A method for recycling and regenerating a tco substrate or a silicon-based cell

Abstract

The application is a recycling and regeneration method of TCO substrate or silicon bottom cell, the TCO substrate is TCO substrate or inorganic oxide / TCO substrate in perovskite device, the silicon bottom cell is silicon bottom cell in perovskite or silicon stack, the method comprises the following steps: soaking the perovskite device in the first solution for a first preset time, separating the preliminarily recycled TCO substrate or silicon bottom cell; transferring the preliminarily recycled TCO substrate or silicon bottom cell to the dipropylamine dialkylamine solution for a second preset time, carrying out regeneration repair, and obtaining the regenerated TCO substrate or silicon bottom cell; removing residual impurities and optimizing the surface state through combined cleaning to obtain the directly usable TCO substrate or silicon bottom cell TCO substrate or silicon bottom cell. The application can realize high repeatability and high reliability regeneration of high-value components in perovskite device, and realize the dual effects of environmental protection and resource saving, reduce the manufacturing cost and cost recovery cycle of low perovskite device, and promote the sustainable development of perovskite device.

Description

Technical Field

[0001] The embodiments of the present invention relate to the field of semiconductor device technology, and in particular to a method for recycling and regenerating TCO substrates or silicon-based solar cells. Background Technology

[0002] Perovskite solar cells have demonstrated enormous commercial potential due to their power conversion efficiency rapidly increasing from 3.8% to 27% in the past decade. However, the water-soluble lead contained in these devices is toxic and can cause serious environmental damage if not properly disposed of. As the commercialization of perovskite solar cell devices progresses, research into their recycling technologies becomes crucial.

[0003] Existing recycling technologies have the following problems: the device performance of recyclable components is far lower than that of fresh components, repeatability is poor, and the inorganic oxide / TCO substrate of recyclable components, which is the main cost factor, cannot be efficiently regenerated.

[0004] Therefore, there is an urgent need to develop a highly reliable and repeatable recycling process to achieve environmentally friendly recycling and low-cost regeneration of high-value recyclable components in perovskite solar cells and similar structural devices.

[0005] It should be noted that this section is intended to provide background or context for the technical solutions of the invention as set forth in the claims. The description herein does not imply acceptance as prior art simply because it is included in this section. Summary of the Invention

[0006] The purpose of this invention is to provide a method for recycling and regenerating TCO substrates or silicon-based solar cells, thereby at least partially solving one or more problems caused by the limitations and defects of related technologies.

[0007] This invention provides a method for recycling and regenerating TCO substrates or silicon-based solar cells, wherein the TCO substrate is a TCO substrate in a perovskite device or an inorganic oxide / TCO substrate, and the silicon-based solar cell is a silicon-based solar cell in a perovskite or silicon tandem configuration, comprising: S1, immerse the device containing the TCO substrate or silicon-based battery in a first solution for a first preset time, and separate the initially recovered TCO substrate or silicon-based battery, wherein the first solution is a chain amine solution, an alcohol solution or an aqueous solution; S2, the initially recovered TCO substrate or silicon-based battery is transferred to a dipropylamine dialkylamine solution and immersed for a second preset time for regeneration and repair, to obtain a regenerated TCO substrate or silicon-based battery; S3 removes residual impurities and optimizes the surface condition through a combination of cleaning methods, resulting in a TCO substrate or silicon-based cell that can be used directly.

[0008] In this invention, the perovskite device is any one of the following devices: perovskite-based solar cells, LEDs, and field-effect transistors.

[0009] In this invention, in S1, the chain amine is at least one of methylamine, ethylamine, propylamine, and butylamine.

[0010] In this invention, in S2, the dialkylamine solution is a diethylamine solution or a dipropylamine solution.

[0011] In this invention, both the first preset duration and the second preset duration are 1 to 10 minutes.

[0012] In this invention, the perovskite refers to perovskite with the general formula AMX3, in which the central metal cation M and anion X form a coordinated octahedral structure, and A exists in the inter-octahedral interstices to balance the charge of the BX3 anion. M is any one or two or more of the metals Ge, Sn, Pb, Cu, Mn, Sb, and Bi, and X is any one or two or more of Cl, Br, and I.

[0013] In this invention, the inorganic oxide / TCO substrate includes a TCO substrate having an inorganic oxide functional layer of nickel oxide, zinc oxide, or titanium oxide.

[0014] In this invention, in step S3, ultrasonic cleaning is performed using deionized water, acetone, and isopropanol. After drying with nitrogen, the substrate is then treated with UV ozone to obtain a TCO substrate or silicon-based battery that can be used directly.

[0015] In this invention, the method further includes: After soaking in S4 and S1, the perovskite-containing solution can be separated. Heating the perovskite-containing solution will remove the amine, thus realizing the recycling and reuse of the solid perovskite material. The removed amine can also be recycled and reused.

[0016] The technical solution provided by this invention may include the following beneficial effects: This invention enables highly repeatable and reliable regeneration of inorganic oxide / TCO substrates, a high-value component in perovskite devices, while achieving both environmental friendliness and resource conservation. It has significant economic benefits and is expected to further reduce the manufacturing cost and cost recovery cycle of perovskite devices, thus promoting the sustainable development of perovskite devices. Attached Figure Description

[0017] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure. It is obvious that the drawings described below are merely some embodiments of this disclosure, and those skilled in the art can obtain other drawings based on these drawings without any inventive effort.

[0018] Figure 1 This diagram illustrates a process flow diagram of a method for recycling and regenerating TCO substrates or silicon-based solar cells in an exemplary embodiment of the present invention. Figure 2 This diagram illustrates the recycling and regeneration of inorganic oxide / TCO substrates in an exemplary embodiment of the present invention. Figure 3 The diagram shows the JV characteristic curves, photoelectric property comparisons, and cycle performance statistics of the regenerating device in an exemplary embodiment of the present invention. Detailed Implementation

[0019] Exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, these exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, they are provided so that the invention will be more comprehensive and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0020] Furthermore, the accompanying drawings are merely illustrative diagrams of embodiments of the present invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and therefore repeated descriptions of them will be omitted. Some block diagrams shown in the drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0021] This example embodiment provides a method for recycling and regenerating a TCO substrate or a silicon-based solar cell. The TCO substrate is a TCO substrate in a perovskite device or an inorganic oxide / TCO substrate, and the silicon-based solar cell is a silicon-based solar cell in a perovskite or silicon tandem configuration. (Refer to...) Figure 1 As shown, the method includes the following steps: S1, immerse the device containing the TCO substrate or silicon-based battery in a first solution for a first preset time, and separate the initially recovered TCO substrate or silicon-based battery, wherein the first solution is a chain amine solution, an alcohol solution or an aqueous solution; S2, the initially recovered TCO substrate or silicon-based battery is transferred to a dipropylamine dialkylamine solution and immersed for a second preset time for regeneration and repair, to obtain a regenerated TCO substrate or silicon-based battery; S3 removes residual impurities and optimizes the surface condition through a combination of cleaning methods, resulting in a TCO substrate or silicon-based cell that can be used directly.

[0022] The method disclosed in this embodiment can achieve highly repeatable and reliable regeneration of TCO substrates or inorganic oxide / TCO substrates in tantalum devices, and silicon-based solar cells in perovskite or silicon stacks. It also achieves the dual benefits of environmental friendliness and resource conservation, resulting in significant economic benefits. This method is expected to further reduce the manufacturing cost and cost recovery cycle of perovskite devices, promoting the sustainable development of perovskite devices. This application can be used for the recycling of TCO substrates or silicon-based solar cells during pilot production or at the end of their lifespan.

[0023] The steps in the above embodiments are described in detail below.

[0024] In S1, the perovskite device is any one of the following devices: perovskite-based solar cells, LEDs, and field-effect transistors. Specifically, the device structure of solar cells and LEDs includes a TCO (FTO and flexible conductive thin film) substrate / electron or hole functional layer / perovskite layer / hole or electron functional layer / back electrode or a variant thereof, and the variant may take the form of adding other functional layers such as interface modification between layers.

[0025] The inorganic oxide / TCO substrate includes a TCO substrate having an inorganic oxide functional layer of nickel oxide, zinc oxide, or titanium oxide.

[0026] The perovskite referred to is a perovskite with the general formula AMX3, in which the central metal cation M and anion X form a coordinated octahedral structure. A exists in the interstices of the octahedrons, playing a role in balancing the charge of the BX3 anion. M can be any one or more of the metals Ge, Sn, Pb, Cu, Mn, Sb, and Bi, and X can be any one or more of Cl, Br, and I. Common examples include CH3NH3PbI3 and NH2CH=NH2PbI3.

[0027] The chain amines are at least one of methylamine, ethylamine, propylamine, and butylamine, and can be flexibly selected or mixed according to the type of perovskite device. Short-chain methylamine and ethylamine have higher reactivity and are suitable for devices with thin perovskite layers or simple structures, allowing for shorter soaking times (1-3 minutes). Propylamine and butylamine have better solubility and are suitable for complex devices with thick perovskite layers or interface modification layers; the soaking time can be adjusted to 5-10 minutes. The soaking process can be carried out at room temperature. If butylamine or propylamine with higher boiling points are selected, moderate heating (not exceeding the boiling point of the amine) can be used to improve the dissolution efficiency of the perovskite layer while maintaining low temperature and low energy consumption characteristics. Alternatively, a solution of water and amines (both long and short chains) can be used for soaking.

[0028] Immersion in chain-type amine solutions allows for precise dissolution of the perovskite layer for devices with different structures, reducing damage to the inorganic oxide functional layer. The dissolved perovskite solution and amines can be recycled and reused, reducing consumable consumption and pollution.

[0029] In step S2, the dialkylamine solution is either diethylamine or dipropylamine. Diethylamine solution has higher reactivity and is suitable for substrates with fewer residual impurities after initial recycling; the immersion time can be set to 1-5 minutes. Dipropylamine solution has better interface passivation effect and is suitable for substrates with more surface defects or complex residual impurities; the immersion time is 3-10 minutes. A single solution can be selected according to the type of inorganic oxide functional layer (nickel oxide / zinc oxide / titanium oxide), or a mixture can be used in proportion. The entire process is performed at room temperature without additional energy consumption. It effectively fills substrate surface defects and optimizes interface conditions; it is compatible with different inorganic oxide / TCO substrates, ensuring regeneration consistency; it paves the way for subsequent combined cleaning, helping to achieve regenerated devices with efficiency comparable to fresh devices; the amines are recyclable and reusable, reducing consumable costs and aligning with green principles.

[0030] In step S3, ultrasonic cleaning is performed using deionized water, acetone, and isopropanol. After drying with nitrogen, the substrate is treated with UV ozone to obtain an inorganic oxide / TCO substrate that can be directly used for assembling perovskite devices. For example, ultrasonic cleaning can be performed stepwise in the order of "deionized water → acetone → isopropanol," with each step using an ultrasonic power of 30-60 kHz and a treatment time of 10-15 minutes at room temperature to remove water-soluble impurities, organic residues, and particulate contaminants. Nitrogen gas with a purity of ≥99.99% is used to uniformly blow along the substrate surface until it is completely dry, avoiding water stains. The UV ozone treatment parameters are set to a power of 100-200 mW / cm². 2 The substrate is treated at room temperature and atmospheric pressure for 15-25 minutes, with the degree of surface activation adjusted as needed. Stepwise ultrasonic treatment thoroughly removes various types of impurities, ensuring substrate cleanliness; UV ozone treatment enhances the substrate's hydrophilicity and interfacial compatibility, facilitating interlayer bonding in subsequent devices; the gentle process does not damage the inorganic oxide functional layer, ensuring stable substrate performance; the treated substrate meets the core requirements for device assembly, simplifying the production process.

[0031] Based on the above embodiments, the method further includes: After soaking in S4 and S1, the perovskite-containing solution can be separated. Heating the perovskite-containing solution will remove the amine, thus realizing the recycling and reuse of the solid perovskite material. The removed amine can also be recycled and reused.

[0032] Experimental Example Discarded inverted planar devices based on CsFAMA mixed-cation perovskite were immersed in butylamine solution (or alcohol solution or aqueous solution) and allowed to stand at room temperature for 1 minute to completely dissolve the perovskite absorber layer, yielding a preliminarily recovered inorganic oxide / TCO substrate (labeled RBA-S). The CsFAMA mixed-cation perovskite is composed of lead halide containing cesium (Cs), formamidinium (FA), and methylamine (MA).

[0033] The obtained inorganic oxide / TCO substrate was transferred to a dipropylamine solution, further cleaned at room temperature, and surface treated to achieve interface passivation, resulting in a regenerated inorganic oxide / TCO substrate (labeled RDPA-S).

[0034] The regenerated inorganic oxide / TCO substrate was ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes each, dried with nitrogen, and then treated with UV ozone for 20 minutes. This process achieved deep purification and surface optimization of the regenerated substrate, ensuring that it meets the requirements for substrate cleanliness, hydrophilicity, and interface compatibility in the fabrication of new perovskite solar cells.

[0035] On a clean, regenerated inorganic oxide / TCO substrate, an inverted planar solar cell based on CsFAMA mixed cation perovskite was constructed using the same configuration as the fresh device, completing the regenerated device assembly (labeled RBA-DPA-D).

[0036] The obtained regenerated device was tested, and the test results are as follows: Figure 3 As shown.

[0037] This application utilizes the synergistic effect of amine solutions to regenerate damaged inorganic oxides (such as TiO2, SnO2, etc.) and transparent conductive glass (TCO) in perovskite components through coordination dissolution, stripping, and surface chemical repair.

[0038] This application is based on a recycling and regeneration reaction mechanism derived from chemical principles, as follows: (1) Coordination exfoliation mechanism of perovskite layer (Step 1: Recovery) In the first stage, short-chain amines (such as methylamine and ethylamine) are soaked in an aqueous or alcoholic solution. The mechanism primarily involves Lewis base coordination and hydrogen bond cleavage. Coordination dissolution: Lead ions (Pb) in perovskite materials (APbX3) 2+ It possesses strong Lewis acidity. Short-chain amines, as strong Lewis bases, react with Pb via lone pair electrons. 2+ Coordination occurs, forming coordination complexes that are readily soluble in alcohols or water: PbI₂ + nR-NH₂ → [PbI₂(R-NH₂)] n ] Interface wetting and penetration: Short-chain amines are highly polar and have small molecular size, enabling them to rapidly penetrate the porous layers of perovskite. Water or alcohol solvents disrupt the electrostatic attraction or hydrogen bonds between the perovskite and inorganic oxide layers, allowing residual organic cations (such as FA) to penetrate. + / MA + Rapid dissolution enables the stripping of inorganic oxide substrates.

[0039] (2) Mechanism of repair by dipropylamine / dialkylamine (Step 2: Regeneration) The initially recovered substrate is transferred to a solution such as dipropylamine. This step is crucial for regeneration, involving the chemical passivation of surface defects and the equilibrium of chemical potentials. Surface defect passivation: The surface of recovered inorganic oxides (such as TiO2, SnO2) often contains oxygen vacancies or adsorbed impurities. Secondary amines fill or neutralize unsaturated coordination sites on the oxide surface through the lone pair electrons of nitrogen atoms.

[0040] Removal of stubborn residues: Dialkylamines possess stronger hydrophobicity and specific alkalinity, enabling them to remove trace amounts of iodide (I-) residues remaining from the first stage through acid-base neutralization or displacement reactions. - (or lead salts) to prevent contamination of newly prepared perovskite during secondary use.

[0041] Chemical energy state restoration: This treatment can adjust the work function of the substrate surface to restore it to an energy level matching degree close to the original state, thereby ensuring the effective transport of photogenerated carriers.

[0042] (3) Surface optimization mechanism of combined cleaning (Step 3: Optimization) Finally, a combined cleaning process is performed (typically involving switching between polar and non-polar solvents, supplemented by ultrasound): Surface tension adjustment: Remove residual amine ligands to prevent excessive amine from negatively affecting the wettability of the subsequent perovskite precursor solution.

[0043] Hydroxylation (Hydroxyl groups) regulation: Optimize the -OH content on the oxide surface. Appropriate surface hydroxyl group distribution helps improve the adhesion of TCO to subsequent electron transport layers (ETLs) or perovskite layers.

[0044] In summary, the technical solutions provided by the embodiments of the present invention have the following beneficial effects: (1) High repeatability: (2) The surface roughness of the regenerated inorganic oxide / TCO substrate decreased from 4.4 nm to 2.6 nm, the size of the nanocrystal agglomerates decreased, the device parameter distribution narrowed, and the repeatability was significantly improved.

[0045] (3) High reliability: The highest power conversion efficiency of the regenerated device on the inorganic oxide / TCO substrate can reach 20%, which is higher than the 17.92% of the fresh device, and its performance is better than that of the fresh device in the first 7 cycles.

[0046] (4) Excellent stability: After the regenerated unpackaged device is stored in a nitrogen atmosphere for 400 days, the power conversion efficiency still remains above 80% of the initial value.

[0047] (5) Environmental protection and economy: It realizes the recycling of inorganic oxide / TCO substrate, reduces device cost, and avoids lead pollution, which is in line with the concept of green environmental protection.

[0048] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example 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. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0049] Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of the invention are indicated by the appended claims.

Claims

1. A method for recycling and regenerating a TCO substrate or a silicon-based solar cell, wherein the TCO substrate is a TCO substrate in a perovskite device or an inorganic oxide / TCO substrate, and the silicon-based solar cell is a silicon-based solar cell in a perovskite or silicon tandem structure, characterized in that... include: S1, immerse the device containing the TCO substrate or silicon-based battery in a first solution for a first preset time, and separate the initially recovered TCO substrate or silicon-based battery, wherein the first solution is a chain amine solution, an alcohol solution or an aqueous solution; S2, the initially recovered TCO substrate or silicon-based battery is transferred to a dipropylamine dialkylamine solution and immersed for a second preset time for regeneration and repair, to obtain a regenerated TCO substrate or silicon-based battery; S3 removes residual impurities and optimizes the surface condition through a combination of cleaning methods, resulting in a TCO substrate or silicon-based cell that can be used directly.

2. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to claim 1, characterized in that, The perovskite device is any one of the following: perovskite-based solar cells, LEDs, and field-effect transistors.

3. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to claim 1, characterized in that, In S1, the chain amine is at least one of methylamine, ethylamine, propylamine, and butylamine.

4. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to claim 1, characterized in that, In S2, the dialkylamine solution is a diethylamine solution or a dipropylamine solution.

5. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to claim 1, characterized in that, Both the first preset duration and the first preset duration are 1 to 10 minutes.

6. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to any one of claims 1 to 5, characterized in that, The perovskite refers to perovskite with the general formula AMX3, in which the central metal cation M and anion X form a coordinated octahedral structure, and A exists in the inter-octahedral interstices to balance the charge of the BX3 anion. M is any one or two or more of the metals Ge, Sn, Pb, Cu, Mn, Sb, and Bi, and X is any one or two or more of Cl, Br, and I.

7. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to any one of claims 1 to 5, characterized in that, The inorganic oxide / TCO substrate includes a TCO substrate having an inorganic oxide functional layer of nickel oxide, zinc oxide, or titanium oxide.

8. The method for recycling and regenerating TCO substrates or silicon-based solar cells according to any one of claims 1 to 5, characterized in that, In S3, ultrasonic cleaning is performed using deionized water, acetone, and isopropanol. After drying with nitrogen, the substrate is then treated with UV ozone to obtain a TCO substrate or silicon-based battery that can be used directly.

9. The method for recycling and regenerating the TCO substrate or silicon-based solar cell according to any one of claims 1-5, characterized in that, The method further includes: After soaking in S4 and S1, the perovskite-containing solution can be separated. Heating the perovskite-containing solution will remove the amine, thus realizing the recycling and reuse of the solid perovskite material. The removed amine can also be recycled and reused.

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