Preparation method of micro-nano printing material based on metal organic ion polymerization

Abstract

The invention discloses a preparation method of a micro-nano printing material based on metal organic ion polymerization, and belongs to the technical field of highly controllable micro-nano. The preparation method comprises the following steps: reacting inorganic ions with organic molecular ions in a reaction environment in the presence of a capping agent to obtain a mixed emulsion, printing a micro-nano structure pattern by using a printing technology, initiating emulsion polymerization by heating to obtain a functional material solid, and carrying out heat treatment crystallization to obtain the highly controllable functional material micro-nano structure. The micro-nano structure provided by the invention has the characteristics of continuous structure, homogeneity inside and flat surface, so that the manufacturing strategy of the micro-nano structure is more flexible and universal than that of a known method; the preparation method is simple, the adopted direct electrojet printing technology greatly simplifies the manufacturing process, and high-precision micro-nano structure manufacturing can be achieved; the material compatibility is wide, and the production efficiency can be improved; the manufacturing of a highly controllable micro-nano structure can be realized, and the high-precision manufacturing of the micro-nano structure can be realized in a wider size range.

Description

Technical Field

[0001] The present invention belongs to the field of materials science and relates to a method for preparing micro-nano printing materials based on metal-organic ionic polymerization. Background Art

[0002] Micro-nano structure fabrication involves creating precise structures and patterns on the microscale (10 -6 meters) to nanoscale (10 -9 meters). The size and shape of these structures are precisely controlled at the microscale, endowing them with unique physical, chemical, or biological properties. Micro-nano structures can be designed to achieve specific functions, such as altering the optical properties of materials, enhancing mechanical strength, or improving the efficiency of chemical reactions. These structures are widely used in multiple fields such as optoelectronics, biomedicine, energy conversion and storage, and sensor technology.

[0003] In the field of modern manufacturing, micro-nano printing technology is an important means for fabricating micro-nano structures, enabling materials to be precisely processed and printed at the micron or even nanoscale. Although this technology is widely applied in the fields of electronics, biomedicine, and optics, it still faces numerous challenges in practical applications. On the one hand, due to the discontinuity of the polycrystalline structure, these materials often encounter problems with structural integrity and functional consistency when forming micro-nano structures. On the other hand, the surface roughness of the materials often exceeds the ideal standard, affecting the performance and appearance quality of the final products. In addition, internal impurities and inhomogeneities also severely affect the mechanical and physical properties of the printed structures, limiting their widespread application. Therefore, seeking a new method that can prepare micro-nano structure printing materials with continuous structures, internal homogeneity, and flat surfaces and wide applicability is crucial for expanding the application of printing manufacturing in high-tech fields.

[0004] In the metal-organic ionic polymerization method, metal ions (such as Cu2+ and Zn2+) have multiple coordination sites; organic ligand ions contain polydentate ligands with multiple carboxylate groups. Metal-organic hybrid materials themselves belong to coordination polymers. At the initial stage of the reaction, metal ions and polydentate organic ligand ions form oligomers through ionic and coordination bond interactions. Through the microscopic regulation of capping agents (such as hydrogen bond interactions), metal ions and organic ligand ions are expected to form stable oligomers. This oligomer forms a fluid with adjustable viscosity and surface tension with the solvent, which can be combined with micro-nano printing technologies such as electrohydrodynamic jet printing to achieve micro-nano scale patterned deposition of the fluid. During the heat treatment process, the capping agent is effectively removed, and the oligomer crosslinks and cures. Further control of the thermal gradient enables the molecules to rearrange to form an ordered micro-nano structure of the hybrid material. This method can avoid grain boundary defects and surface roughness problems caused by polycrystalline growth, thereby obtaining a micro-nano structure of the hybrid material with continuous structure, flat surface, and nanoscale feature size, providing a reliable new material for the highly controllable printing manufacturing of micro-nano structures of hybrid materials. Summary of the Invention

[0005] To address the deficiencies of the above-mentioned method for preparing micro-nano printing materials, the present invention proposes a new method for preparing micro-nano printing materials based on metal-organic ion polymerization. A fluid with a relatively high viscosity is prepared through the metal-organic ion polymerization method, and a micro-nano structure is printed using an electrohydrodynamic jet printing device. Finally, a highly controllable micro-nano structure with homogeneous interior, continuous structure, and flat surface is obtained. The micro-nano structure printing materials include oxides, sulfides, hybrid materials, etc.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing micro-nano printing materials based on ion polymerization, which includes: First, prepare an oligomer solution. Second, separate the solid and prepare an oligomer fluid. Third, use an electrohydrodynamic jet printing device to print a micro-nano structure. Finally, cure and form the micro-nano structure by heating.

[0008] The first step is to prepare an oligomer solution

[0009] 1.1) Add M to organic solvent a to obtain solution A. The M includes zinc nitrate hexahydrate and copper nitrate tetrahydrate. The organic solvent a includes methanol, ethanol, and isopropanol. In the solution A, the concentration of M is 0.122M - 0.609M. In this step, the metal salt of M is dispersed in a.

[0010] 1.2) Add capping agent N to solution A to obtain solution B. The N includes diethylamine, pyridine, and dimethyl sulfoxide. In the solution B, the concentration of N is 0.089M - 0.222M. In this step, N is dispersed in A, and N and M have not reacted yet.

[0011] 1.3) Add O to organic solvent a to obtain solution C. The O includes benzene-1,3,5-tricarboxylic acid, terephthalic acid, and 2-methylimidazole. In the solution C, the concentration of O is 0.122M - 0.609M.

[0012] 1.4) Slowly add the solution B obtained in step 1.2) to the solution C obtained in step 1.3), and magnetically stir at room temperature for 30 - 60 minutes to obtain a suspension D, which is used as an ionic oligomer solution. The volume ratio of solution A to solution B is 1:1. In this step, M ions react with O, that is, inorganic-organic ion polymerization reaction occurs between metal ions and organic ligand ions. Since N can form hydrogen bonds with O, the polymerization reaction will not proceed infinitely. Finally, the oligomer P molecules are stabilized at 2 - 10 molecules.

[0013] M + O + N → P…N

[0014] Step 2: Separate the oligomer solution and prepare the oligomer fluid

[0015] 2.1) Centrifuge the oligomer solution obtained in the first step to completely separate the oligomer from the reaction mother liquor. Discard the supernatant and take the solid. The rotation speed of the centrifugation is 8000 - 10000 revolutions per minute, and the centrifugation time is 20 - 40 minutes.

[0016] 2.2) Disperse the solid obtained in step 2.1) in solvent a to prepare oligomer fluid b, and obtain an oligomer fluid with adjustable viscosity and surface tension by adjusting the amount of solvent added. The solvent a includes methanol, ethanol, and isopropanol. The mass fraction of the solid in the oligomer fluid is 1.0% - 5.0%.

[0017] Step 3: Prepare highly controllable micro - nano structures

[0018] 3.1) Prepare a layer of SiO2 insulating layer on the surface of substrate I. The substrate I includes silicon wafers, glass, quartz, polyimide, copper sheets, and aluminum sheets. Among them, the methods for preparing the insulating layer include chemical vapor deposition, sputtering, thermal evaporation, atomic layer deposition, and sol - gel method. The thickness of the insulating layer is 1 - 10 microns.

[0019] 3.2) Place the selected substrate I on a levelled and heated workbench. Use an electro - jet printing device for micro - nano structure printing. The specific operation is as follows: The syringe is filled with fluid b and fixed on the bracket through a syringe clamp. The bracket is installed on the Z - axis of the motor. The high - voltage power supply is connected to the syringe to provide a high - voltage electric field, and the air pump provides a stable air pressure to the syringe through the air pressure control cabinet. Under the control of the computer, the drive power adjusts the movement of the Z - axis, X - axis, and Y - axis of the motor to achieve precise printing. Under the action of the high - voltage electric field between the syringe and substrate I, the ink is refined into a conical jet and gradually ejected. The computer controls the movement of the motor to print micro - nano structures with a line width of 500 nanometers to 50 microns on various substrates. The equipment parameters are adjusted as follows: The electric field strength is 0.5 kV / cm - 3 kV / cm, the nozzle diameter is 30 - 100 microns, the distance between the nozzle and the substrate is 1 - 5 mm, the liquid flow rate is 0.1 - 10 μL / min, the temperature of the printing environment is 20 - 25 °C, and the relative humidity is 40% - 60% to prevent the solvent from evaporating too quickly and keep the solution properties stable. The printing speed is between 1 mm / s and 10 mm / s. Monitor the relative position between the syringe and the substrate and the printed micro - nano structure through an observation camera to ensure the smooth completion of the printing process.

[0020] Step 4: Heat - form the highly controllable micro - nano structures

[0021] Using the LinKam temperature control system, the micro-nano structures printed by electrohydrodynamic jet printing were heat-treated. The heating parameters were set as follows: the temperature range was 120 - 300 degrees Celsius, the heating and cooling rate was 0.1 - 20 degrees Celsius per minute, and the temperature control accuracy was 0.1 degree Celsius. The expected micro-nano structures were finally obtained.

[0022] The beneficial effects of the present invention are as follows:

[0023] (1) The preparation method of the present invention is simple. The direct electrohydrodynamic jet printing technology adopted by the present invention greatly simplifies the traditional micro-nano structure manufacturing process. By directly printing the pre-designed micro-nano structures on the target substrate through the electrohydrodynamic jet technology, high-precision micro-nano structure manufacturing is realized, without the need for complex templates or expensive lithography equipment, and multiple steps of lithography and etching processes are omitted, thus reducing the required equipment and materials and significantly reducing the manufacturing cost.

[0024] (2) The present invention has broad material compatibility: Compared with traditional methods, the present invention shows high compatibility with various materials, including combinations of different metal salts, organic solvents, and capping agents. This broad material compatibility makes the design more flexible, enabling the selection of the most suitable material system according to specific application requirements, and then preparing micro-nano structures with different properties.

[0025] (3) The present invention can achieve highly controllable micro-nano structure manufacturing: The present invention can achieve high-precision manufacturing of micro-nano structures in a wider size range. Through fine adjustment of electrohydrodynamic jet printing parameters such as electric field strength, nozzle diameter and distance, liquid flow rate, etc., high-precision micro-nano structures with line widths ranging from 500 nanometers to 50 micrometers are realized. This improved size control and precision provide strong technical support for applications in the fields of precision micro-nano electronics, optical components, and biomedicine.

[0026] (4) The present invention can improve production efficiency: The rapid prototyping and batch production capabilities achieved by the present invention significantly improve production efficiency. Compared with traditional micro-nano structure manufacturing methods, the electrohydrodynamic jet printing technology can complete the design and manufacturing of complex structures in a short time, while maintaining high repeatability and consistency. This is fully verified in the embodiments. Whether it is the rapid prototyping of a single sample or the batch production of the same structure, it can be completed efficiently and accurately, meeting the rapidly developing market demand. Description of the Drawings

[0027] Figure 1 is the flow chart of the present invention;

[0028] Figure 2 is the 400-fold magnification microscopic characterization diagram of the oligomer fluid composed of zinc nitrate and 2-methylimidazole on a glass slide

[0029] Figure 3 Microscopic 400x magnification characterization diagram of the oligomeric fluid composed of copper nitrate and trimesic acid on a glass slide

[0030] Figure 4 Microscopic 400x magnification characterization diagram of the oligomeric fluid composed of zirconium tetrachloride and terephthalic acid on a glass slide

[0031] Figure 5 Initial XRD pattern of the oligomeric fluid composed of zirconium tetrachloride and terephthalic acid

[0032] Figure 6 XRD pattern of the oligomeric fluid composed of zirconium tetrachloride and terephthalic acid after heat treatment

[0033] Figure 7 Initial XRD pattern of the oligomeric fluid composed of copper nitrate and trimesic acid

[0034] Figure 8 Initial XRD pattern of the oligomeric fluid composed of zinc nitrate and 2-methylimidazole Detailed implementation manners

[0035] The present invention will be further described below in conjunction with specific embodiments.

[0036] A method for preparing a micro-nano printing material based on ionic polymerization, which includes: First, prepare an oligomer solution. Second, separate the solid and prepare an oligomeric fluid. Third, use an electrohydrodynamic jet printing device to print micro-nano structures. Finally, cure and form the micro-nano structures by heating. Figure 1 A conceptual schematic diagram of the micro-nano structure manufacturing process of the present invention is presented. In this process, first, the material precursor forms a stable ionic oligomer solution through an inorganic-organic ionic polymerization reaction process under the stabilizing action of a capping agent, and the oligomeric fluid is separated and prepared. Subsequently, this oligomeric fluid is directly printed onto a substrate through electrohydrodynamic jet printing technology, and a SiO2 insulating layer is pre-prepared on the substrate surface to ensure good adhesion and electrical properties of the printed layer. The printing process uses a precisely controlled motor to extrude the oligomeric fluid through a fine nozzle to form the micro-nano structure in the shape of "H" shown in the figure. This control mechanism allows for the precise deposition of complex three-dimensional structures.

[0037] Example 1

[0038] Preparation of an oligomer solution of zirconium salt and terephthalic acid based on ionic polymerization and direct writing of its metal-organic hybrid material, the steps include:

[0039] The first step, prepare an oligomer solution

[0040] 1.1) Take 34.95 grams of zirconium tetrachloride and add it to 500 mL of methanol to obtain solution A, where the concentration of zirconium tetrachloride is 0.3 M.

[0041] 1.2) Add 8.67 grams of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.17 M.

[0042] 1.3) Add 25 grams of terephthalic acid to 500 mL of methanol to obtain solution C, where the concentration of terephthalic acid is 0.3 M.

[0043] 1.4) Slowly add solution B to solution C and stir magnetically at room temperature for 45 minutes to obtain suspension D as the ionic oligomer solution. The volume ratio of solution A to solution B is 1:1.

[0044] The second step is to separate the oligomer solution and prepare the oligomer fluid

[0045] 2.1) Centrifuge the oligomer solution obtained in the first step at a speed of 9000 revolutions per minute for 30 minutes to separate oligomer a, discard the supernatant, and take the solid.

[0046] 2.2) Disperse the obtained solid in 500 milliliters of ethanol to prepare oligomer fluid b, adjust the mass fraction of the solid to 3%, and the viscosity is 1000 cp.

[0047] The third step is to prepare highly controllable micro-nano structures

[0048] 3.1) Prepare a SiO2 insulating layer with a thickness of 5 micrometers on the surface of the silicon wafer using chemical vapor deposition.

[0049] 3.2) Use a direct writing printing device to print micro-nano structures. The device parameters are set as follows: nozzle diameter 50 micrometers, distance between the nozzle and the substrate 2 millimeters, liquid flow rate 10 microliters per minute, temperature of the printing environment 20 degrees Celsius, relative humidity 40%; printing speed 1 millimeter per second, monitor the relative position between the syringe and the substrate and the printed micro-nano structures through an observation camera to ensure the smooth completion of the printing process.

[0050] The fourth step is to heat and form the highly controllable micro-nano structures

[0051] Heat the printed micro-nano structures, set the temperature to 150 degrees Celsius, the heating rate to 10 degrees Celsius per minute, and the holding time to 2 hours to form the expected micro-nano structures.

[0052] Through the above steps, micro-nano structures with a line width of about 50 μm are successfully prepared. These structures exhibit good morphological consistency and repeatability, verifying the effectiveness and feasibility of the technical solution.

[0053] Example 2

[0054] Preparation of an oligomer solution of zirconium salt and terephthalic acid based on ionic polymerization and its metal-organic hybrid material by electrohydrodynamic printing, the steps including:

[0055] The first step is to prepare the oligomer solution

[0056] 1.1) Take 11.65 grams of zirconium tetrachloride and add it to 500 mL of methanol to obtain solution A, where the concentration of zirconium tetrachloride is 0.1 M.

[0057] 1.2) Add 8.67 grams of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.17 M.

[0058] 1.3) Add 25 grams of terephthalic acid to 500 mL of methanol to obtain solution C, where the concentration of terephthalic acid is 0.3 M.

[0059] 1.4) Slowly add solution B to solution C and stir magnetically at room temperature for 45 minutes to obtain suspension D as the ionic oligomer solution. The volume ratio of solution A to solution B is 1:1.

[0060] The second step is to separate the oligomer solution and prepare the oligomer fluid

[0061] 2.1) Centrifuge the oligomer solution obtained in the first step at a rotation speed of 9000 revolutions per minute for 30 minutes to separate the oligomer a, discard the supernatant, and take the solid.

[0062] 2.2) Disperse the obtained solid in 500 milliliters of ethanol to prepare oligomer fluid b, adjust the mass fraction of the solid to 2%, and the viscosity is 1500 cp.

[0063] The third step is to prepare highly controllable micro-nano structures

[0064] 3.1) Prepare a SiO2 insulating layer with a thickness of 5 micrometers on the surface of the silicon wafer using chemical vapor deposition.

[0065] 3.2) Use an electrohydrodynamic printing device to print micro-nano structures. The device parameters are set as follows: the electric field strength is 3 kV / cm, the nozzle diameter is 30 micrometers, the distance between the nozzle and the substrate is 1 millimeter, the liquid flow rate is 10 microliters per minute, the temperature of the printing environment is 20 degrees Celsius, and the relative humidity is 40%; the printing speed is 1 millimeter per second, and the relative position between the syringe and the substrate and the printed micro-nano structures are monitored through an observation camera to ensure the smooth completion of the printing process.

[0066] The fourth step is to heat and form the highly controllable micro-nano structures

[0067] The printed micro-nano structure is heat-treated with the temperature set at 150 degrees Celsius, the heating rate at 10 degrees Celsius per minute, and the holding time at 2 hours to form the expected micro-nano structure.

[0068] Through the above steps, micro-nano structures with a line width of approximately 600 nanometers were successfully prepared. These structures exhibited good morphological consistency and repeatability, verifying the effectiveness and feasibility of this technical solution.

[0069] Example 3

[0070] Based on the direct writing preparation of an oligomer solution of zinc salt and 2-methylimidazole by ionic polymerization and its metal-organic hybrid material, the steps include:

[0071] The first step is to prepare the oligomer solution

[0072] 1.1) Take 35 grams of zinc nitrate hexahydrate and add it to 500 mL of methanol to obtain solution A, where the concentration of zinc nitrate hexahydrate is 0.24 M.

[0073] 1.2) Add 11.06 grams of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.11 M.

[0074] 1.3) Add 25 grams of methylimidazole to 500 mL of methanol to obtain solution C, where the concentration of methylimidazole is 0.609 M.

[0075] 1.4) Slowly add solution B to solution C and stir magnetically at room temperature for 45 minutes to obtain suspension D as the ionic oligomer solution. The volume ratio of solution A to solution B is 1:1.

[0076] The second step is to separate the oligomer solution and prepare the oligomer fluid

[0077] 2.1) Centrifuge the oligomer solution obtained in the first step at a rotation speed of 8000 revolutions per minute for 30 minutes to separate oligomer a, discard the supernatant, and take the solid.

[0078] 2.2) Disperse the obtained solid in 500 milliliters of ethanol to prepare oligomer fluid b, adjust the mass fraction of the solid to 4%, and the viscosity to 1000 cp.

[0079] The third step is to prepare highly controllable micro-nano structures

[0080] 3.1) Prepare a SiO2 insulating layer with a thickness of 5 micrometers on the surface of the silicon wafer using chemical vapor deposition.

[0081] 3.2) Use a direct-write printing device to print micro-nano structures. The device parameters are set as follows: nozzle diameter 30 microns, distance between the nozzle and the substrate 1 mm, liquid flow rate 10 microliters per minute, temperature of the printing environment at 20 degrees Celsius, relative humidity 40%; printing speed 1 mm / s. Monitor the relative position between the syringe and the substrate and the printed micro-nano structures through an observation camera to ensure the smooth completion of the printing process.

[0082] The fourth step, high-controllable heating and forming of micro-nano structures

[0083] Heat-treat the printed micro-nano structures. Set the temperature to 150 degrees Celsius, the heating rate to 10 degrees Celsius per minute, and the holding time to 2 hours to form the expected micro-nano structures.

[0084] Through the above steps, micro-nano structures with a line width of approximately 800 nm were successfully prepared. These structures exhibited good morphological consistency and repeatability, verifying the effectiveness and feasibility of this technical solution.

[0085] Example 4

[0086] Based on the ion polymerization of zinc salts and 2-methylimidazole oligomer solution and its preparation by electrohydrodynamic printing of metal-organic hybrid materials, the steps include:

[0087] The first step, configure the oligomer solution

[0088] 1.1) Take 35 grams of zinc nitrate hexahydrate and add it to 500 L of methanol to obtain solution A, where the concentration of zinc nitrate hexahydrate is 0.24 M.

[0089] 1.2) Add 11.06 grams of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.11 M.

[0090] 1.3) Add 8.2 grams of 2-methylimidazole to 500 mL of methanol to obtain solution C, where the concentration of 2-methylimidazole is 0.2 M.

[0091] 1.4) Slowly add solution B to solution C and magnetically stir at room temperature for 35 minutes to obtain suspension D as the ionic oligomer solution. The volume ratio of solution A to solution B is 1:1.

[0092] The second step, separate the oligomer solution and prepare the oligomer fluid

[0093] 2.1) Centrifuge the oligomer solution obtained in the first step. Set the rotation speed to 8000 revolutions per minute and the centrifugation time to 30 minutes to separate oligomer a, discard the supernatant, and take the solid.

[0094] 2.2) The obtained solid was dispersed in 500 mL of ethanol to prepare oligomer fluid b, and the mass fraction of the solid was adjusted to 5%, with a viscosity of 1200 cp.

[0095] The third step is to prepare highly controllable micro-nano structures

[0096] 3.1) A SiO2 insulating layer with a thickness of 5 μm was prepared on the surface of a silicon wafer using chemical vapor deposition.

[0097] 3.2) Micro-nano structure printing was carried out using an electrohydrodynamic printing device. The device parameters were set as follows: the electric field strength was 3 kV / cm, the nozzle diameter was 30 μm, the distance between the nozzle and the substrate was 5 mm, the liquid flow rate was 10 μL / min, the temperature of the printing environment was 20 °C, and the relative humidity was 40%; the printing speed was 1 mm / s. The relative position between the syringe and the substrate and the printed micro-nano structure were monitored through an observation camera to ensure the smooth completion of the printing process.

[0098] The fourth step is the heating and forming of highly controllable micro-nano structures

[0099] The printed micro-nano structure was heat-treated with the temperature set at 150 °C, the heating rate at 10 °C / min, and the holding time at 2 h to form the expected micro-nano structure.

[0100] Through the above steps, micro-nano structures with a line width of approximately 500 nm were successfully prepared. These structures exhibited good morphological consistency and repeatability, verifying the effectiveness and feasibility of the technical solution.

[0101] Example 5

[0102] Preparation based on direct writing printing of an oligomer solution of a copper salt and benzene-1,3,5-tricarboxylic acid by ionic polymerization and its metal-organic hybrid material, the steps including:

[0103] The first step is to prepare an oligomer solution

[0104] 1.1) 79 g of copper(II) nitrate tetrahydrate was added to 500 mL of methanol to obtain solution A, in which the concentration of copper(II) nitrate tetrahydrate was 0.609 M.

[0105] 1.2) 5 g of triethylamine was added to solution A to obtain solution B, in which the concentration of triethylamine was 0.098 M.

[0106] 1.3) 64 g of benzene-1,3,5-tricarboxylic acid was added to 500 mL of methanol to obtain solution C, in which the concentration of benzene-1,3,5-tricarboxylic acid was 0.609 M.

[0107] 1.4) Solution B was slowly added to solution C and magnetically stirred at room temperature for 45 minutes to obtain suspension D as an ionic oligomer solution. The volume ratio of solution A to solution B was 1:1.

[0108] Step 2: Separate the oligomer solution and prepare the oligomer fluid

[0109] 2.1) Centrifuge the oligomer solution obtained in the first step at a rotation speed of 8000 revolutions per minute for 40 minutes to separate oligomer a, discard the supernatant, and take the solid.

[0110] 2.2) Disperse the obtained solid in 500 ml of ethanol to prepare oligomer fluid b, adjust the mass fraction of the solid to 3%, and the viscosity is 1300 cp.

[0111] Step 3: Prepare highly controllable micro-nano structures

[0112] 3.1) Prepare a SiO2 insulating layer with a thickness of 5 microns on the silicon wafer surface using chemical vapor deposition.

[0113] 3.2) Use a direct writing printing device to print micro-nano structures. The equipment parameters are set as follows: nozzle diameter 30 microns, distance between the nozzle and the substrate 1 mm, liquid flow rate 10 μl / min, temperature of the printing environment 20 °C, relative humidity 40%; printing speed 1 mm / s, monitor the relative position between the syringe and the substrate and the printed micro-nano structures through an observation camera to ensure the smooth completion of the printing process.

[0114] Step 4: Heat and form the highly controllable micro-nano structures

[0115] Heat-treat the printed micro-nano structures at a temperature of 150 °C, a heating rate of 10 °C / min, and a holding time of 2 hours to form the expected micro-nano structures.

[0116] Through the above steps, micro-nano structures with a line width of about 600 nm were successfully prepared. These structures showed good morphological consistency and repeatability, verifying the effectiveness and feasibility of the technical solution.

[0117] Example 6

[0118] Preparation of an oligomer solution based on ion polymerization of copper salt and benzene tricarboxylic acid and its metal-organic hybrid material by electrohydrodynamic printing, the steps include:

[0119] Step 1: Configure the oligomer solution

[0120] 1.1) Take 40 g of copper nitrate tetrahydrate and add it to 500 mL of methanol to obtain solution A, where the concentration of copper nitrate tetrahydrate is 0.31 M.

[0121] 1.2) Add 5 g of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.098 M.

[0122] 1.3) 64 g of benzene tricarboxylic acid was added to 500 mL of methanol to obtain Solution C, where the concentration of benzene tricarboxylic acid was 0.609 M.

[0123] 1.4) Solution B was slowly added to Solution C and magnetically stirred at room temperature for 60 minutes to obtain Suspension D as an ionic oligomer solution. The volume ratio of Solution A to Solution B was 1:1.

[0124] The second step is to separate the oligomer solution and prepare an oligomer fluid

[0125] 2.1) The oligomer solution obtained in the first step was centrifuged at a speed of 6000 revolutions per minute for 30 minutes to separate oligomer a. The supernatant was discarded and the solid was taken.

[0126] 2.2) The obtained solid was dispersed in 500 mL of ethanol to prepare oligomer fluid b, and the mass fraction of the solid was adjusted to 4%, with a viscosity of 1000 cp.

[0127] The third step is to prepare highly controllable micro-nano structures

[0128] 3.1) A SiO2 insulating layer with a thickness of 5 μm was prepared on the surface of a silicon wafer using chemical vapor deposition.

[0129] 3.2) Micro-nano structure printing was carried out using an electrohydrodynamic printing device. The device parameters were set as follows: the electric field strength was 1 kV / cm, the nozzle diameter was 30 μm, the distance between the nozzle and the substrate was 1 mm, the liquid flow rate was 10 μL / min, the temperature of the printing environment was 20 °C, and the relative humidity was 40%; the printing speed was 1 mm / s. The relative position between the syringe and the substrate and the printed micro-nano structure were monitored through an observation camera to ensure the smooth completion of the printing process.

[0130] The fourth step is to heat and form the highly controllable micro-nano structure

[0131] The printed micro-nano structure was heat-treated at a temperature of 150 °C, a heating rate of 10 °C / min, and a holding time of 2 hours to form the expected micro-nano structure.

[0132] Through the above steps, micro-nano structures with a line width of approximately 50 μm were successfully prepared. These structures exhibited good morphological consistency and repeatability, verifying the effectiveness and feasibility of the technical solution.

[0133] The above-described embodiments only represent the implementation modes of the present invention, but should not be construed as limiting the scope of the patent for the present invention. It should be noted that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention.

Claims

1. A method for preparing a micro-nano printing material based on metal-organic ion polymerization, characterized in that, First, inorganic ions and organic molecular ions react in the presence of a capping agent to obtain a mixed emulsion, which serves as an oligomer solution fluid. Second, a micro-nano structure is printed using an electrohydrodynamic printing device; finally, a highly controllable functional material, i.e., a micro-nano structure, is obtained through heat treatment crystallization; the micro-nano structure has the characteristics of continuous structure, internal homogeneity, and flat surface.

2. The preparation method of a micro-nano printing material based on metal-organic ion polymerization according to claim 1, characterized in that, It includes the following steps: The first step is to prepare an oligomer solution. 1.1) Add metal salt M to organic solvent a to obtain solution A, where the concentration of metal salt M is 0.122M - 0.609M. 1.2) Add capping agent N to solution A to obtain solution B, where the concentration of capping agent N is 0.089M - 0.222M. 1.3) Add organic ligand O to organic solvent a to obtain solution C, where the concentration of organic ligand O is 0.122M - 0.609M. 1.4) Slowly add the solution B obtained in step 1.2) to the solution C obtained in step 1.3), and stir magnetically to obtain suspension D, which serves as an ionic oligomer solution; the volume ratio of solution A to solution B is 1:1; M ions react with O, and metal ions and organic ligand ions undergo an inorganic-organic ion polymerization reaction. Since N can form hydrogen bonds with O, the polymerization reaction will not proceed infinitely, and the finally obtained oligomer P molecules are stabilized at 2 - 10 molecules. The second step is to separate the oligomer solution and prepare an oligomer solution fluid. 2.1) Centrifuge the oligomer solution obtained in the first step to separate the oligomer solution from the reaction mother liquor and take the solid. 2.2) Disperse the solid obtained in step 2.1) in solvent a to prepare oligomer solution fluid b, where the mass fraction of the solid in the oligomer solution fluid is 1.0% - 5.0%, and an oligomer solution fluid with adjustable viscosity and surface tension is obtained by adjusting the amount of solvent added. The third step is to prepare a highly controllable micro-nano structure. 3.1) Prepare a layer of SiO2 insulating layer on the substrate surface. 3.2) Position the substrate on a levelled and heated workbench and use an electrohydrodynamic printing device to print a micro-nano structure. Load oligomer solution fluid b into the syringe of the electrohydrodynamic printing device as ink; the syringe is provided with a high-voltage electric field by a high-voltage power supply, a stable air pressure by an air pump, and is installed on a motor through a bracket to achieve precise printing; under the action of the high-voltage electric field between the syringe and the substrate, the ink is refined into a conical jet and gradually ejected, and a micro-nano structure with a line width of 500 nanometers to 50 micrometers is printed on the substrate surface by controlling the movement of the motor. The fourth step is to heat and form the highly controllable micro-nano structure. Use a temperature control system to heat-treat the micro-nano structure printed by electrohydrodynamic printing to obtain the expected micro-nano structure.

3. According to the method for preparing a micro-nano printing material based on metal-organic ion polymerization described in claim 2, wherein in the first step: In 1.1), the metal salt M includes zinc nitrate hexahydrate, copper nitrate tetrahydrate, zirconium tetrachloride; the organic solvent a includes methanol, ethanol, isopropanol. In 1.2), the N includes diethylamine, pyridine, dimethyl sulfoxide, triethylamine. In the above 1.3), the organic ligand O includes benzene tricarboxylic acid, terephthalic acid, and 2-methylimidazole; In the above 1.4), the magnetic stirring is carried out at room temperature for 30 to 60 minutes.

4. A method for preparing a micro-nano printing material based on metal-organic ion polymerization according to claim 2, wherein, In the second step: In the above 2.1), the rotation speed of the centrifugation treatment is 8000 to 10000 revolutions per minute, and the centrifugation time is 20 to 40 minutes; In the above 2.2), the solvent a includes methanol, ethanol, and isopropanol.

5. The preparation method of a micro-nano printing material based on metal-organic ion polymerization according to claim 2, characterized in that In the above 3.1), the substrate I includes silicon wafers, glass, quartz, polyimide, copper sheets, and aluminum sheets; the methods for preparing the insulating layer include chemical vapor deposition, sputtering, thermal evaporation, atomic layer deposition, and sol-gel methods; the thickness of the insulating layer is 1 to 10 micrometers.

6. The preparation method of a micro-nano printing material based on metal-organic ion polymerization according to claim 2, wherein, In the above 3.2, the parameters of the electrohydrodynamic printing device are: the electric field strength is 0.5 kV / cm to 3 kV / cm, the nozzle diameter is 30 to 100 micrometers, the distance between the nozzle and the substrate is 1 to 5 millimeters, the liquid flow rate is 0.1 to 10 microliters per minute, the temperature of the printing environment is 20 to 25 degrees Celsius, and the relative humidity is 40% to 60%; The printing speed is between 1 mm / s and 10 mm / s. The relative position between the syringe and the substrate and the printed micro-nano structure are monitored by an observation camera to ensure the smooth completion of the printing process.

7. A method for preparing a micro-nano printing material based on metal-organic ion polymerization according to claim 2, characterized in that, In the fourth step, the heating parameters are set as follows: the temperature range is 120 to 300 degrees Celsius, the heating and cooling rate device is 0.1 to 20 degrees Celsius per minute, and the temperature control accuracy is 0.1 degrees Celsius.

Images