Unmodified layer transversal perovskite solar cell and its processing technology
By employing an unmodified layer structure in perovskite solar cells, using NiOx and Y:SnO2-doped oxide layers, the problems of low conductivity and high potential barrier of SnO2 films are solved, achieving cost reduction and performance improvement.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JINGDEZHEN CERAMIC UNIV
- Filing Date
- 2026-06-08
- Publication Date
- 2026-07-21
AI Technical Summary
In existing perovskite solar cells, the low conductivity of the SnO2 film and the high potential barrier between the perovskite layers lead to increased manufacturing costs, and the commonly used high-vacuum atomic layer deposition method limits cost reduction.
An unmodified layer structure is employed, using a NiOx hole transport layer and a Y:SnO2 electron transport layer, prepared via a solution method in an air environment. Combining the bilayer NiOx hole transport layer and the doped Y:SnO2 electron transport layer improves conductivity and reduces cost.
It effectively reduced the manufacturing cost of perovskite solar cells by more than 30%, broke through the limitations of high vacuum deposition equipment, and improved the electrical performance of the electron transport layer and light absorption layer.
Smart Images
Figure CN122438457A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of solar cell structure, and in particular to an unmodified inverted perovskite solar cell and its processing technology. Background Technology
[0002] Significant progress has been made in the field of perovskite solar cells (PSCs) in the current technology, with PSC efficiency increasing from 3.8% to over 27%. In most of the high-efficiency formal PSC device structures reported so far, NiO... x The hole transport layer uses 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), priced at 700-3000 RMB / gram. In most high-efficiency trans-PSCs device structures, the Y:SnO2 electron transport layer uses one or both of fullerene C60 and 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP) (priced at 300-3000 RMB / gram). These expensive small-molecule materials further increase the manufacturing cost of PSCs devices; therefore, reducing costs is an important task in promoting the commercial application of PSCs.
[0003] NiO x Two oxide materials, SnO2 and SnO2, were used as NiO. x Hole transport layer and Y:SnO2 electron transport layer materials are widely used in PSCs devices. Furthermore, NiO... x The price of SnO2 is 30-80 yuan / gram, only 1 / 10 of that of small molecule materials such as Spiro-OMeTAD, C60, and BCP. Therefore, using SnO2 instead of C60 and BCP as the electron transport layer material in inverse-structured PSCs devices can reduce the manufacturing cost of PSCs devices. However, SnO2 films suffer from low conductivity and a high potential barrier with perovskite. The common dispersion for preparing SnO2 films is SnO2 hydrogel dispersion, but water severely damages the crystal structure of perovskite, making direct solution deposition on the perovskite surface impossible. Therefore, the commonly used method for directly depositing SnO2 on the perovskite surface is high-vacuum atomic layer deposition.
[0004] Fabricating PSCs devices in air and using solution methods to prepare SnO2 films reduces the need for glove boxes and high-vacuum atomic layer deposition equipment, which is an important way to lower the cost of PSCs devices. Meanwhile, to overcome the problems of high potential barriers between perovskite and SnO2 and poor conductivity of SnO2 films, several interface modification strategies have been reported. Introducing thin C60 and BCP layers helps improve the conductivity of the Y:SnO2 electron transport layer and lower the electron transport barrier between perovskite and SnO2. However, this increases the overall fabrication cost of PSCs devices. Summary of the Invention
[0005] The main objective of this invention is to provide an unmodified inverted perovskite solar cell and its processing technology, aiming to solve the problems of improving the electrical performance of the electron transport layer and light absorption layer and reducing production costs.
[0006] To achieve the above objectives, the present invention provides an unmodified inverse perovskite solar cell, comprising: Conductive substrate; NiO x A hole transport layer is fabricated on the conductive substrate; Perovskite light-absorbing layer, processed on the NiO x On the hole transport layer; A Y:SnO2 electron transport layer is fabricated on the perovskite light-absorbing layer, wherein the Y doping ratio is 1.0 to 3.0 at%; The electrode layer is fabricated on the Y:SnO2 electron transport layer.
[0007] Furthermore, the NiO x Hole transport layer includes a first NiO x Hole transport layer and second NiO x Hole transport layer, the first NiO x The hole transport layer is laminated with the conductive substrate, and the second NiO x Hole transport layer and the first NiO x Hole transport layer stacking, wherein the first NiO x NiO in hole transport layer x The D50 parameter of the powder particle size is the second NiO x NiO in hole transport layer x The first NiO has a particle size D50 parameter that is 0.7 times that of the powder. x The thickness of the hole transport layer and the second NiO x The hole transport layer has a uniform thickness.
[0008] Furthermore, the D50 and D90 of the Y:SnO2 powder in the Y:SnO2 electron transport layer are 3 to 5 nm and 8 to 12 nm, respectively.
[0009] Furthermore, the thickness of the perovskite light-absorbing layer is 500 to 800 nm.
[0010] Furthermore, the thickness of the Y:SnO2 electron transport layer is 80nm to 100nm.
[0011] Furthermore, the electrode layer is prepared by a thermal evaporation process; the NiO xThe hole transport layer has a thickness of 30 to 50 nm, and the electrode layer has a thickness of 80 to 120 nm.
[0012] The present invention also provides a processing technology applied to the above-mentioned unmodified inverted perovskite solar cell, comprising: S1. Clean the conductive substrate; S2, NiO x NiO is formed by spin-coating an aqueous dispersion onto a conductive substrate and then annealing it. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S3, NiO x Aqueous dispersion spin-coated onto NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S4, Preparation of FA 0.8 MA 0.2 PbI3 solution was spin-coated onto the substrate / NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x / FA 0.8 MA 0.2 PbI3 layer, where FA 0.8 MA 0.2 The PbI3 solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The spin coating speed is 3500-4500 rpm, the spin coating time is 20 to 40 s, and 0.5 mL of ethyl acetate is added dropwise during the spin coating process. The annealing temperature is 80 to 150℃, and the annealing time is 15 to 25 min. S5. After diluting the acetic acid dispersion of Y:SnO2 nanomaterials with a concentration of 8% to 20% to 2% to 3% with isopropanol to obtain a Y:SnO2 nanoparticle dispersion, the Y:SnO2 nanoparticle dispersion is spin-coated onto a substrate / NiO. x / FA 0.8 MA 0.2 After annealing the PbI3 layer, a substrate / NiO is obtained. x / FA 0.8 MA 0.2 PbI3 / Y:SnO2 layer; S6, on substrate / NiO x / FA 0.8 MA 0.2A trans-perovskite solar cell without modification layer is obtained by thermally evaporating the upper electrode layer on a PbI3 / Y:SnO2 layer.
[0013] Furthermore, in step S2, NiO x The D50 parameter is the NiO in step S3. x It is 0.7 times the D50 parameter.
[0014] Furthermore, in step S4, FA 0.8 MA 0.2 The solutes in the PbI3 solution are PbI2, FAI, MAI, and MACl. 0.8 MA 0.2 PbI3, with N,N-dimethylformamide / N-methylpyrrolidone in a volume ratio of 4:1.
[0015] Further, step S5 includes: Y:SnO2 nanoparticles were dispersed in a mixed solution of acetic acid and isopropanol to obtain a Y:SnO2 nanoparticle dispersion, wherein the ratio of acetic acid to isopropanol was between 1:3 and 1:5. The Y:SnO2 nanoparticle dispersion was spin-coated onto the perovskite light-absorbing layer and then annealed. The spin-coating speed was 3000-4000 rpm, the spin-coating time was 30 to 50 s, the annealing temperature was 80-120℃, and the annealing time was 15 to 25 min.
[0016] This invention provides an unmodified inverted perovskite solar cell and its fabrication process. Based on the design of Y:SnO2, a novel inverted perovskite solar cell with dual oxide functional layers is presented. Using oxides as functional layers effectively reduces device fabrication costs. The oxide layers serve as the electron transport layer for Y:SnO2 and NiO. x Hole transport layers can reduce raw material and manufacturing costs by more than 30%; the fabrication of unmodified inverse perovskite solar cells in an air environment overcomes the limitations of glove box and high-vacuum atomic layer deposition conditions. Attached Figure Description
[0017] Figure 1 This is a schematic diagram of the structure of the unmodified inverted perovskite solar cell of Embodiment 1 of the present invention; Figure 2 This is the JV curve of the unmodified inverted perovskite solar cell of Embodiment 1 of the present invention; Figure 3 This is the JV curve of Comparative Example 1 of the present invention; Figure 4 This is a comparison of the IV curves of Embodiment 1 and Comparative Example 1 of the present invention; Figure 5These are the SEM and EDS images of Embodiment 1 of the present invention, wherein the first image is an SEM image, and the latter three images are the elemental distributions of Sn, O and Y, respectively; Figure 6 The NiO in Embodiment 1 of this invention x SEM image of the thin film; Figure 7 NiO in Comparative Example 2 of this invention x AFM images; Figure 8 NiO in Embodiment 1 of the present invention x AFM image. Detailed Implementation
[0018] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0019] Those skilled in the art will understand that, unless specifically stated otherwise, the singular forms “a,” “an,” “the,” “the,” and “the” used herein may also include the plural forms. It should be further understood that the term “comprising” as used in this specification means the presence of the stated features, integers, steps, operations, elements, units, modules, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, units, modules, components, and / or groups thereof. It should be understood that when we say an element is “connected” or “coupled” to another element, it can be directly connected or coupled to the other element, or there may be intermediate elements. Furthermore, “connected” or “coupled” as used herein can include wireless connection or wireless coupling. The term “and / or” as used herein includes all or any of the units and all combinations of one or more associated listed items.
[0020] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.
[0021] Reference Figures 1 to 8 In one embodiment of the present invention, an unmodified inverse perovskite solar cell includes: Conductive substrate 100; NiO x Hole transport layer 200 is fabricated on the conductive substrate 100; The perovskite light-absorbing layer 300 is processed on the NiO. xHole transport layer 200; A Y:SnO2 electron transport layer 400 is fabricated on the perovskite light-absorbing layer 300, wherein the Y doping ratio is 1.0 to 3.0 at%; Electrode layer 500 is fabricated on the Y:SnO2 electron transport layer 400.
[0022] In existing technologies, there is a contradiction between improving the electrical performance of the electron transport layer and the light absorption layer and controlling costs.
[0023] The unmodified inverse perovskite solar cell provided by this invention includes a conductive substrate 100 and NiO. x Hole transport layer 200, perovskite light absorption layer 300, Y:SnO2 electron transport layer 400 and electrode layer 500.
[0024] The conductive substrate 100 can be made of FTO conductive glass or ITO conductive glass, and different materials can be selected in different embodiments.
[0025] NiO x Hole transport layer 200 is fabricated on conductive substrate 100. NiO x The hole transport layer 200 can be fabricated by using NiO. x The aqueous dispersion is formed by spin-coating onto a conductive substrate 100 and then annealing.
[0026] Perovskite light-absorbing layer 300 is processed on NiO x On hole transport layer 200. In a fabrication process, FA is prepared. 0.8 MA 0.2 PbI3 solution was spin-coated onto the substrate / NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x / FA 0.8 MA 0.2 PbI3 layer, where FA 0.8 MA 0.2 The PbI3 solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
[0027] A Y:SnO2 electron transport layer 400 is fabricated on a perovskite light-absorbing layer 300. In one preparation process, an acetic acid dispersion of Y:SnO2 nanomaterials with a concentration of 8% to 20% isopropanol is diluted to 2% to 3% to obtain a Y:SnO2 nanoparticle dispersion. This Y:SnO2 nanoparticle dispersion is then spin-coated onto a substrate / NiO2 substrate. x / FA 0.8 MA 0.2 After annealing the PbI3 layer, a substrate / NiO is obtained. x / FA0.8 MA 0.2 PbI3 / Y:SnO2 layer. The doping ratio of Y is 1.0 to 3.0 at%.
[0028] Electrode layer 500 is fabricated on Y:SnO2 electron transport layer 400. The fabrication method for electrode layer 500 can be thermal evaporation, etc.
[0029] In a typical structure, the conductive substrate 100 is an ITO glass sheet, and NiO is used. x The hole transport layer 200 has a thickness of 30 to 50 nm, the perovskite light absorption layer 300 has a thickness of 500 to 800 nm, the Y:SnO2 electron transport layer 400 has a thickness of 80 nm to 100 nm, and the electrode layer 500 has a thickness of 80 to 120 nm. For specific processing techniques, please refer to the following embodiments.
[0030] In summary, a novel inverse perovskite solar cell with a dual oxide functional layer was designed based on Y:SnO2. Using oxides as the functional layer can effectively reduce the device fabrication cost. The oxide layer is used as the electron transport layer of Y:SnO2 and NiO. x The hole transport layer 200 can reduce raw material and manufacturing costs by more than 30%; the fabrication of unmodified inverse perovskite solar cells in an air environment overcomes the limitations of glove box and high vacuum atomic layer deposition conditions.
[0031] In one embodiment, the NiO x Hole transport layer 200 includes a first NiO x Hole transport layer and second NiO x Hole transport layer, the first NiO x The hole transport layer is laminated with the conductive substrate 100, and the second NiO x Hole transport layer and the first NiO x Hole transport layer stacking, wherein the first NiO x NiO in hole transport layer x The D50 parameter of the powder particle size is the second NiO x NiO in hole transport layer x The first NiO has a particle size D50 parameter that is 0.7 times that of the powder. x The thickness of the hole transport layer and the second NiO x The hole transport layer has a uniform thickness.
[0032] In this embodiment, considering NiO x The hole transport layer 200 has a relatively large thickness, so NiO... x Hole transport layer 200 is divided into the first NiO x Hole transport layer and second NiO xHole transport layer and independently fabricated, and second NiO x The hole transport layer has a relatively large particle size, forming a perovskite light-absorbing layer 300 in the second NiO. x The combination on the hole transport layer provides a more favorable interface.
[0033] In one embodiment, the D50 and D90 of the Y:SnO2 powder in the Y:SnO2 electron transport layer 400 are 3 to 5 nm and 8 to 12 nm, respectively.
[0034] In this embodiment, to improve the conductivity of the Y:SnO2 electron transport layer 400 and reduce the potential barrier between it and the perovskite light absorption layer 300, the gradation of the Y:SnO2 powder is restricted. This results in improved uniformity and density of the Y:SnO2 electron transport layer 400.
[0035] In one embodiment, the conductive substrate 100 is selected from FTO conductive glass and ITO conductive glass.
[0036] In this embodiment, two common and easy-to-implement conductive substrate 100 material choices are given.
[0037] In one embodiment, the thickness of the perovskite light-absorbing layer 300 is 500 to 800 nm.
[0038] In this embodiment, the thickness of the perovskite light-absorbing layer 300 is limited, thereby taking into account the relationship between performance and process, making it easy to process while also having qualified performance parameters.
[0039] In one embodiment, the thickness of the Y:SnO2 electron transport layer 400 is 80 nm to 100 nm.
[0040] In this embodiment, the thickness of the Y:SnO2 electron transport layer 400 is limited, thereby combining the relationship between performance and process, making it easy to process while also having qualified performance parameters.
[0041] In one embodiment, the electrode layer 500 is prepared by a thermal evaporation process; the NiO x The hole transport layer 200 has a thickness of 30 to 50 nm, and the electrode layer 500 has a thickness of 80 to 120 nm.
[0042] In this embodiment, a convenient processing technology for the electrode layer 500 is provided, and a suitable thickness for the electrode layer 500 is defined.
[0043] The present invention also provides a processing technology applied to the above-mentioned unmodified inverted perovskite solar cell, comprising: S1. Clean the conductive substrate 100; S2, NiOx NiO is formed by spin-coating an aqueous dispersion onto a conductive substrate 100 and then annealing it. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S3, NiO x Aqueous dispersion spin-coated onto NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S4, Preparation of FA 0.8 MA 0.2 PbI3 solution was spin-coated onto the substrate / NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x / FA 0.8 MA 0.2 PbI3 layer, where FA 0.8 MA 0.2 The PbI3 solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The spin coating speed is 3500-4500 rpm, the spin coating time is 20 to 40 s, and 0.5 mL of ethyl acetate is added dropwise during the spin coating process. The annealing temperature is 80 to 150℃, and the annealing time is 15 to 25 min. S5. After diluting the acetic acid dispersion of Y:SnO2 nanomaterials with a concentration of 8% to 20% to 2% to 3% with isopropanol to obtain a Y:SnO2 nanoparticle dispersion, the Y:SnO2 nanoparticle dispersion is spin-coated onto a substrate / NiO. x / FA 0.8 MA 0.2 After annealing the PbI3 layer, a substrate / NiO is obtained. x / FA 0.8 MA 0.2 PbI3 / Y:SnO2 layer; S6, on substrate / NiO x / FA 0.8 MA 0.2 A trans-perovskite solar cell without modification layer is obtained by thermally evaporating the upper electrode layer on a PbI3 / Y:SnO2 layer for 500 seconds.
[0044] In this embodiment, in step S1, the conductive substrate 100 is cleaned. The cleaning process can be performed using deionized water, acetone, or anhydrous ethanol for ultrasonic cleaning for 20 to 30 minutes, followed by drying with a hairdryer and ultraviolet ozone treatment for 15 to 25 minutes.
[0045] In step S2, NiO x NiO is formed by spin-coating an aqueous dispersion onto a conductive substrate 100 and then annealing it. x Layer. Spin coating speed is 3500-4500 rpm, spin coating time is 20 to 40 seconds, annealing temperature is 120-170℃, annealing time is 15 to 25 minutes. In step S3, NiO... x Aqueous dispersion spin-coated onto NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x Layer. Spin coating speed is 3500-4500 rpm, spin coating time is 20 to 40 seconds, annealing temperature is 120-170℃, annealing time is 15 to 25 minutes. NiO x The particle size is between 10 and 25 nm.
[0046] Reference Figure 6 and Figure 7 It can be observed that monolayer NiO x The thin film could not completely cover the ITO surface, resulting in pores. (Double spin coating of NiO) x It can effectively reduce holes and suppress leakage current.
[0047] In step S4, FA is prepared. 0.8 MA 0.2 PbI3 solution was spin-coated onto the substrate / NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x / FA 0.8 MA 0.2 PbI3 layer. FA 0.8 MA 0.2 The PbI3 solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The spin coating speed is 3500-4500 rpm, the spin coating time is 20 to 40 s, and 0.5 mL of ethyl acetate is added dropwise during the spin coating process. The annealing temperature is 80 to 150℃, and the annealing time is 15 to 25 min.
[0048] In step S5, after diluting the 8% to 20% Y:SnO2 nanomaterial acetic acid dispersion to 2% to 3% with isopropanol to obtain a Y:SnO2 nanoparticle dispersion, the Y:SnO2 nanoparticle dispersion is spin-coated onto a substrate / NiO. x / FA 0.8 MA 0.2 After annealing the PbI3 layer, a substrate / NiO is obtained. x / FA 0.8 MA 0.2 PbI3 / Y:SnO2 layer.
[0049] In step S6, on the substrate / NiO x / FA 0.8 MA 0.2 An unmodified inverse perovskite solar cell is obtained by thermally evaporating an electrode layer 500 on a PbI3 / Y:SnO2 layer. Electrode layer 500 can be silver. Specific evaporation parameters include: vacuum level: 10... -3 Pa to 10 - 5 Pa, vapor deposition rate: 0.1 to 1 Å / s.
[0050] In summary, a novel inverse perovskite solar cell with a dual oxide functional layer based on Y:SnO2 was designed, and a solution preparation method for PSCs in an air environment was provided. Using oxides as functional layers can effectively reduce the fabrication cost of PSCs. Current challenges include: 1. Dispersion of nano-SnO2 materials; 2. Improving the conductivity of the SnO2 film; 3. Fabrication of unmodified inverse perovskite solar cells in an air environment. This method, fabricated in an air environment, overcomes the limitations of glove box and high-vacuum atomic layer deposition conditions; simultaneously, oxide layers are used as the electron transport layer for Y:SnO2 and NiO. x Hole transport layer 200 can reduce raw material and manufacturing costs by more than 30%.
[0051] In one embodiment, NiO in step S2 x The D50 parameter is the NiO in step S3. x It is 0.7 times the D50 parameter.
[0052] In this embodiment, considering NiO x The hole transport layer 200 has a relatively large thickness, so NiO... x Hole transport layer 200 is divided into the first NiO x Hole transport layer and second NiO x Hole transport layer and independently fabricated, and second NiO x The hole transport layer has a relatively large particle size, forming a perovskite light-absorbing layer 300 in the second NiO. x The combination on the hole transport layer provides a more favorable interface.
[0053] In one embodiment, in step S4, FA 0.8 MA 0.2 The solutes in the PbI3 solution are PbI2, FAI, MAI, and MACl. 0.8 MA 0.2 PbI3, with N,N-dimethylformamide / N-methylpyrrolidone in a volume ratio of 4:1.
[0054] In this embodiment, a material basis for the perovskite light-absorbing layer 300 is provided, which ultimately achieves superior electrical performance.
[0055] In one embodiment, step S5 includes: Y:SnO2 nanoparticles were dispersed in a mixed solution of acetic acid and isopropanol to obtain a Y:SnO2 nanoparticle dispersion, wherein the ratio of acetic acid to isopropanol was between 1:3 and 1:5. The Y:SnO2 nanoparticle dispersion was spin-coated onto the perovskite light-absorbing layer 300 and then annealed. The spin-coating speed was 3000-4000 rpm, the spin-coating time was 30 to 50 s, the annealing temperature was 80-120℃, and the annealing time was 15 to 25 min. Example
[0056] The unmodified inverted perovskite solar cell involved in this embodiment has a band gap of approximately 1.50-1.55 eV for the perovskite light-absorbing layer 300, and its structure is as follows. Figure 1 As shown, from bottom to top, there are (ITO) conductive substrate 100, NiO... x Hole transport layer 200, perovskite light absorption layer 300, Y:SnO2 electron transport layer 400 and electrode layer 500.
[0057] The unmodified inverted perovskite solar cell in this embodiment was prepared in an air environment by a one-step spin-coating method, the specific steps of which are as follows: Step 1: Cleaning and pretreatment of conductive substrate 100. The ITO glass slide is ultrasonically cleaned sequentially with deionized water, acetone and anhydrous ethanol for 20 to 30 minutes. After ultrasonic cleaning, it is dried with a hair dryer and treated with ultraviolet ozone for 15 to 25 minutes.
[0058] Step 2, NiO x Hole transport layer 200 preparation: (1) NiO x The solution was dispersed by ultrasonication in an ultrasonic cleaner for 20 minutes to obtain dispersed NiO. x Solution; (2) Take 65 μL NiO x The solution was spin-coated onto an ITO substrate at a speed of 3500-4500 rpm for 30 seconds to obtain NiO. x wet film, NiO x The wet film was transferred to a hot plate at 150°C and annealed for 20 minutes. (3) Step (2) was repeated once to obtain ITO / NiO. x Layer. NiO x The particle size is between 10 and 25 nm. NiO x The hole transport layer 200 has a thickness of 30 nm.
[0059] Step 3, Preparation of perovskite light-absorbing layer 300: (1) Preparation of precursor solution: Dissolve PbI2 (700-750mg), FAI (200-220mg), MAI (48-52mg), and MACl (35-39mg) in a mixed solvent (DMF:NMP=4:1 volume ratio); (2) Pretreated ITO / NiO x Using a pipette as a substrate, 60 µL of FA was aspirated. 0.8 MA 0.2 PbI3 solution, dropped onto ITO / NiO x Spin-coating was performed on the sample; the low spin speed was 600 rpm for 5 seconds, and the high spin speed was 4000 rpm for 30 seconds. After 20 seconds of high-speed spin-coating, 0.5 mL of ethyl acetate was rapidly added dropwise to obtain FA. 0.8 MA 0.2 PbI3 wet film; (3) FA 0.8 MA 0.2 The PbI3 wet film was transferred to a hot plate at 120°C and annealed for 20 min to obtain ITO / NiO. x / FA 0.8 MA 0.2 The PbI3 layer contains a perovskite light-absorbing layer with a thickness of 500 nm.
[0060] Step 4, Preparation of Y:SnO2 electron transport layer 400: (1) Dilute the 12% yttrium-doped tin dioxide (Y:SnO2) nanomaterial acetic acid solution to 2% to 3% with isopropanol, and sonicate the diluted Y:SnO2 solution in an ultrasonic cleaner for 10 to 30 min to obtain a dispersed Y:SnO2 solution; (2) Take 95µL of Y:SnO2 solution and drop it onto FA 0.8 MA 0.2 On PbI3, a spin coater was used to spin coat Y:SnO2 wet film at a speed of 3000 rpm for 45 s; (3) The Y:SnO2 wet film was transferred to a hot plate at 100℃ and annealed for 20 min to obtain ITO / NiO x / FA 0.8 MA 0.2 The PbI3 / Y:SnO2 layer has a thickness of 80 nm to 100 nm.
[0061] Step 5: Preparation of silver electrode: A silver counter electrode with a thickness of approximately 80 nm was prepared on Y:SnO2 using a thermal evaporation method to obtain an unmodified inverse perovskite solar cell device; specific evaporation parameters included: vacuum degree: 10 -3 Pa to 10 -5 Pa, vapor deposition rate: 0.1 to 1 Å / s.
[0062] Step 6, Photovoltaic Performance Testing: The effective area of the unmodified inverse perovskite solar cell device prepared by the above method is 0.07 cm². 2 At 100mW / cm 2 Measurements were taken under illumination (AM1.5G), with a scanning range of -1.2V to 0V and a scanning step size of 0.01V.
[0063] The JV characteristic curves of the obtained Y:SnO2-based unmodified inverse perovskite solar cell device are as follows: Figure 2 As shown, by Figure 2 It can be seen that the open-circuit voltage of the unmodified inverse perovskite solar cell based on Y:SnO2 is -0.953V, and the short-circuit current density is -23.55mA / cm. 2 The fill factor is 60.45% and the photoelectric efficiency is 13.56%. Example
[0064] The difference between Example 2 and Example 1 is that the D50 and D90 of the Y:SnO2 powder in the Y:SnO2 electron transport layer 400 are 3 to 5 nm and 8 to 12 nm, respectively. The thickness of the perovskite light absorption layer 300 is 800 nm; the thickness of the Y:SnO2 electron transport layer 400 is 100 nm; and the thickness of the NiO is... x The hole transport layer 200 has a thickness of 50 nm; the electrode layer 500 has a thickness of 120 nm.
[0065] Comparative Example 1 Comparative Example 1 provides an unmodified inverse perovskite solar cell structure, wherein the device structure, from bottom to top, consists of a conductive substrate 100 and a NiO layer. x Hole transport layer 200, perovskite light absorption layer 300 (FA) 0.8 MA 0.2 PbI3)(3), Y:SnO2 electron transport layer 400 (SnO2) (4) and electrode layer 500. The biggest difference between Comparative Example 1 and Example 1 is the material of Y:SnO2 electron transport layer 400. The comparative example uses SnO2 as Y:SnO2 electron transport layer 400.
[0066] This comparative example also uses the all-solution spin-coating method in an air environment to fabricate the device structure. The specific steps include the following: Step 1: Cleaning and pretreatment of conductive substrate 100. The ITO glass slide is ultrasonically cleaned sequentially with deionized water, acetone and anhydrous ethanol for 20 to 30 minutes. After ultrasonic cleaning, it is dried with a hair dryer and treated with ultraviolet ozone for 15 to 25 minutes.
[0067] Step 2, NiO x Hole transport layer 200 preparation: (1) NiOx The solution was dispersed by ultrasonication in an ultrasonic cleaner for 20 minutes to obtain dispersed NiO. x Solution; (2) Take 65 μL NiO x The solution was spin-coated onto an ITO substrate at a speed of 3500-4500 rpm for 30 seconds to obtain NiO. x wet film, NiO x The wet film was transferred to a hot plate at 150°C and annealed for 20 min; (3) Step (2) was repeated once to obtain ITO / NiO. x layer.
[0068] Step 3, Preparation of perovskite light-absorbing layer 300: (1) Preparation of precursor solution: Dissolve PbI2 (700-750mg), FAI (200-220mg), MAI (48-52mg), and MACl (35-39mg) in a mixed solvent (DMF:NMP=4:1 volume ratio); (2) Pretreated ITO / NiO x Using a pipette as a substrate, 60 µL of FA was aspirated. 0.8 MA 0.2 PbI3 solution, dropped onto ITO / NiO x Spin-coating was performed on the sample; the low spin speed was 600 rpm for 5 seconds, and the high spin speed was 4000 rpm for 30 seconds. After 20 seconds of high-speed spin-coating, 0.5 mL of ethyl acetate was rapidly added dropwise to obtain FA. 0.8 MA 0.2 PbI3 wet film; (3) FA 0.8 MA 0.2 The PbI3 wet film was transferred to a hot plate at 120°C and annealed for 20 min to obtain ITO / NiO. x / FA 0.8 MA 0.2 The PbI3 layer, also known as the perovskite light-absorbing layer 300.
[0069] Step 4, Preparation of Y:SnO2 electron transport layer 400: (1) Disperse tin dioxide (SnO2) nanomaterials in isopropanol at a concentration of 2% to 3%, and sonicate for 10 to 30 min to obtain a dispersed SnO2 solution; (2) Take 95 µL of SnO2 solution and drop it onto FA 0.8 MA 0.2 On PbI3, a spin coater was used to spin coat SnO2 wet film at a speed of 3000 rpm for 45 s; (3) the SnO2 wet film was transferred to a hot plate at 100℃ for annealing for 20 min to obtain ITO / NiO x / FA 0.8 MA 0.2 PbI3 / SnO2 layer.
[0070] Step 5: Preparation of silver electrode: A silver counter electrode with a thickness of approximately 100 nm is prepared on SnO2 using a thermal evaporation method to obtain an unmodified inverse perovskite solar cell device; specific evaporation parameters include: vacuum degree: 10 -3 Pa to 10 -5 Pa, vapor deposition rate: 0.1 to 1 Å / s.
[0071] Step 6, Photovoltaic Performance Testing: The effective area of the unmodified inverse perovskite solar cell device prepared by the above method is 0.07 cm². 2 At 100mW / cm 2 Measurements were taken under illumination (AM1.5G), with a scanning range of -1.2V to 0V and a scanning step size of 0.01V.
[0072] The JV characteristic curves of the SnO2-based unmodified inverse perovskite solar cell device obtained in the comparative example are shown below. Figure 3 As shown, by Figure 3 It can be seen that the open-circuit voltage of the SnO2-based unmodified inverse perovskite solar cell is -0.955V, and the short-circuit current density is -23.07mA / cm². 2 The fill factor is 36.61% and the photoelectric efficiency is 8.06%, which is significantly worse than that of Example 1.
[0073] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that in step 2, 130 μL of NiO is taken. x The solution was spin-coated onto an ITO substrate at a speed of 3500-4500 rpm for 30 seconds to obtain NiO. x wet film, NiO x The wet film was transferred to a hot plate at 150°C and annealed for 20 minutes. (Refer to...) Figure 6 The surface properties of a single spin coating are relatively weaker than those of a two-spin coating. Example
[0074] The difference between Example 3 and Example 1 is that (1) NiO is used. x The solution was dispersed by ultrasonication in an ultrasonic cleaner for 20 minutes to obtain dispersed NiO. x Solution; (2) Take 65 μL NiO x The solution was spin-coated onto an ITO substrate at a speed of 3500-4500 rpm for 30 seconds to obtain NiO. x wet film, NiO x The wet film was transferred to a hot plate at 150°C and annealed for 20 minutes to form the first NiO. xHole transport layer. (3) Repeat step (2) once more to form the second NiO. x Hole transport layer. First NiO x The thickness of the hole transport layer and the second NiO x The hole transport layer has a uniform thickness, and the first NiO x NiO in hole transport layer x The D50 parameter of the powder particle size is the second NiO x NiO in hole transport layer x 0.7 times the D50 parameter of the powder particle size. First NiO x NiO in hole transport layer x The powder particle size is 15 nm. The final unmodified inverse perovskite solar cell exhibits an open-circuit voltage of -0.943 V and a short-circuit current density of -23.77 mA / cm². 2 The fill factor is 61.32% and the photoelectric efficiency is 14.32%.
[0075] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.
Claims
1. A trans-perovskite solar cell without a modification layer, characterized in that, include: Conductive substrate (100); NiO x A hole transport layer (200) is fabricated on the conductive substrate (100); Perovskite light-absorbing layer (300), processed on the NiO x On the hole transport layer (200); A Y:SnO2 electron transport layer (400) is fabricated on the perovskite light-absorbing layer (300), wherein the Y doping ratio is 1.0 to 3.0 at%; An electrode layer (500) is fabricated on the Y:SnO2 electron transport layer (400).
2. The unmodified inverted perovskite solar cell according to claim 1, characterized in that, The NiO x Hole transport layer (200) includes a first NiO x Hole transport layer and second NiO x Hole transport layer, the first NiO x The hole transport layer is laminated with the conductive substrate (100), and the second NiO x Hole transport layer and the first NiO x Hole transport layer stacking, wherein the first NiO x NiO in hole transport layer x The D50 parameter of the powder particle size is the second NiO x NiO in hole transport layer x The first NiO has a particle size D50 parameter that is 0.7 times that of the powder. x The thickness of the hole transport layer and the second NiO x The hole transport layer has a uniform thickness.
3. The unmodified inverted perovskite solar cell according to claim 1, characterized in that, The D50 and D90 of the Y:SnO2 powder in the Y:SnO2 electron transport layer (400) are 3 to 5 nm and 8 to 12 nm, respectively.
4. The unmodified inverted perovskite solar cell according to claim 1, characterized in that, The thickness of the perovskite light-absorbing layer (300) is 500 to 800 nm.
5. The unmodified inverted perovskite solar cell according to claim 1, characterized in that, The thickness of the Y:SnO2 electron transport layer (400) is 80 nm to 100 nm.
6. The unmodified inverted perovskite solar cell according to claim 1, characterized in that, The electrode layer (500) is prepared by a thermal evaporation process; the NiO x The hole transport layer (200) has a thickness of 30 to 50 nm, and the electrode layer (500) has a thickness of 80 to 120 nm.
7. A processing technique applied to the unmodified inverted perovskite solar cell according to any one of claims 1 to 6, characterized in that, include: S1. Clean the conductive substrate (100). S2, NiO x NiO is formed by spin-coating an aqueous dispersion onto a conductive substrate (100) and then annealing. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S3, NiO x Aqueous dispersion spin-coated onto NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x The layers are prepared by spin coating at a speed of 3500-4500 rpm for 20 to 40 seconds, annealing at a temperature of 120-170℃ for 15 to 25 minutes. S4, Preparation of FA 0.8 MA 0.2 PbI3 solution was spin-coated onto the substrate / NiO x After the layer is applied, annealing is performed to obtain the substrate / NiO. x / FA 0.8 MA 0.2 PbI3 layer, where FA 0.8 MA 0.2 The PbI3 solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The spin coating speed is 3500-4500 rpm, the spin coating time is 20 to 40 s, and 0.5 mL of ethyl acetate is added dropwise during the spin coating process. The annealing temperature is 80 to 150℃, and the annealing time is 15 to 25 min. S5. After diluting the acetic acid dispersion of Y:SnO2 nanomaterials with a concentration of 8% to 20% to 2% to 3% with isopropanol to obtain a Y:SnO2 nanoparticle dispersion, the Y:SnO2 nanoparticle dispersion is spin-coated onto a substrate / NiO. x / FA 0.8 MA 0.2 After annealing the PbI3 layer, a substrate / NiO is obtained. x / FA 0.8 MA 0.2 PbI3 / Y:SnO2 layer; S6, on substrate / NiO x / FA 0.8 MA 0.2 A modified inverted perovskite solar cell was obtained by thermally evaporating an upper electrode layer (500) on a PbI3 / Y:SnO2 layer.
8. The processing technology according to claim 7, characterized in that, NiO in step S2 x The D50 parameter is the NiO in step S3. x It is 0.7 times the D50 parameter.
9. The processing technology according to claim 7, characterized in that, In step S4, FA 0.8 MA 0.2 The solutes in the PbI3 solution are PbI2, FAI, MAI, and MACl. 0.8 MA 0.2 PbI3, with N,N-dimethylformamide / N-methylpyrrolidone in a volume ratio of 4:
1.
10. The processing technology according to claim 7, characterized in that, The steps in S5 include: Y:SnO2 nanoparticles were dispersed in a mixed solution of acetic acid and isopropanol to obtain a Y:SnO2 nanoparticle dispersion, wherein the ratio of acetic acid to isopropanol was between 1:3 and 1:
5. The Y:SnO2 nanoparticle dispersion was spin-coated onto the perovskite light-absorbing layer (300) and then annealed. The spin-coating speed was 3000-4000 rpm, the spin-coating time was 30 to 50 s, the annealing temperature was 80-120℃, and the annealing time was 15 to 25 min.