Method for preparing super-hydrophilic ITO conductive glass and super-hydrophilic ITO conductive glass

Abstract

The invention discloses a method for preparing super-hydrophilic ITO (Indium Tin Oxide) conductive glass. The method comprises the following steps: S1, preparing a treating fluid, namely preparing ammonium citrate, potassium persulfate, sodium molybdate, PBTCA (Polybutyronitrile) and deionized water in proportion; s2, chemical bath: immersing the ITO conductive glass in the treating fluid; s3, rinsing with pure water: rinsing the ITO conductive glass prepared in S2 with pure water; s4, blow-drying: blow-drying the ITO conductive glass treated in S3 through inert gas to obtain a finished product. The super-hydrophilic ITO conductive glass is prepared by the method provided by the invention. According to the method for preparing the super-hydrophilic ITO conductive glass and the super-hydrophilic ITO conductive glass, a permanent hydrophilic effect is obtained through a one-step super-hydrophilic ITO modification technology driven by a quaternary synergistic chemical system, and efficient'cleaning-protecting-modifying 'on an indium-based surface is realized.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cell technology, specifically to ITO conductive glass, and more particularly to a method for preparing superhydrophilic ITO conductive glass and the superhydrophilic ITO conductive glass itself. Background Technology

[0002] With the rapid development of photovoltaic technology, perovskite solar cells have become the core development direction of the next generation of photovoltaic devices due to their high efficiency (certified efficiency >26%), low manufacturing cost, and solution processing advantages. As a key transparent electrode in perovskite cells, the surface properties of indium tin oxide (ITO) glass directly affect the uniformity and interface stability of the perovskite layer.

[0003] However, existing technologies face two major bottlenecks: 1. Hydrophilic defects: Conventional ITO surfaces contain organic contaminants (such as alkyl chain C16-C18) and metal ion residues, resulting in strong hydrophobicity (initial contact angle >60°), which hinders the uniform spread of perovskite precursor solution and easily forms pinhole or island defects. 2. The conflict between stability and environmental protection: Mainstream treatment methods fall into two categories: Organic solvent cleaning method (ultrasound → baking → ozone treatment): relies on volatile organic solvents such as acetone / isopropanol, poses a risk of toxic residues and is a complicated process (>120 minutes). Strong acid etching (such as HCl / HNO3 mixture): Although it can rapidly reduce the contact angle (<10°), excessive etching leads to indium dissolution (etching depth >5nm), significantly increasing sheet resistance (increase >20%), and generating waste liquid containing heavy metals (In). 3+ (Concentration > 100 ppm), high treatment costs.

[0004] Current research attempts to improve hydrophilicity through plasma treatment or ultraviolet ozone modification, but these still require high-energy-consuming equipment (temperature >100℃), cannot be compatible with flexible substrates, and cannot build a durable hydrophilic layer (contact angle rebound >15°). Summary of the Invention

[0005] The technical problem to be solved by this invention is: in order to solve the technical problem that the hydrophilic layer cannot be durable in the prior art, this invention provides a method for preparing superhydrophilic ITO conductive glass and superhydrophilic ITO conductive glass. Through a one-step superhydrophilic ITO modification technology driven by a quaternary synergistic chemical system, a permanent hydrophilic effect is obtained, realizing efficient "cleaning-protection-modification" of indium-based surfaces.

[0006] The technical solution adopted by this invention to solve its technical problem is: a method for preparing superhydrophilic ITO conductive glass, comprising the following steps: S1. Preparing the treatment solution: ammonium citrate, potassium persulfate, sodium molybdate, PBTCA and deionized water are prepared in proportion; S2. Chemical bath: the ITO conductive glass is immersed in the treatment solution; S3. Rinsing with pure water: the ITO conductive glass obtained in S2 is rinsed with pure water; S4. Drying: the ITO conductive glass treated in S3 is dried with inert gas to obtain the finished product.

[0007] Furthermore, in order to provide the correct ratio of the treatment solution, in step S2, ammonium citrate is 0.08-0.12 mol / L, potassium persulfate is 0.04-0.06 mol / L, sodium molybdate is 0.008-0.015 mol / L, and PBTCA is 0.8-1.2 mmol / L.

[0008] Furthermore, the ammonium citrate gently chelates residual metal ions, and the potassium persulfate generates reactive oxygen free radicals (•OH) at room temperature.

[0009] Furthermore, in order to suppress In 3+ Excessive etching causes the sodium molybdate to form a MoO4@In passivation layer with a surface thickness of 0.5-1.2 nm and a coverage of ≥95% of the grain boundary region.

[0010] Furthermore, the PBTCA molecule self-assembles a -PO3-In- bond / -COOH hydrophilic end, and the -PO3H2 end of the PBTCA molecule is bonded to In... 3+ In-OP bonds are formed, resulting in a permanent hydration layer.

[0011] Furthermore, in order to obtain a permanent hydrophilic effect, the initial contact angle of the permanent hydration layer is ≤5°; the contact angle after aging at 85%RH / 7 days is ≤10°, and the ITO sheet resistance change rate is ±0.5%.

[0012] Furthermore, in order to be compatible with flexible materials, the temperature of the chemical bath in S2 is 25±2℃, and the treatment time is 3-5 min.

[0013] Furthermore, in step S3, the water is rinsed with pure water for 5-10 seconds.

[0014] Furthermore, the inert gas in S4 is nitrogen, with a dew point ≤ -40℃.

[0015] The technical solution adopted by the present invention to solve its technical problem is: a superhydrophilic ITO conductive glass, which is prepared by the above method.

[0016] Compared with the prior art, the beneficial effects of the present invention are: 1. The present invention provides a method for preparing superhydrophilic ITO conductive glass and the superhydrophilic ITO conductive glass. Through ammonium citrate chelation for impurity removal, potassium persulfate oxidation activation, sodium molybdate for passivation layer construction, and PBTCA self-assembly functionalization, it achieves efficient "cleaning-protection-modification" of indium-based surfaces. Through the synergistic effect of the four components and the precise design of interface chemistry, it provides a simple and environmentally friendly surface treatment solution for high-performance electronic devices or biological interfaces.

[0017] 2. The method for preparing superhydrophilic ITO conductive glass and the superhydrophilic ITO conductive glass of the present invention adopt a one-step process design of chemical bath, rinsing and drying, with zero energy input during the process, shortening the processing time to about 3 minutes, greatly improving efficiency and reducing energy consumption.

[0018] 3. The present invention provides a method for preparing superhydrophilic ITO conductive glass and the superhydrophilic ITO conductive glass. PBTCA decomposes residual alkyl chains, resulting in a 99% reduction in carbon residue detected by TOF-SIMS. The self-assembly of the molybdate passivation layer and PBTCA molecules resolves the "etching-hydrophilicity tradeoff" and verifies permanent hydrophilicity. Attached Figure Description

[0019] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0020] Figure 1 This is a parameter comparison table for Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0021] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0022] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings and are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention. Furthermore, features defined with "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0023] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0024] A method for preparing superhydrophilic ITO conductive glass includes the following steps: S1. Prepare the treatment solution: Prepare ammonium citrate, potassium persulfate, sodium molybdate, PBTCA and deionized water in the specified proportions.

[0025] Specifically, ammonium citrate is 0.08-0.12 mol / L, potassium persulfate is 0.04-0.06 mol / L, sodium molybdate is 0.008-0.015 mol / L, and PBTCA is 0.8-1.2 mmol / L.

[0026] Ammonium citrate gently chelates residual metal ions, thus removing impurities through chelation.

[0027] Among them, potassium persulfate is activated by oxidation, and at room temperature, potassium persulfate generates reactive oxygen free radicals (•OH).

[0028] Sodium molybdate is used to construct the MoO4@In passivation layer to inhibit In. 3+ Excessive etching acts as a corrosion inhibitor. Molybdate ions preferentially deposit at grain boundaries and inhibit ITO etching (etching depth <1 nm).

[0029] Preferably, the surface thickness of the MoO4@In passivation layer is 0.5-1.2 nm, and the coverage is ≥95% of the grain boundary region. Specifically, the PBTCA molecule self-assembles the -PO3-In- bond / -COOH hydrophilic end, and the -PO3H2 end of the PBTCA molecule is linked to In... 3+ In-OP bonds with bond energies ≥300kJ / mol are formed to obtain a permanent hydration layer.

[0030] Preferably, the initial contact angle of the permanent hydrophilic layer is ≤5°; the contact angle after aging at 85% RH for 7 days is ≤10°, and the ITO sheet resistance change rate is ±0.5%, verifying the phenomenon of permanent hydrophilicity and the spatially uniform aggregation of atoms or molecules to form crystal nuclei during crystallization (referencing classical definitions, such as the Cahn-Hilliard equation). In this invention, the permanent hydrophilic layer (contact angle ≤3°) ensures the isothermal spreading of the precursor solution on the ITO surface (spreading coefficient >90%), eliminating local energy barriers and achieving a uniform nucleus density (>10) during perovskite layer deposition.9 pcs / cm 2 This reduces pinhole defects. Experiments show that this method improves nucleation uniformity by more than 3 times compared to the comparative example (contact angle increased to 42°+).

[0031] PBTCA decomposes residual alkyl chains (C16-C18), resulting in a 99% reduction in carbon residue detected by TOF-SIMS.

[0032] S2. Chemical bath: Immerse the ITO conductive glass in the treatment solution.

[0033] Specifically, the chemical bath temperature is 25±2℃, and the treatment time is 3-5 minutes. At a temperature of around 25℃, the chemical bath is compatible with flexible materials.

[0034] S3. Rinse with pure water: Rinse the ITO conductive glass obtained in S2 with pure water for 5-10 seconds.

[0035] S4. Drying: The ITO conductive glass treated in S3 is dried by blowing with an inert gas to obtain the finished product.

[0036] The inert gas is nitrogen, and the dew point is ≤-40℃.

[0037] By precisely proportioning the four functional components of chelation, oxidation, passivation, and bonding, and through a one-step process design, the entire preparation process consumes zero energy. The self-assembly of the molybdate passivation layer and PBTCA molecules resolves the "etching-hydrophilicity trade-off" and verifies permanent hydrophilicity.

[0038] Example 1: The treatment solution contained 0.1 mol / L ammonium citrate, 0.05 mol / L potassium persulfate, 0.01 mol / L sodium molybdate, and 1 mmol / L PBTCA.

[0039] ITO glass was treated with a chemical bath (25℃, 3 min), rinsed with pure water (5 s), and dried with nitrogen (nitrogen dew point -45℃). The treatment time was 3.08 min, and the energy consumption was 0.01 kWh / m³. 2 .

[0040] The contact angle of the ITO glass before treatment was 78°. The contact angle of the ITO glass after treatment was 2.1°, the sheet resistance change was +1.7%, and the etching depth was 0.8nm.

[0041] Example 2: The treatment solution contained 0.12 mol / L ammonium citrate, 0.04 mol / L potassium persulfate, 0.08 mol / L sodium molybdate, and 1.2 mmol / L PBTCA. The treatment time was 3.1 min, and the energy consumption was 0.01 kWh / m³. 2 .

[0042] ITO glass is treated with a chemical bath (25°C, 3 min), rinsed with pure water (6 s), and dried with nitrogen (nitrogen dew point -42°C).

[0043] The contact angle of the ITO glass before treatment was 78°. The contact angle of the ITO glass after treatment was 3.8°, the sheet resistance change was +2.9%, and the etching depth was 1.1 nm.

[0044] Example 3: The treatment solution contained 0.08 mol / L ammonium citrate, 0.06 mol / L potassium persulfate, 0.15 mol / L sodium molybdate, and 0.8 mmol / L PBTCA. The treatment time was 3.1 min, and the energy consumption was 0.01 kWh / m³. 2 .

[0045] ITO glass is treated with a chemical bath (25°C, 3 min), rinsed with pure water (6 s), and dried with nitrogen (nitrogen dew point -45°C).

[0046] The contact angle of the ITO glass before treatment was 78°. The contact angle of the ITO glass after treatment was 4.2°, the sheet resistance change was +3.2%, and the etching depth was 1.1 nm.

[0047] Comparative Example 1: A traditional multi-step cleaning process was used, involving ITO glass. The process included: detergent + pure water → pure water → acetone → isopropanol, each ultrasonicated for 30 minutes → drying at 80°C for 1 hour → ozone treatment after drying for 20 minutes. The total treatment time was 200 minutes, and the energy consumption was 1.22 kWh / m³. 2 The contact angle of the ITO glass before treatment was 78°. The contact angle of the ITO glass after treatment was 18°, and the 0.5-1.2nm range recovered to 42° after 24 hours, with a sheet resistance change of +8.5%.

[0048] Comparative Example 2. Etching was performed using concentrated acid hydroxylation in a chemical bath (H₂SO₄:H₂O₂ = 7:3, 75℃ for 15 seconds). The processing time was 0.25 min, and the energy consumption was 0.08 kWh / m². 2 The contact angle of the ITO glass before treatment was 78°. The contact angle of the ITO glass after treatment was 6°, which rebounded to 47° after 24 hours. The sheet resistance changed by +22.3%, and the etching depth was 4.2nm.

[0049] This processing method involves concentrated sulfuric acid, resulting in high wastewater treatment costs. Furthermore, the PET substrate deforms at 75°C.

[0050] The contact angles mentioned above are those in a perovskite precursor solution environment.

[0051] The method for preparing superhydrophilic ITO conductive glass according to this invention reduces processing energy consumption to 0.001 kWh / m³. 2(Compared to 1.22kWh / m³ for multi-step cleaning) 2 Cost savings >99%. Combined with a one-step process, total production costs are reduced by >80%. Zero thermal or electrical energy requirements reduce carbon emissions by >95%, with no VOC emissions (99% reduction in carbon residue from PBTCA decomposition), meeting green manufacturing standards (such as ISO 14001). Room temperature maintains the flexibility of the substrate (PET) without deformation (Comparative Example 2 shows PET deformation at 75°C), ensuring flexible battery applications; and maintaining solution stability (no degradation caused by temperature fluctuations).

[0052] In summary, the method for preparing superhydrophilic ITO conductive glass and the superhydrophilic ITO conductive glass of this invention achieve permanent hydrophilicity through a one-step superhydrophilic ITO modification technology driven by a quaternary synergistic chemical system, realizing efficient "cleaning-protection-modification" of indium-based surfaces.

[0053] The above description is based on the preferred embodiments of the present invention. Through the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of the present invention. The technical scope of the present invention is not limited to the contents of the specification, but must be determined by the scope of the claims.

Claims

1. A method for preparing superhydrophilic ITO conductive glass, characterized in that, Includes the following steps: S1. Preparation of treatment solution: Prepare ammonium citrate, potassium persulfate, sodium molybdate, PBTCA and deionized water in proportion; S2. Chemical bath: Immerse the ITO conductive glass in the treatment solution; S3. Rinsing: The ITO conductive glass obtained in S2 is rinsed with pure water; S4. Drying: The ITO conductive glass treated in S3 is dried by blowing with an inert gas to obtain the finished product.

2. The method for preparing superhydrophilic ITO conductive glass according to claim 1, characterized in that, In step S2, ammonium citrate is 0.08-0.12 mol / L, potassium persulfate is 0.04-0.06 mol / L, sodium molybdate is 0.008-0.015 mol / L, and PBTCA is 0.8-1.2 mmol / L.

3. The method for preparing superhydrophilic ITO conductive glass according to claim 2, characterized in that, The ammonium citrate gently chelates residual metal ions, and the potassium persulfate generates reactive oxygen free radicals (•OH) at room temperature.

4. The method for preparing superhydrophilic ITO conductive glass according to claim 2, characterized in that, The sodium molybdate forms a MoO4@In passivation layer with a surface thickness of 0.5-1.2 nm and a coverage of ≥95% of the grain boundary region.

5. The method for preparing superhydrophilic ITO conductive glass according to claim 2, characterized in that, The PBTCA molecule self-assembles a -PO3-In- bond / -COOH hydrophilic end, and the -PO3 H2 end of the PBTCA molecule is linked to the In... 3+ In-OP bonds are formed, resulting in a permanent hydration layer.

6. The method for preparing superhydrophilic ITO conductive glass according to claim 5, characterized in that, The initial contact angle of the permanent hydration layer is ≤5°; the contact angle after aging at 85% RH for 7 days is ≤10°, and the ITO sheet resistance change rate is ±0.5%.

7. The method for preparing superhydrophilic ITO conductive glass according to claim 1, characterized in that, The temperature of the chemical bath in S2 is 25±2℃, and the treatment time is 3-5 min.

8. The method for preparing superhydrophilic ITO conductive glass according to claim 1, characterized in that, The S3 rinse is performed with pure water for 5-10 seconds.

9. The method for preparing superhydrophilic ITO conductive glass according to claim 1, characterized in that, The inert gas in S4 is nitrogen, with a dew point ≤ -40℃.

10. A superhydrophilic ITO conductive glass, characterized in that, It is prepared by the method described in any one of claims 1-9.

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