin-coated. X Nanoparticles were annealed at 110°C for 15 minutes, then transferred to a nitrogen glove box in an anhydrous and oxygen-free environment, where PTAA was spin-coated onto NiO. X Anneal at 100°C for 10 minutes to obtain a hole transport layer;
[0027] (2) The perovskite precursor solution is spin-coated and annealed to form a thin film. Then, using perovskite as a substrate, an interface modification layer is prepared according to the preparation method of the interface modification layer provided in the fourth aspect. Then, an electron transport layer PCBM is spin-coated on the interface modification layer, and a buffer layer zirconium acetylacetonate is spin-coated. An Ag electrode with a thickness of 80-100 nm is deposited on zirconium acetylacetonate using a vapor deposition apparatus to obtain a perovskite solar cell that is not sensitive to the concentration of the interface modification ink.
[0028] The beneficial effects of this invention are as follows: This invention provides an interface modification material, which can be used to prepare interface modification ink. The interface modification ink is then spin-coated onto the photoactive layer of a perovskite solar cell to prepare an interface modification layer. Since the interface modification material includes bulky amines and bulky organic acids, the active substances they constitute can only act on the upper interface of the photoactive layer due to their significant steric hindrance effect. This characteristic effectively reduces the sensitivity of the perovskite solar cell to the thickness of the interface modification layer. When the concentration of the interface modification ink is in the range of 2-8 mg / mL, the photoelectric conversion efficiency of the perovskite solar cell remains above 15.43%. Compared to the 14.1% photoelectric conversion efficiency of a perovskite solar cell without an interface modification layer, the photovoltaic performance is improved by at least 9% after interface modification and passivation. Furthermore, the photovoltaic performance exhibits insensitivity to the interface modification ink, which will contribute to the large-scale commercial production of perovskite solar cells. Attached Figure Description
[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0030] Figure 1 This is a schematic diagram of the perovskite solar cell structure of the present invention.
[0031] Figure 2 Examples 6-9 and Comparative Example 1 of this invention are based on Cs 0.15 FA 0.7 MA 0.15 PbBr 0.6 I 2.4 Current-voltage curves of the perovskite solar cells in the system.
[0032] Figure 3 The graph shows the stable output efficiency of the perovskite solar cells in Embodiment 8 and Comparative Example 1 of this invention. Detailed Implementation
[0033] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.
[0034] Example 1: An interface modification ink
[0035] An interface-modifying ink was prepared by mixing and preparing MeO-2PACz and phenylethylamine as interface modification materials, and a mixture of toluene and isopropanol as solvent. The molar ratio of MeO-2PACz to phenylethylamine was 1:2, the volume ratio of toluene to isopropanol was 4:1, and the concentration of the interface-modifying ink was 2 mg / mL.
[0036] Example 2: An interface modification ink
[0037] The preparation method is the same as in Example 1, except that the concentration of the interface modification ink is 4 mg / mL.
[0038] Example 3: An Interface Modification Ink
[0039] The preparation method is the same as in Example 1, except that the concentration of the interface modification ink is 8 mg / mL.
[0040] Example 4: An Interface Modification Ink
[0041] The preparation method is the same as in Example 1, except that MeO-2PACz is replaced with triphenylamine ethyl phosphoric acid, the molar ratio of triphenylamine ethyl phosphoric acid to phenylethylamine is 1:2, and the concentration of the interface modification ink is 8 mg / mL.
[0042] Example 5: An interface modification layer
[0043] 20 μl of the interface-modified ink prepared in Example 1 was dropped onto the perovskite film as the photoactive layer. After standing for 10 seconds, spin coating was started. The spin coating rate was set to 3000 rpm for 30 seconds. After spin coating stopped, the film was transferred to a hot stage at 100°C and annealed for 5 minutes to obtain the interface-modified layer.
[0044] In some implementations, the interface-modified inks of Examples 2-4 can also be used to obtain interface-modified layers of different thicknesses and formulations using the preparation method of Example 5.
[0045] This invention also provides a perovskite solar cell. For example... Figure 1 As shown, the perovskite solar cell has a multilayered structure, consisting of, from bottom to top, a substrate, a transparent electrode, a hole transport layer, a photoactive layer, an interface modification layer, an electron transport layer, a buffer layer, and a metal electrode layer. The remaining structural layers can be adjusted according to specific requirements and are not restricted.
[0046] In some implementations, the specific materials for each layer are selected as follows: the substrate is glass, the transparent electrode is ITO, and the hole transport layer is NiO. X The PTAA bilayer structure has a photoactive layer of three-dimensional Cs. 0.15 FA 0.7 MA 0.15 PbBr0.6 I 2.4 The system is perovskite, the interface modification layer is the interface modification layer of Example 5 or the interface modification ink of Examples 2-4 obtained by the preparation method of Example 5, the electron transport layer is PCBM, the buffer layer is zirconium acetylacetonate, and the metal electrode layer is silver.
[0047] Example 6: A perovskite solar cell
[0048] Solutions of CsPbI2Br, FAPbI3, and MAPbBr3 were prepared using FAI, MABr, PbI2, PbBr2, and CsI as raw materials, respectively, in a 3:2 volume ratio of DMF and DMSO at a concentration of 1.5 M. One hour before spin-coating, the three solutions were mixed at a volume ratio of 0.15:0.70:0.15, and then MACl powder was added until the MACl concentration reached 25 mg / mL, thus obtaining the perovskite precursor solution.
[0049] Transparent conductive glass with striped ITO (anode) etched on its surface was sequentially cleaned with a cleaning agent, deionized water, acetone, and isopropanol using ultrasonic vibration for 15 minutes, dried with nitrogen gas, and then treated with ultraviolet ozone for 20 minutes; then a layer of NiO was spin-coated. X Nanoparticles (using deionized water as a dispersant, concentration 20 mg / mL, spin-coating parameters 4000 rpm for 30 s) were then annealed at 110 °C for 15 min; subsequently, they were transferred to a nitrogen-atmospheric glove box environment free of anhydrous and oxygen-free atmosphere, where a 1 mg / mL PTAA toluene solution was spin-coated onto NiO. X Anneal at 100°C for 10 minutes to obtain the hole transport layer.
[0050] During spin-coating of perovskite, 60 μL of perovskite precursor solution was rapidly added dropwise onto the hole transport layer. The spin-coating rate was set to 1000 rpm for 10 s, followed by 6000 rpm for 30 s. 170 μL of toluene was added dropwise 10 s before the end of spin-coating. After spin-coating was stopped, the mixture was transferred to a hot stage at 100 °C and annealed for 40 min to obtain the photoactive layer.
[0051] An interface modification layer was prepared on the photoactive layer according to the formulation and method of Example 5.
[0052] After annealing and cooling, the electron transport layer PCBM (chlorobenzene solvent, concentration 20 mg / mL) and the hole blocking layer zirconium acetylacetonate (isopropanol solvent, concentration 1 mg / mL) were spin-coated at 3000 rpm. Finally, an Ag electrode with a thickness of 80-100 nm was deposited on the zirconium acetylacetonate using an evaporator to obtain a perovskite solar cell.
[0053] Example 7: A perovskite solar cell
[0054] The preparation method is the same as in Example 6, except that the interface modification layer is different. In this example, the interface modification ink of Example 2 is used to prepare the interface modification layer using the method of Example 5.
[0055] Example 8: A perovskite solar cell
[0056] The preparation method is the same as in Example 6, except that the interface modification layer is different. In this example, the interface modification ink of Example 3 is used to prepare the interface modification layer using the method of Example 5.
[0057] Example 9: A perovskite solar cell
[0058] The preparation method is the same as in Example 6, except that the interface modification layer is different. In this example, the interface modification ink of Example 4 is used to prepare the interface modification layer using the preparation method of Example 5.
[0059] Example 10: A perovskite solar cell
[0060] The preparation method is the same as in Example 6, except that the perovskite precursor solution and the interface modification layer are different.
[0061] Perovskite precursor solution: Using FAI, MABr, PbI2, PbBr2, and CsI as raw materials, solutions of CsPbI2Br, FAPbI2Br, and MAPbBr3 were prepared respectively. The solvent was a mixture of DMF and DMSO (volume ratio 3:2) at a concentration of 1.5 M. One hour before spin coating, the three solutions were mixed at a volume ratio of 0.2:0.3:0.5, and then MACl powder was added until the MACl concentration reached 25 mg / mL, thus obtaining the perovskite precursor solution.
[0062] Interface modification layer: 20 μl of the interface modification ink prepared in Example 1 was dropped onto the perovskite film as the photoactive layer and spin-coated. The spin-coating rate was set to 3000 rpm for 30 s. After the spin-coating stopped, the film was transferred to a hot stage at 80°C and annealed for 1 min to obtain the interface modification layer.
[0063] Example 11: A perovskite solar cell
[0064] The preparation method is the same as in Example 6, except that the perovskite precursor solution and the interface modification layer are different.
[0065] Perovskite precursor solution: Using FAI, MABr, PbI2, PbBr2, and CsI as raw materials, solutions of CsPbI2Br, FAPbI2Br, and MAPbBr3 were prepared respectively. The solvent was a mixture of DMF and DMSO (volume ratio 3:2) at a concentration of 1.5 M. One hour before spin coating, the three solutions were mixed at a volume ratio of 0.35:0.25:0.4, and then MACl powder was added until the MACl concentration reached 25 mg / mL, thus obtaining the perovskite precursor solution.
[0066] Interface modification layer: 20 μl of the interface modification ink prepared in Example 1 was dropped onto the perovskite film as the photoactive layer. After standing for 20 seconds, spin coating was started. The spin coating rate was set to 3000 rpm for 30 seconds. After spin coating stopped, the film was transferred to a hot stage at 100°C and annealed for 5 minutes to obtain the interface modification layer.
[0067] Comparative Example 1: Perovskite Solar Cell without Interface Modification Layer
[0068] The preparation method is the same as in Example 6, except that instead of spin-coating an interface modification layer onto the photoactive layer, an electron transport layer is directly spin-coated.
[0069] At a light intensity of 100mW / cm 2 Under AM1.5G simulated sunlight irradiation, the current-voltage curves of Examples 6-9 and Comparative Example 1 were tested. Efficiency stability tests were performed on Examples 8 and Comparative Example 1 under a fixed bias voltage.
[0070] result:
[0071] like Figure 2 As shown, Example 6 is V OC =1.24V, J SC =16.24mA / cm 2 FF=76.58%, PCE=15.43%; Example 7 is V OC =1.24V, J SC =16.11mA / cm 2 FF=78.46%, PCE=15.69%; Example 8 is V OC =1.25V, J SC =16.44mA / cm 2 FF=81.10%, PCE=16.59%; Example 9 is V OC =1.24V, JSC =16.30mA / cm -2 FF=80.58%, PCE=16.20%; Comparative Example 1 is V OC =1.24V, J SC =16.22mA / cm 2 FF=70.39%, PCE=14.10%.
[0072] Compared to reference perovskite solar cells without an interface modification layer, perovskite solar cells with an interface modification layer prepared using the interface modification ink of this invention show improved PCE. Furthermore, when the concentration of the interface modification ink varies in the range of 2-8 mg / mL, the change in the concentration of the interface modification ink has little impact on the PCE of the perovskite solar cells. This indicates that the interface modification ink provided by this invention, when applied to perovskite solar cells, makes the perovskite solar cells thickness-insensitive, reduces the process requirements for preparing perovskite solar cells, and is beneficial to improving the performance of perovskite solar cells.
[0073] Depend on Figure 3 It can be seen that, over time, the photoelectric conversion efficiency of the perovskite solar cell in Example 8 can be stably output, while the photoelectric conversion efficiency of the perovskite solar cell in Comparative Example 1, which is not modified by the interface modification ink, decreases rapidly over time. This indicates that the interface modification ink and interface modification layer of the present invention can also improve the stability of the perovskite solar cell.
[0074] Although the present invention has been described in detail with reference to the accompanying drawings and preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. 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 also be covered within the protection scope of the present invention.
Claims
1. An interface modification ink characterized by, The solution includes a solvent and an interface modification material, wherein the interface modification material comprises a bulk amine and a bulk organic acid, the bulk amine being phenylethylamine and the bulk organic acid being MeO-2PACz; the molar ratio of MeO-2PACz to phenylethylamine is 1:1-2; the solvent is a mixed solution of toluene and isopropanol with a volume ratio of 4:1, and the mass concentration of the interface modification ink is 2-8 mg / mL.
2. An interface decoration layer, characterized in that, The interface modification layer is mainly formed by the interface modification ink as described in claim 1.
3. A method for preparing an interface modification layer as described in claim 2, characterized in that, Interface modification ink is dropped onto the surface of the photoactive layer, left to stand, spin-coated, and annealed to obtain the interface modification layer; wherein the standing time is 0-20s, the annealing temperature is 80-150℃, and the annealing time is 1-20min.
4. A perovskite solar cell, comprising, from bottom to top, a substrate, a transparent electrode, a hole transport layer, a photoactive layer, an interface modification layer, an electron transport layer, and a metal electrode layer, characterized in that, It also includes the interface modification layer as described in claim 2, wherein the interface modification layer is located between the photoactive layer and the electron transport layer.
5. The perovskite solar cell as described in claim 4, characterized in that, It also includes a buffer layer, which is BCP or zirconium acetylacetonate, located between the electron transport layer and the metal electrode; the substrate is glass, quartz, PET, or PEN; the transparent electrode is indium tin oxide or fluorine-doped tin oxide; the hole transport layer is nickel oxide, PTAA, PEDOT:PSS, or Poly-TPD; the electron transport layer is zinc oxide, PCBM, or C60; and the metal electrode is silver, gold, aluminum, magnesium, or copper.
6. The application of the interface-modified ink as described in claim 1 or the interface-modified layer as described in claim 2 in the fabrication of perovskite solar cells.