Functional film having a grid pattern and method of manufacturing the same

Abstract

The present application belongs to the field of patterning material preparation, and particularly relates to a functional film with a grid pattern and a preparation method thereof. The preparation method comprises the following steps: step 1): spontaneously generating carbonate hemispheres at a gas-liquid interface and organizing into an ordered carbonate hemispheres array; step 2): transferring the carbonate hemispheres array to a substrate surface; step 3): depositing a functional material on the substrate surface covered with the carbonate hemispheres array mask; and step 4): removing the carbonate hemispheres array mask and the deposition layer thereon to obtain the functional film with the grid pattern. The present application has the advantages of fundamental improvement and simplification, and can also integrate a plurality of previously independent processes into a coherent whole, thereby greatly reducing the complexity of the whole system and the required investment cost, and making the present application have a large-scale application prospect in a wider industrial field.

Description

Technical Field

[0001] This invention belongs to the field of patterned material preparation, specifically relating to a functional thin film with a grid pattern and its preparation method. Background Technology

[0002] As a rapidly developing patterned material deposition technology, colloidal lithography has attracted much attention in recent years due to its low operating cost and convenient large-area pattern generation, which has broad prospects for industrial applications.

[0003] The core of this method lies in the preparation, arrangement, and pattern transfer techniques of colloidal particles.

[0004] Traditionally, monodisperse microspheres ranging from tens of nanometers to tens of micrometers can be obtained through emulsion polymerization or sol-gel techniques, followed by further sieving. Organizing and arranging these uniformly sized and shaped monodisperse microspheres on a liquid surface yields an orderly two-dimensional array. Using this two-dimensional array as a mask pattern, a functional material is deposited onto the substrate surface. After removing the mask, a functional thin film with the pattern coated on its surface is obtained.

[0005] Currently, among all colloidal particles used to construct masking materials, polystyrene microspheres are the most common. However, if they are used as the basic building block of masking materials in the colloidal patterning process, and a corresponding functional thin film production process is established based on them, the following obvious defects and shortcomings exist:

[0006] (1) During large-scale production, the synthesis of polystyrene microspheres involves the use and consumption of a large amount of organic petrochemical raw materials, such as styrene and divinylbenzene. These microspheres, which are used as masking materials, are eventually dissolved and discarded during the mask removal process, resulting in unnecessary material waste.

[0007] (2) Obtaining nano- and micron-sized monodisperse microspheres requires a complex process of cleaning, sieving and collecting. In addition, the polystyrene particles of other sizes separated from the monodisperse microspheres need to be processed separately, which greatly reduces the utilization rate of raw materials and increases the preparation cost of mask materials.

[0008] (3) The entire operation is complex and relatively separate, involving multiple independent steps and links that are not subordinate to each other, such as polystyrene microsphere synthesis, sieving, dispersion, organization, and erosion, which makes the coupling of the system difficult and increases the cost of integrated construction.

[0009] (4) The operation process is complicated and lengthy, which increases the input of manpower and equipment, consumes a lot of energy and raw materials, and limits the widespread application of the technology in large-scale industrial production.

[0010] (5) The mask removal process involves dissolving polystyrene microspheres, which requires the use of organic solvents such as toluene or N-methyl-2-pyrrolidone. Their use and emission will have a negative impact on the surrounding environment. Summary of the Invention

[0011] The purpose of this invention is to overcome the shortcomings of the prior art and provide a functional thin film with a grid pattern and its preparation method.

[0012] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0013] A method for preparing a functional thin film with a grid pattern includes the following steps: Step 1): Spontaneously generating carbonate hemispheres at the gas-liquid interface and organizing them into an ordered array of carbonate hemispheres; Step 2): Transferring the carbonate hemisphere array to the surface of a substrate; Step 3): Depositing a functional material on the surface of the substrate covered with a carbonate hemisphere array mask; Step 4): Removing the carbonate hemisphere array mask and the deposited layer above it to obtain a functional thin film with a grid pattern.

[0014] The specific steps of step 1) are as follows: prepare a mixed clear aqueous solution of metal cation and surfactant, stir and mix thoroughly, transfer it to an open container, and let it stand in the air environment. By absorbing carbon dioxide from the air, a carbonate hemispherical array is formed at the gas-liquid interface.

[0015] The metal cation is a carbonate metal ion that is insoluble in water; the metal cation is Ca, Mg, or Zn; and the concentration of the metal cation is ≤50g / L.

[0016] The surfactant is a Tween-type, Span-type, polyether-type, polyester-type, or amino acid-type surfactant; the concentration of the surfactant is less than or equal to its corresponding critical micelle concentration (CMC).

[0017] The substrate mentioned in step 2) is an inorganic, organic, or inorganic-organic composite material with a smooth surface, specifically a PET substrate, a PI substrate, a glass substrate, etc.; its shape and thickness can be selected according to actual needs.

[0018] In step 2), the transfer method is either the substrate is transferred from the air side to the carbonate hemispherical array through contact transfer, or from the solution side to the carbonate hemispherical array through contact transfer.

[0019] The functional material mentioned in step 3) is a metallic material or a compound material; the metallic material is gold, silver, or copper, etc.; the compound material is ITO or AZO, etc., which can be selected according to actual needs; the surface deposition method is thermal evaporation, electron beam evaporation, or magnetron sputtering technology.

[0020] In step 4), the carbonate hemispherical array mask and the deposited layer thereon are removed by tape peeling, natural immersion, or ultrasonic cleaning.

[0021] When the deposition layer thickness is less than 50 nm, the tape peeling method or natural immersion method should be selected; when the deposition layer thickness is 50 nm or more, the ultrasonic cleaning method should be selected.

[0022] The present invention also includes a functional thin film with a grid pattern obtained by the preparation method described above, wherein the thickness of the functional thin film is ≤1μm.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] The technical solution of this application uses inorganic metal carbonates instead of polystyrene as the mask material. Through the spontaneous generation and organization behavior of carbonate hemispherical particles at the gas-liquid interface, a two-dimensional array for colloidal pattern forming is formed, and it is used as a mask material to prepare functional thin films with grid patterns.

[0025] First, the technical solution of this application does not require the use of styrene and divinylbenzene petrochemical raw materials, nor does it require the use of harmful organic solvents such as toluene in the subsequent mask removal process. Therefore, it avoids the potential harm to the environment, which is of great significance in terms of environmental protection and has broad industrial application prospects.

[0026] Secondly, the technical solution of this application, by adopting a water-based system throughout the entire process, demonstrates a unique advantage in terms of eco-friendliness. The technological innovation proposed in this invention not only significantly reduces the environmental harm caused by organic matter but also promotes the practice and development of green chemistry and sustainable processes.

[0027] Furthermore, the carbonate hemispherical particles spontaneously form on the solution surface at room temperature and pressure, requiring no additional energy consumption or external force intervention. Therefore, compared with the traditional polystyrene microsphere production process, it is simpler, more economical, energy-saving, and more efficient. Simultaneously, since the raw materials such as metal cations calcium, magnesium, and zinc are widely available and inexpensive, and the carbonate portion is directly obtained from atmospheric carbon dioxide, this invention has a greater advantage in creating carbon sinks and reducing the consumption of petrochemical resources. It exhibits outstanding advantages in energy saving, emission reduction, and consumption reduction, fully conforming to the principles of green chemistry and fully meeting the stringent requirements of modern chemical industry for energy saving, emission reduction, and consumption reduction.

[0028] Finally, the technical approach proposed in this invention closely aligns with the development trends of the chemical industry. By integrating multiple independent operational steps into a single technical processing solution, it optimizes the production process and significantly improves production efficiency. Specifically, this invention enables the in-situ preparation and ordered organization of carbonate hemispheres directly at the gas-liquid interface in one step, forming a patterned array, which facilitates subsequent mask preparation and deposition operations.

[0029] In summary, the fundamental improvements and simplifications proposed in this invention not only eliminate multiple steps in the traditional polystyrene microsphere process, such as particle washing, collection, sieving, redispersion in solvents, and spreading and arranging on the water surface, but also integrate several previously independent processes into a coherent whole. This greatly reduces the complexity of the entire system and the required investment costs, making this invention promising for large-scale application in a wider range of industrial fields. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the process flow for preparing the functional thin film with a grid pattern according to the present invention.

[0031] Figure 2 This is a surface morphology diagram of the mask formed by the contact between the planar portion of the carbonate hemisphere and the substrate in Embodiment 1 of the present invention;

[0032] Figure 3 This is a surface morphology diagram of the mask formed by the contact between the spherical portion of the carbonate hemisphere and the substrate in Embodiment 1 of the present invention.

[0033] Figure 4 The surface morphology image of the functional thin film with a grid pattern prepared in Example 1 of the present invention;

[0034] Figure 5 The surface morphology image of the functional thin film with a grid pattern prepared in Example 2 of this invention;

[0035] Figure 6 The surface morphology image of the functional thin film with a grid pattern prepared in Example 3 of this invention;

[0036] Figure 7 The surface morphology image of the functional thin film with a grid pattern prepared in Example 4 of this invention;

[0037] Figure 8 The surface morphology image of the functional thin film with a grid pattern prepared in Example 5 of the present invention is shown. Detailed Implementation

[0038] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.

[0039] Example 1

[0040] A method for preparing a functional thin film with a grid pattern. Figure 1 The schematic diagram of the preparation method is shown; it specifically includes the following steps:

[0041] Step 1) Carbonate hemispheres spontaneously form at the gas-liquid interface and are organized into an ordered array 1; specifically, the following steps are included: preparing a clear aqueous solution of calcium hydroxide and polyether F127 surfactant, wherein the concentration of calcium hydroxide is 1.5 g / L and the concentration of surfactant is 0.1 g / L, after thorough stirring and mixing, the solution is transferred to an open container and left to stand in an air environment for 30 min, so as to form a calcium carbonate hemisphere array at the gas-liquid interface by absorbing carbon dioxide from the air.

[0042] Step 2) Transfer the carbonate hemispherical array 1 to the surface of the substrate 2; bring the PET substrate into contact with the array from the air side. Due to van der Waals forces, the array is successfully transferred to the substrate surface, resulting in a template where the planar portion of the calcium carbonate hemispheres faces the substrate, as shown. Figure 2 As shown.

[0043] Step 3) Deposit functional material on the surface of the substrate covered with a carbonate hemispherical array mask; deposit a 20 nm thick titanium dioxide layer on the surface of the PET substrate covered with a calcium carbonate hemispherical array using thermal evaporation technology.

[0044] Step 4) Remove the mask and the deposited layer above it to obtain a functional thin film 3 with a grid pattern. The mask and the deposited layer above it are removed using a tape peeling method to obtain a titanium dioxide thin film with a grid pattern, the surface morphology of which is as follows: Figure 4 As shown.

[0045] Example 2

[0046] A method for preparing a functional thin film with a grid pattern includes the following steps:

[0047] Step 1) Carbonate hemispheres spontaneously form at the gas-liquid interface and are organized into an ordered array; prepare a clear aqueous solution of magnesium chloride and Tween 40 surfactant, wherein the concentration of magnesium chloride is 3.0 g / L and the concentration of surfactant is 30 mg / L. After thorough mixing, transfer the solution to an open container and let it stand in the air for 30 min to absorb carbon dioxide from the air to form an array of magnesium carbonate hemispheres at the gas-liquid interface.

[0048] Step 2) Transfer the carbonate hemispherical array to the substrate surface; bring the glass substrate into contact with the array from the solution side. Due to van der Waals forces, the array is successfully transferred to the substrate surface, resulting in a template where the spherical portion of the magnesium carbonate hemispheres faces the substrate. Figure 3As shown.

[0049] Step 3) Deposit functional material on the surface of the substrate covered with a carbonate hemispherical array mask; deposit a 50 nm thick ITO (indium tin oxide) layer on the surface of the glass substrate covered with a magnesium carbonate hemispherical array using magnetron sputtering technology.

[0050] Step 4): Remove the mask and the deposited layer above it to obtain a functional thin film with a grid pattern; use ultrasonic cleaning to remove the mask and the deposited ITO layer above it to obtain an ITO thin film with a grid pattern, the surface morphology of which is as follows. Figure 5 As shown.

[0051] Example 3

[0052] A method for preparing a functional thin film with a grid pattern includes the following steps:

[0053] Step 1) Carbonate hemispheres spontaneously form at the gas-liquid interface and are organized into an ordered array; prepare a clear aqueous solution of zinc citrate and Span 20 surfactant, wherein the concentration of zinc citrate is 2.0 g / L and the concentration of surfactant is 50 mg / L. After thorough mixing, transfer the solution to an open container and let it stand in the air for 30 minutes to absorb carbon dioxide from the air to form an array of zinc carbonate hemispheres at the gas-liquid interface.

[0054] Step 2) Transfer the carbonate hemispherical array to the substrate surface; bring the ceramic substrate into contact with the array from the air side. Due to the van der Waals forces, the array is successfully transferred to the substrate surface, resulting in a template with the planar portion of the zinc carbonate hemisphere facing the substrate.

[0055] Step 3) Deposit functional material on the surface of the substrate covered with a carbonate hemispherical array mask; use thermal evaporation technology to deposit a 200 nm thick Al q3 (8-hydroxyquinoline aluminum) layer on the surface of the ceramic substrate covered with the zinc carbonate hemispherical array.

[0056] Step 4) Remove the mask and the deposited layer above it to obtain a functional thin film with a grid pattern. The mask and the Alq3 layer deposited above it are removed using ultrasonic cleaning to obtain an Alq3 thin film with a grid pattern, the surface morphology of which is as follows: Figure 6 As shown.

[0057] Example 4

[0058] A method for preparing a functional thin film with a grid pattern includes the following steps:

[0059] Step 1) Carbonate hemispheres spontaneously form at the gas-liquid interface and are organized into an ordered array; prepare a clear aqueous solution of calcium hydroxide and polyether F127 series surfactant, wherein the concentration of calcium hydroxide is 1.0 g / L and the concentration of surfactant is 0.1 g / L. After thorough mixing, transfer the solution to an open container and let it stand in an air environment for 30 min. By absorbing carbon dioxide from the air, a calcium carbonate hemisphere array is formed at the gas-liquid interface.

[0060] Step 2) Transfer the carbonate hemispherical array to the substrate surface; bring the quartz substrate into contact with the array from the solution side. Due to van der Waals forces, the array is successfully transferred to the substrate surface, resulting in a template with the spherical portion of the calcium carbonate hemisphere facing the substrate.

[0061] Step 3) Deposit functional material on the surface of the substrate covered with a carbonate hemispherical array mask; deposit a 10 nm thick molybdenum layer on the surface of the quartz substrate covered with a calcium carbonate hemispherical array using electron beam evaporation technology.

[0062] Step 4) Remove the mask and the deposited layer above it to obtain a functional thin film with a grid pattern. The mask and the molybdenum layer deposited above it are removed using a natural immersion method, resulting in a molybdenum film with a grid pattern, the surface morphology of which is as follows: Figure 7 As shown.

[0063] Example 5

[0064] A method for preparing a functional thin film with a grid pattern includes the following steps:

[0065] Step 1) Carbonate hemispheres spontaneously form at the gas-liquid interface and are organized into an ordered array; prepare a clear aqueous solution of calcium hydroxide and Tween 20 surfactant, wherein the concentration of calcium hydroxide is 1.5 g / L and the concentration of surfactant is 20 mg / L. After thorough mixing, transfer the solution to an open container and let it stand in the air for 30 min. By absorbing carbon dioxide from the air, a calcium carbonate hemisphere array is formed at the gas-liquid interface.

[0066] Step 2) Transfer the carbonate hemispherical array to the substrate surface; the carbon fiber reinforced composite substrate is brought into contact with the array from the air side. Due to the van der Waals forces, the array is successfully transferred to the substrate surface, resulting in a template with the planar portion of the calcium carbonate hemisphere facing the substrate.

[0067] Step 3) Deposit functional material on the surface of the substrate covered with a carbonate hemispherical array mask; deposit a 100 nm thick copper layer on the surface of the carbon fiber reinforced composite substrate covered with a calcium carbonate hemispherical array using thermal evaporation technology.

[0068] Step 4): Remove the mask and the deposited layer above it to obtain a functional thin film with a grid pattern; use ultrasonic cleaning to remove the mask and the deposited copper layer above it to obtain a copper film with a grid pattern, the surface morphology of which is as follows. Figure 8 As shown.

[0069] In summary, the fundamental improvements and simplifications proposed in this invention not only eliminate multiple steps in the traditional polystyrene microsphere process, such as particle washing, collection, sieving, redispersion in solvents, and spreading and arranging on the water surface, but also integrate several previously independent processes into a coherent whole. This greatly reduces the complexity of the entire system and the required investment costs, making this invention promising for large-scale application in a wider range of industrial fields.

[0070] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a functional thin film with a grid pattern, characterized in that, Includes the following steps: Step 1): Carbonate hemispheres spontaneously form at the gas-liquid interface and organize into an ordered array of carbonate hemispheres; prepare a clear aqueous solution of metal cations and surfactants, stir thoroughly and mix evenly, transfer to an open container, and let it stand in an air environment. By absorbing carbon dioxide from the air, a carbonate hemisphere array is formed at the gas-liquid interface; the metal cations are water-insoluble metal ions of carbonates; the metal cations are Ca, Mg, or Zn; the concentration of the metal cations is ≤50g / L; the surfactants are Tween, Span, polyether, polyester, or amino acid surfactants; the concentration of the surfactants is less than or equal to their corresponding critical micelle concentration; Step 2): Transfer the carbonate hemispherical array to the substrate surface; The substrate is transferred to the carbonate hemispherical array from the air side or from the solution side. Step 3): Deposit functional materials on the surface of a substrate covered with a carbonate hemispherical array mask; Step 4): Remove the carbonate hemispherical array mask and the deposited layer above it to obtain a functional film with a grid pattern.

2. The method for preparing a functional thin film with a grid pattern according to claim 1, characterized in that, The substrate mentioned in step 2) is an inorganic, organic, or inorganic-organic composite material with a smooth surface.

3. The method for preparing a functional thin film with a grid pattern according to claim 1, characterized in that, The functional material mentioned in step 3) is a metallic material or a compound material; the metallic material is gold, silver, or copper; the compound material is ITO or AZO; and the surface deposition method is thermal evaporation, electron beam evaporation, or magnetron sputtering.

4. The method for preparing a functional thin film with a grid pattern according to claim 1, characterized in that, In step 4), the carbonate hemispherical array mask and the deposited layer above it can be removed by tape peeling, natural immersion, or ultrasonic cleaning.

5. The method for preparing a functional thin film with a grid pattern according to claim 4, characterized in that, When the deposition layer thickness is less than 50 nm, the tape peeling method or natural immersion method should be selected; when the deposition layer thickness is 50 nm or more, the ultrasonic cleaning method should be selected.

6. A functional thin film with a grid pattern obtained by the preparation method according to any one of claims 1-5; the thickness of the functional thin film is ≤1μm.

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