A method for processing a metal oxide layer-perovskite layer interface
By coating a mixed solution of ligand reagent and SAM material onto the surface of a metal oxide layer and then annealing it, a ligand-coupled SAM layer is formed, which solves the problems of interface delamination and self-assembly uniformity in perovskite solar cells and improves charge transport characteristics and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- 华能青海发电有限公司
- Filing Date
- 2024-12-10
- Publication Date
- 2026-06-09
Smart Images
Figure BDA0005180837640000061
Abstract
Description
Technical Field
[0001] This invention belongs to the field of perovskite solar cell technology, specifically relating to a method for processing the interface between a metal oxide layer and a perovskite layer. Background Technology
[0002] Perovskite solar cells are a revolutionary new photovoltaic technology, selected by the journal *Science* as one of the top ten scientific breakthroughs of 2013. They possess advantages such as high efficiency, low cost, and the ability to be fabricated using low-temperature solution methods. In just over a decade, perovskite solar cells have become one of the most popular branches of next-generation photovoltaic technology, attracting significant attention and R&D investment from academic and industrial communities both domestically and internationally.
[0003] In recent years, self-assembled monolayers (SAMs), as a novel class of ultrathin materials, have played a crucial role in various solution-processed thin-film electronic devices (including OFETs, PSCs, OSCs, and OLEDs), attracting extensive exploration from researchers in academia and industry. Due to their excellent structural versatility and ease of fabrication, SAMs can effectively passivate and optimize interfaces in solution-processed thin-film electronic devices, facilitating the fabrication of efficient, functionalized, large-size, or flexible devices for complex circuits and integrated systems. Furthermore, their biocompatibility, derived from their organic nature, provides new solutions for emerging fields, such as IoT sensors for wearable electronics and biomedical applications.
[0004] In the field of perovskite solar cells, there are also studies utilizing SAM as a hole transport layer. For example, patent application CN118555884A discloses a method for optimizing the NiOx / SAM hole transport layer in perovskite solar cells, belonging to the field of perovskite solar cell fabrication technology. This method achieves uniform and robust anchoring of SAM molecules by improving the surface of the NiOx thin film, thereby promoting charge extraction and suppressing interfacial nonradiative recombination. This invention mainly improves the surface properties of the NiOx thin film by subjecting it to oxygen-air plasma treatment (O2-plasma). O2-plasma treatment increases the conductivity of NiOx, promoting hole extraction from perovskite to NiOx / SAM. SAM molecules form a uniform, dense, and robust monolayer on the O2-plasma-treated NiOx surface, achieving high-quality perovskite thin films and efficient charge extraction.
[0005] However, in existing technologies, when fabricating perovskite layers on SAM layers, delamination easily occurs between the conductive substrate, metal oxide layer, and SAM layer, and the self-assembly uniformity of the SAM layer also needs improvement. This results in insufficient charge transport characteristics of perovskite solar cells. Therefore, it is urgent to design a method for treating the interface between the metal oxide layer and the perovskite layer, which can improve the adhesion between the conductive substrate, metal oxide layer, and SAM layer, and improve the self-assembly uniformity of the SAM layer, thereby optimizing the charge transport characteristics of perovskite solar cells. Summary of the Invention
[0006] This invention aims to at least partially solve one of the technical problems in related technologies. To this end, embodiments of this invention propose a method for processing the interface between a metal oxide layer and a perovskite layer.
[0007] This invention provides a method for processing the interface between a metal oxide layer and a perovskite layer, comprising the following steps:
[0008] S1. Dissolve the ligand reagent and SAM material in a solvent to obtain a mixed solution, wherein the ligand reagent has at least one group selected from -OH group, -COOH group and -NH2 group;
[0009] S2. The mixed solution is coated onto the surface of the metal oxide layer to obtain a wet film;
[0010] S3. Anneal the wet film to obtain a ligand-coupled SAM layer.
[0011] The advantages and technical effects of the processing method in this embodiment of the invention are as follows:
[0012] (1) The ligand reagent and SAM material are mixed and then coated on the surface of the metal oxide layer. The ligand reagent and SAM material react to form ionic bonds, and the -OH group and / or -COOH group and / or -NH2 group in the ligand reagent can form hydrogen bonds with the conductive substrate and / or metal oxide layer, which further enhances the adhesion of the metal oxide layer to the conductive substrate and the adhesion of the ligand-coupled SAM layer to the metal oxide layer. This combination is beneficial for them to adhere to the conductive substrate in the subsequent perovskite layer processing.
[0013] (2) The ligand reagent has -OH groups and / or -COOH groups and / or -NH2 groups, which helps to improve the self-assembly uniformity of the ligand-coupled SAM layer.
[0014] (3) The ligand reagent has -OH groups and / or -COOH groups and / or -NH2 groups, which helps the ligand couple the SAM layer to react with the subsequently formed perovskite layer. Therefore, it helps to form a two-dimensional perovskite layer under the three-dimensional perovskite layer, thereby improving the overall stability of the perovskite layer.
[0015] In some embodiments, the ligand reagent is at least one of 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza), 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza), and mercapto-polyethylene glycol-amino.
[0016] In some embodiments, the SAM material is at least one of 2PACz, Meo-2PACz, and Me-4PACz.
[0017] In some embodiments, the mass ratio of the ligand reagent to the SAM material is 1:3 to 3:1.
[0018] In some embodiments, the solvent is at least one of isopropanol, ethanol, and N,N-dimethylformamide.
[0019] In some embodiments, the concentration of the ligand reagent in the mixed solution is 1–10 mg / mL.
[0020] In some embodiments, the concentration of the SAM material in the mixed solution is 1–10 mg / mL.
[0021] In some embodiments, the holding temperature of the annealing treatment is 50–150°C, and the holding time of the annealing treatment is 1–30 min.
[0022] In some embodiments, the thickness of the ligand-coupled SAM layer is 10–30 nm. Detailed Implementation
[0023] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.
[0024] This invention provides a method for processing the interface between a metal oxide layer and a perovskite layer, comprising the following steps:
[0025] S1. Dissolve the ligand reagent and SAM material in a solvent to obtain a mixed solution, wherein the ligand reagent has at least one group selected from -OH group, -COOH group and -NH2 group;
[0026] S2. The mixed solution is coated onto the surface of the metal oxide layer to obtain a wet film;
[0027] S3. Anneal the wet film to obtain a ligand-coupled SAM layer.
[0028] Working Principle: The processing method of this invention mixes a ligand reagent and a SAM material, then coats them onto the surface of a metal oxide layer. The ligand reagent and SAM material react to form ionic bonds, and the -OH and / or -COOH and / or -NH2 groups in the ligand reagent can form hydrogen bonds with the conductive substrate and / or the metal oxide layer. This further enhances the adhesion of the metal oxide layer to the conductive substrate and the adhesion of the ligand-coupled SAM layer to the metal oxide layer. This combination facilitates their adhesion to the conductive substrate during subsequent perovskite layer processing. Furthermore, the -OH and / or -COOH and / or -NH2 groups in the ligand reagent help improve the self-assembly uniformity of the ligand-coupled SAM layer. In addition, the -OH and / or -COOH and / or -NH2 groups in the ligand reagent facilitate the reaction between the ligand-coupled SAM layer and the subsequently formed perovskite layer, thus helping to form a two-dimensional perovskite layer beneath the three-dimensional perovskite layer, thereby improving the overall stability of the perovskite layer.
[0029] In some embodiments, the ligand reagent includes, but is not limited to, at least one of 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza), 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza), and mercapto-polyethylene glycol-amino. The ligand reagents listed above have abundant -OH groups and / or -COOH groups and / or -NH2 groups, which is beneficial for optimizing the interface between the metal oxide layer and the perovskite layer, and improving the charge transport characteristics of perovskite solar cells.
[0030] In some embodiments, the SAM material includes, but is not limited to, at least one of 2PACz, Meo-2PACz, and Me-4PACz. The SAM materials listed above can improve the uniformity and stability of the subsequently formed perovskite layer.
[0031] In some embodiments, the mass ratio of the ligand reagent to the SAM material is 1:3 to 3:1, such as 1:3, 1:2, 1:1, 2:1, 3:1, etc. When the mass ratio of the ligand reagent to the SAM material is too low, it is detrimental to improving the adhesion between the conductive substrate, the metal oxide layer, and the ligand-coupled SAM layer, and also detrimental to improving the self-assembly uniformity of the ligand-coupled SAM layer. When the mass ratio of the ligand reagent to the SAM material is too high, it is detrimental to improving the uniformity and stability of the subsequently formed perovskite layer.
[0032] In some embodiments, the solvent is at least one selected from isopropanol, ethanol, and N,N-dimethylformamide. The solvents listed above can dissolve the ligand reagent, facilitating uniform coating of the mixed solution onto the metal oxide layer.
[0033] In some embodiments, the concentration of the ligand reagent in the mixed solution is 1–10 mg / mL, for example, 1 mg / mL, 2 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL, 10 mg / mL, etc. When the concentration of the ligand reagent in the mixed solution is too low, it is detrimental to improving the adhesion between the conductive substrate, the metal oxide layer, and the ligand-coupled SAM layer, and also detrimental to improving the self-assembly uniformity of the ligand-coupled SAM layer. When the concentration of the ligand reagent in the mixed solution is too high, it is detrimental to cost reduction and efficiency improvement.
[0034] In some embodiments, the concentration of the SAM material in the mixed solution is 1–10 mg / mL, for example, 1 mg / mL, 2 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL, 10 mg / mL, etc. When the concentration of the SAM material in the mixed solution is too low, it is detrimental to improving the uniformity and stability of the subsequently formed perovskite layer. When the concentration of the SAM material in the mixed solution is too high, it is detrimental to improving the self-assembly uniformity of the ligand-coupled SAM layer.
[0035] In some embodiments, the holding temperature of the annealing treatment is 50–150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 150°C, etc., and the holding time of the annealing treatment is 1–30 min, such as 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, etc. When the holding temperature of the annealing treatment is too low or the holding time is too short, it is not conducive to improving the crystallinity of the ligand-coupled SAM layer, thereby hindering the improvement of the charge transport characteristics of the perovskite solar cell. When the holding temperature of the annealing treatment is too high or the holding time is too long, it is not conducive to cost reduction and efficiency improvement.
[0036] In some embodiments, the thickness of the ligand-coupled SAM layer is 10–30 nm, such as 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, etc. When the thickness of the ligand-coupled SAM layer is too small, it is not conducive to optimizing the interface between the metal oxide layer and the perovskite layer. When the thickness of the ligand-coupled SAM layer is too large, it is not conducive to improving carrier transport efficiency, thereby hindering the improvement of the photoelectric conversion efficiency of the perovskite solar cell.
[0037] The present invention will now be described in detail with reference to the embodiments.
[0038] Example 1
[0039] (1) A NiOx layer with a thickness of 200 nm was obtained by vapor deposition on the surface of a cleaned and dried ITO conductive glass.
[0040] (2) Dissolve the SAM material 2PACz in anhydrous ethanol, and then dissolve the ligand reagent 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in the above anhydrous ethanol to obtain a mixed solution. The concentration of the SAM material 2PACz in the above mixed solution is 5 mg / mL, and the concentration of the ligand reagent 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in the above mixed solution is also 5 mg / mL.
[0041] The above mixed solution was spin-coated onto the upper surface of the NiOx layer to obtain a wet film; the wet film was annealed to obtain a ligand-coupled SAM layer with a thickness of 20 nm; wherein the annealing temperature was 80 °C and the annealing time was 15 min.
[0042] (3) A perovskite CH3NH3PbI3 wet film was prepared on the surface of the ligand-coupled SAM layer by one-step spin coating. The wet film was then annealed to obtain a perovskite CH3NH3PbI3 layer with a thickness of 500 nm. The annealing temperature was 100 °C and the annealing time was 30 min.
[0043] (4) A 60 nm thick C layer was prepared on the surface of the above perovskite CH3NH3PbI3 layer. 60 layer.
[0044] (5) In the above C 60 A 60 nm thick Au electrode was fabricated on the upper surface of the layer to obtain a perovskite solar cell.
[0045] Example 2
[0046] This embodiment is the same as Embodiment 1, except that 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza) is used instead of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in Embodiment 1, and the mass ratio of 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza) to 2PACz in this embodiment is 1:2.
[0047] Example 3
[0048] This embodiment is the same as Embodiment 1, except that HS-PEG-NH2 (thiol-polyethylene glycol-amino) is used instead of the siloxane in Embodiment 1, and the mass ratio of HS-PEG-NH2 to 2PACz is 2:1.
[0049] Example 4
[0050] This embodiment is the same as Embodiment 1, except that in this embodiment, a combination of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) + 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza) in a mass ratio of 1:1 is used instead of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in Embodiment 1.
[0051] Example 5
[0052] This embodiment is the same as Embodiment 1, except that in this embodiment, a combination of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) + HS-PEG-NH2 with a mass ratio of 1:1 is used instead of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in Embodiment 1.
[0053] Example 6
[0054] This embodiment is the same as Embodiment 1, except that in this embodiment, a combination of 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza) + HS-PEG-NH2 with a mass ratio of 1:1 is used instead of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in Embodiment 1.
[0055] Example 7
[0056] This embodiment is the same as Embodiment 1, except that in this embodiment, a combination of siloxane + 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza) + HS-PEG-NH2 in a mass ratio of 1:1:1 is used instead of 3-(1H-1,2,4-triazol-1-yl)benzoic acid (3-Hbza) in Embodiment 1.
[0057] Comparative Example 1
[0058] This comparative example is the same as Example 1, except that no ligand reagent is added in step (2).
[0059] Comparative Example 2
[0060] This comparative example is the same as Example 1, except that a SAM layer is used instead of a ligand-coupled SAM layer, and a ligand-coupled perovskite layer is prepared on the SAM layer. The specific preparation method is as follows:
[0061] (1) A NiOx layer with a thickness of 200 nm was obtained by vapor deposition on the surface of a cleaned and dried ITO conductive glass.
[0062] (2) Dissolve the SAM material 2PACz in anhydrous ethanol to obtain a SAM solution. The concentration of the SAM material 2PACz in the above SAM solution is 5 mg / mL.
[0063] The above SAM solution was spin-coated onto the upper surface of the NiOx layer to obtain a wet film; the wet film was annealed to obtain a SAM layer with a thickness of 20 nm; wherein the annealing temperature was 80 °C and the annealing time was 15 min.
[0064] (3) Add ligand reagent siloxane to the perovskite precursor solution. The concentration of siloxane in the perovskite precursor solution is 5 mg / mL. Prepare a ligand-coupled perovskite CH3NH3PbI3 wet film on the surface of the SAM layer by one-step spin coating. Anneal the above wet film to obtain a ligand-coupled perovskite CH3NH3PbI3 layer with a thickness of 500 nm. The annealing temperature is 100 °C and the annealing time is 30 min.
[0065] (4) A 60 nm thick C layer was prepared on the surface of the above ligand-coupled perovskite CH3NH3PbI3 layer. 60 layer.
[0066] (5) In the above C 60 A 60 nm thick Au electrode was fabricated on the upper surface of the layer to obtain a perovskite solar cell.
[0067] Comparative Example 3
[0068] The comparative example is the same as that of comparative example 2, except that the ligand reagent is 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Hbza).
[0069] Comparative Example 4
[0070] The comparative example is the same as comparative example 2, except that the ligand reagent is HS-PEG-NH2.
[0071] The photoelectric conversion efficiency of the perovskite solar cells in Examples 1-7 and Comparative Examples 1-4 was tested, and the test results are shown in Table 1.
[0072] Table 1. Photovoltaic conversion efficiency of perovskite solar cells in Examples 1-7 and Comparative Examples 1-4
[0073]
[0074] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0075] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.
Claims
1. A method for treating the interface between a metal oxide layer and a perovskite layer, characterized in that, Includes the following steps: S1. Dissolve the ligand reagent and SAM material in a solvent to obtain a mixed solution, wherein the ligand reagent has at least one of the following groups: -OH group, -COOH group and -NH2 group, and the ligand reagent is composed of siloxane, 4-(1H-1,2,4-triazol-1-yl)benzoic acid and mercapto-polyethylene glycol-amino in a mass ratio of 1:1:1; S2. The mixed solution is coated onto the surface of the metal oxide layer to obtain a wet film; S3. Anneal the wet film to obtain a ligand-coupled SAM layer.
2. The processing method according to claim 1, characterized in that, The SAM material is at least one of 2PACz, Meo-2PACz, and Me-4PACz.
3. The processing method according to claim 1, characterized in that, The mass ratio of the ligand reagent to the SAM material is 1:3 to 3:
1.
4. The processing method according to claim 1, characterized in that, The solvent is at least one of isopropanol, ethanol, and N,N-dimethylformamide.
5. The processing method according to claim 1, characterized in that, In the mixed solution, the concentration of the ligand reagent is 1~10 mg / mL.
6. The processing method according to claim 1, characterized in that, In the mixed solution, the concentration of the SAM material is 1~10 mg / mL.
7. The processing method according to claim 1, characterized in that, The holding temperature for the annealing treatment is 50~150℃, and the holding time for the annealing treatment is 1~30min.
8. The processing method according to claim 1, characterized in that, The thickness of the ligand-coupled SAM layer is 10~30nm.