An array type gas sensitive film and parallel manufacturing method thereof

Abstract

The present invention belongs to the field of electronic component manufacturing, and specifically relates to an array-type gas-sensitive film and a parallel manufacturing method thereof, wherein the method first mixes a gas-sensitive material with a photocurable component to make a photocurable gas-sensitive slurry, controls the thickness of the photocurable slurry film by an atomizing spraying method, and then selectively photocures the photocurable slurry film with high precision by laser direct writing to control the length and width dimensional accuracy of the film, and can obtain a gas-sensitive film with high consistency in film thickness and length and width on the substrate surface, and the gas-sensitive film has good gas-sensitive response performance, and can still maintain high consistency even after repeated superposition manufacturing. The manufacturing method of the present invention has high process flexibility, high repeatability, and high manufacturing efficiency, and can prepare gas-sensitive films with various performance requirements at one time, which can meet the detection of complex atmospheres.

Description

Technical Field

[0001] The invention belongs to the field of electronic component manufacturing, and in particular relates to an array type gas sensitive film and a parallel manufacturing method thereof. Background Art

[0002] Metal oxide gas sensors have the characteristics of small size, low price, high sensitivity and long life, and are very suitable for large-scale and wide-ranging applications. At present, the gas-sensitive membrane structures of metal oxide gas sensors are single-layer, stacked and multi-layer, and the components are mainly inorganic substances. The stacked and multi-layer structures are to cover one or several layers of membranes with other functions on the gas-sensitive membrane. Through the catalytic and filtering effects of this layer of membrane, the stability or selectivity of the gas sensor is increased, such as isolating dust and moisture, improving anti-siloxane stability, and improving selectivity for specific gases. At the same time, the development trend of metal oxide gas sensors is array integration, that is, integrating multiple different gas-sensitive membrane sensing units on a device, which can realize the detection of complex atmospheres. Therefore, it is necessary to realize the stacking and parallel film formation of gas-sensitive membranes, but the stacking and parallel manufacturing of multiple types of membranes have high requirements for film formation consistency and efficiency.

[0003] At present, the gas-sensitive film forming method of MEMs devices mainly adopts the method of piezoelectric or electrostatic spraying. The main process is to make the gas-sensitive material into a slurry with low viscosity and spray it into a film by piezoelectric drive or electrostatic drive. Since the viscosity of the slurry is low after spraying, it has fluidity before the solvent evaporates completely. Affected by factors such as surface tension, temperature and humidity, its cast expansion size is uncontrollable, and the error is generally in the order of tens of microns. At the same time, the nozzle size of piezoelectric and electrostatic spraying is generally tens of microns, so it is difficult to achieve micron-level length, width, and thickness precision film formation. At the same time, in the stacking and parallel manufacturing of multiple types of membranes, this error will be superimposed, resulting in a significant reduction in the consistency of the device. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an array-type gas-sensitive film and a method for manufacturing the same. The method first mixes a gas-sensitive material with a photocurable component to make a photocurable gas-sensitive slurry, deposits the slurry on the surface of a substrate by an atomizing spraying method to form a photocurable slurry film and controls the thickness of the photocurable slurry film, and then selectively photocures the photocurable slurry film by laser direct writing to control the length and width dimensional accuracy of the film, thereby obtaining a gas-sensitive film with high consistency in film thickness, length and width on the substrate surface.

[0005] The present invention first provides a parallel manufacturing method for an array type gas sensitive film, comprising the following steps:

[0006] S1: mixing a photocurable component, a gas-sensitive material and a first organic solvent to prepare a photocurable gas-sensitive slurry;

[0007] S2: atomizing the photocurable gas-sensitive slurry into nano-scale droplets by an atomizing spray device, and depositing the nano-scale droplets into a plurality of forming areas in an array on the same plane of the substrate surface to form a plurality of photocurable gas-sensitive slurry films with a predetermined thickness;

[0008] S3: controlling the laser beam to selectively expose and cure the plurality of photocurable gas-sensitive paste films in the plurality of molding areas according to a predetermined program;

[0009] S4: placing the substrate in a second organic solvent to dissolve the uncured portion, and after drying and sintering to remove the organic matter, a plurality of gas-sensitive films in an array are simultaneously obtained on the surface of the substrate.

[0010] According to one embodiment of the present invention, the gas-sensitive material in step S1 is a metal oxide or a metal oxide doped / modified / compounded with another metal, and the metal oxide is preferably one or more of SnO2, WO3, In2O3, ZnO, MnO2, TiO2, CuO, Co3O4, NiO, LaFeO3, Zn2SnO4, MoO2, CrO3, and the other metal is preferably Ru, Pd or Pt.

[0011] According to one embodiment of the present invention, the photocurable component includes a photosensitive prepolymer, a reactive diluent and a photoinitiator.

[0012] According to one embodiment of the present invention, the photosensitive prepolymer is one of acrylated epoxy resin, unsaturated polyester or polythiol-polyene system photocurable resin, preferably one of bisphenol A epoxy resin, novolac epoxy resin, alicyclic epoxy resin, aliphatic polyurethane acrylate, and aromatic polyurethane acrylate; the active diluent is one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate; the photoinitiator is one of photoinitiator 184, photoinitiator 1173, photoinitiator 907, photoinitiator 819, photoinitiator 369, Irgacure OXE 01, Irgacure OXE 02, and photoinitiator ITX.

[0013] According to one embodiment of the present invention, the substrate in step S2 is a heatable micro-hotplate.

[0014] According to one embodiment of the present invention, the first solvent is one of isopropanol, anhydrous ethanol, toluene, dichloromethane, acetonitrile, acetone, pyridine, cyclohexane, n-pentane, and diethyl ether; the second organic solvent is one of anhydrous ethanol, isopropanol, toluene, dichloromethane, acetonitrile, acetone, pyridine, cyclohexane, n-pentane, and diethyl ether.

[0015] According to one embodiment of the present invention, the method further comprises:

[0016] S5: Repeat steps S2-S4 to form a plurality of multilayer films in an array on the surface of the substrate.

[0017] According to one embodiment of the present invention, the method further comprises step S6:

[0018] After forming the multiple multilayer gas-sensitive films, continue to repeat S1-S4, replace the gas-sensitive material in S1 with the catalytic material, and correspondingly replace the preset pattern contained in the preset program in S3, to form a catalytic film on the multiple multilayer gas-sensitive films to form multiple gas-sensitive-catalytic stacked films; wherein, in the preset program S3 after replacement, the length, width and thickness dimensions of the preset pattern of the photocurable catalytic slurry film are all larger than the preset pattern of the photocurable gas-sensitive slurry film before replacement.

[0019] According to one embodiment of the present invention, the catalytic material is a metal catalyst, a metal oxide catalyst, a metal sulfide catalyst, a molecular sieve catalyst, a non-metallic nanocatalyst or a combination of the above substances. The metal catalyst, metal oxide catalyst, metal sulfide catalyst, molecular sieve catalyst, non-metallic nanocatalyst is preferably Pt, PtCu alloy, Al2O3, TiO2, LaCrO3, ZnS, ZSM-5, MCM-41, CNTs. The composition is preferably a complex of Ag and TiO2, a complex of Pt and Al2O3, a complex of Al2O3 and ZnS, a complex of Pt and Fe2O3, Ag-modified molecular sieve ZSM-5 or Pd-modified molecular sieve MCM-41.

[0020] According to another aspect of the present invention, the present invention also provides a gas-sensitive film manufactured by the above method.

[0021] In general, the above technical solution conceived by the present invention has the following technical advantages compared with the prior art:

[0022] 1) The present invention combines the atomization spraying of photocurable slurry with the laser direct writing molding for the first time, and can prepare the gas-sensitive film with high consistency. Based on the atomization spraying of the photocurable slurry, the thickness of the gas-sensitive film can be controlled within 1-10um, and the thickness error can be controlled within 50nm. Based on the laser direct writing molding of the photocurable slurry, the length and width of the gas-sensitive film can be controlled within 10-1000um, and the length and width error of the film can be controlled within 2.5um. In addition, since multiple molding areas are set on the substrate at the same time, the rapidity of laser direct writing and the automation of the atomization spraying device can be used to achieve continuous and efficient production;

[0023] 2) The method of the present invention is based on multiple choices of slurry components and repeated atomization spraying-laser direct writing operations, and can prepare single-layer, multi-layer and even laminated gas-sensitive films with various properties at one time. The prepared gas-sensitive film has good gas-sensitive response performance. The gas-sensitive film can detect complex atmospheres, and even after repeated superposition manufacturing, the consistency of the gas-sensitive film can still be highly maintained. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The process flow of preparing a high-consistency single film by atomizing and spraying a photocurable slurry and laser direct writing in Example 1 of the present invention is shown.

[0025] Figure 2 The diagram shows the size statistics of multiple gas-sensitive films of the same component obtained in Example 1 of the present invention.

[0026] Figure 3 The gas-sensitive response distribution curves of multiple gas-sensitive films of the same components obtained in Example 1 of the present invention to 100 ppm ethanol are shown.

[0027] Figure 4 The process flow of preparing a high-consistency array film by atomizing and spraying a photocurable slurry and laser direct writing in Example 2 of the present invention is shown.

[0028] Figure 5 The diagram shows the size statistics of multiple array gas-sensitive films obtained in Example 2 of the present invention.

[0029] Figure 6 The process flow of the third embodiment of the present invention for the simultaneous manufacture of a gas-sensitive-catalytic laminated film by atomizing and spraying a photocurable slurry and laser direct writing is shown.

[0030] Figure 7 A size statistical diagram of multiple laminated films obtained in Example 3 of the present invention is shown.

[0031] Figure 8 The size statistics of the gas sensitive film obtained in Comparative Example 1 are shown.

[0032] Fig. 9 The size statistics of the gas-sensitive film obtained in Comparative Example 2 are shown. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0034] The present invention needs to first prepare a photocurable slurry, and the raw materials used are easily purchased photosensitive prepolymers, reactive diluents, photoinitiators, gas-sensitive materials and solvents. The photosensitive prepolymers, reactive diluents, photoinitiators, gas-sensitive materials and solvents are mechanically mixed, and the above-mentioned photocurable slurry is atomized into nano-scale droplets through an atomizing spray device and deposited on multiple array-type molding areas on a substrate to form a photocurable slurry film. The high-precision laser beam is controlled by a computer to scan according to a predetermined program, and the atomized area on the substrate is directly exposed to write the predetermined gas-sensitive film pattern, and the above-mentioned substrate is placed in a solvent to dissolve and remove the uncured part, and then dried and sintered at high temperature to remove organic matter to obtain a gas-sensitive film. The atomized photocurable slurry can be sprayed to form a uniform and dense photocurable slurry film, and then combined with the gas-sensitive film pattern designed by laser direct writing and direct molding, the film thickness and film length and width can be controlled with high precision, and single-layer, stacked, multi-layer and other gas-sensitive film structures can be prepared with high consistency, which can reduce the difficulty of film consistency and high efficiency, and greatly improve the efficiency of preparing metal oxide gas sensors.

[0035] A parallel manufacturing method for an array type gas sensitive film comprises the following steps:

[0036] S1: mixing a photocurable component, a gas-sensitive material and a first organic solvent to prepare a photocurable gas-sensitive slurry;

[0037] S2: atomizing the photocurable gas-sensitive slurry into nano-scale droplets by an atomizing spray device, and depositing the droplets into a plurality of forming areas in an array on the same plane of the substrate surface to form a plurality of photocurable gas-sensitive slurry films with a predetermined thickness;

[0038] S3: controlling the laser beam to selectively expose and cure the plurality of photocurable gas-sensitive paste films in the plurality of molding areas according to a predetermined program;

[0039] S4: placing the substrate in a second organic solvent to dissolve the uncured portion, and after drying and sintering to remove the organic matter, a plurality of gas-sensitive films in an array are simultaneously obtained on the surface of the substrate.

[0040] In some embodiments, a plurality of forming regions are arranged in an array, which may be a common arrangement in the art, including but not limited to 2×2, 2×3, 3×3, 3×4, 4×4, and 4×5 arrays.

[0041] In some embodiments, the gas-sensitive material uses a metal oxide or a metal oxide doped / modified / compounded with another metal, preferably one or more of SnO2, WO3, In2O3, ZnO, MnO2, TiO2, CuO, Co3O4, NiO, LaFeO3, Zn2SnO4, MoO2, CrO3, SnO2-Ru, SnO2-Pd, Pt@SnO2, where the "- " between each two substances represents doping or compounding, and the "@" represents modification.

[0042] In some embodiments, the photosensitive prepolymer can be a photosensitive resin commonly used in the art, such as an acrylated epoxy resin, an unsaturated polyester, or a polythiol / polyene system photocurable resin. Specifically, it can be one of bisphenol A epoxy resin, phenolic epoxy resin, alicyclic epoxy resin, aliphatic polyurethane acrylate, or aromatic polyurethane acrylate.

[0043] In some embodiments, the reactive diluent is different from a general organic solvent and may be one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate.

[0044] In some embodiments, the photoinitiator can be a common photoinitiator in the art, such as photoinitiator 184, photoinitiator 1173, photoinitiator 907, photoinitiator 819, photoinitiator 369, Irgacure OXE 01, Irgacure OXE02, or photoinitiator ITX.

[0045] In some embodiments, the first and second organic solvents may be common types in the art, including but not limited to isopropanol, anhydrous ethanol, toluene, dichloromethane, acetonitrile, acetone, pyridine, cyclohexane, n-pentane, and ether.

[0046] In some embodiments, step S5 is also included, repeating steps S1-S4 to form multiple multilayer films in an array on the surface of the substrate. The number of repetitions completely corresponds to the number of layers of the multilayer film actually designed, which is usually designed to be 2-6 layers. Of course, in order to save procedures, the corresponding number of gas-sensitive film slurry portions can be prepared according to the designed number of layers of the multilayer film in S1, and then only S2-S4 can be repeated.

[0047] Similarly, when it is necessary to prepare a multilayer film of the same size but each gas-sensitive film needs to have different detection performance, multiple groups of different gas-sensitive slurries can be prepared simultaneously in step S1, and then steps S2-S4 can be repeated. Note that the gas-sensitive slurry used each time is different.

[0048] Similarly, the gas-sensitive slurry may be replaced every 2 / 3 / 4 layers according to actual needs.

[0049] Similarly, in some embodiments, step S6 is also included: after forming the multiple multilayer gas-sensitive membranes, continue to repeat S1-S4, replace the gas-sensitive material in S1 with the catalytic material, and correspondingly replace the preset graphics contained in the predetermined program in S3 in the computer to form the outermost catalytic film on the multiple multilayer gas-sensitive membranes to obtain multiple gas-sensitive-catalytic stacked membranes.

[0050] In some embodiments, in the predetermined program S3 after replacement, the length, width and thickness of the preset pattern of the photocurable catalytic slurry film are all larger than the preset pattern of the photocurable gas-sensitive slurry film before replacement. After it is cured into a catalytic film, it can play a certain protective role on the gas-sensitive film and increase the catalytic area.

[0051] In some embodiments, the catalytic material is a metal catalyst, a metal oxide catalyst, a metal sulfide catalyst, a molecular sieve catalyst, a non-metallic nanocatalyst, or a combination thereof.

[0052] In some embodiments, the metal catalyst, metal oxide catalyst, metal sulfide catalyst, molecular sieve catalyst, non-metallic nanocatalyst is Pt, PtCu alloy, Al2O3, TiO2, LaCrO3, ZnS, ZSM-5, MCM-41 or CNTs, and the composition is Ag-TiO2, Pt-Al2O3, Al2O3-ZnS, Pt-Fe2O3, Ag@ZSM-5 or Pd@MCM-41, where "-" represents doping or composite, and "@" represents modification.

[0053] The following are specific embodiments:

[0054] Example 1

[0055] (1) Preparation of photocurable slurry

[0056] 7.125 g of polyurethane acrylate, 1.1875 g of 1,6-hexanediol diacrylate, 1.1875 g of trimethylolpropane triacrylate, 0.05 g of photoinitiator 184, 10 g of SnO2 powder, and 25 ml of isopropanol were added to a ball mill and ball milled for 4 hours to obtain a photocurable slurry.

[0057] (2) Photocuring slurry atomization spraying

[0058] A total of 16 4×4 array areas are designed on the micro-hotplate. After 5 μL of photocurable slurry is sucked with a micro-syringe and the micro-syringe is fixed, a high-voltage electrostatic field is applied by electrostatic spraying to atomize the liquid at the needle of the micro-syringe into nano-scale droplets, and the droplets are deposited on the first array area on the micro-hotplate, i.e., the first slurry film area to be photocured. The electrostatic field is turned off, and the micro-hotplate is continued to be moved to apply a high electrostatic field to atomize and spray the second slurry film area to be photocured. Figure 1 As shown, this process is repeated to obtain 16 photocurable gas-sensitive paste film regions in total.

[0059] (3) Laser direct writing of photocurable slurry

[0060] The gas-sensitive film pattern pre-designed by the drawing software is imported into the computer, and the computer is used to control the laser head to perform high-precision selective laser beam scanning on the 16 atomized forming areas on the surface of the micro-hotplate to obtain the cured gas-sensitive film pattern.

[0061] (4) Dissolving to remove glue and high temperature sintering to remove organic matter

[0062] The micro-hotplate was ultrasonically cleaned in anhydrous ethanol and deionized water for 2 minutes each. After removing the uncured part, the micro-hotplate was dried at 70°C. After removing the anhydrous ethanol and deionized water, 16 identical single-layer gas-sensitive films were obtained after annealing at 550°C in a muffle furnace.

[0063] Figure 1 The figure shows the preparation process of photocuring slurry atomization spraying and laser direct writing with high consistency to prepare multiple single-layer gas-sensitive films in batches. Figure 2 It can be seen that the gas-sensitive films prepared in Examples 1-3 are uniform and dense, with a thickness controlled at about 2.35 um, and a length and width of the film controlled at about 100 um. In addition, the prepared gas-sensitive films have high consistency, with a thickness error within 50 nm, and a length and width error within 2.5 um, with an error of less than 5%. Figure 3 It can be seen that the prepared 16 SnO2 gas-sensitive films have high consistency in gas-sensitive response to 100 ppm ethanol, and the response values ​​are all around 25, showing the high consistency of batch preparation of single-layer gas-sensitive films by photocuring slurry atomization spraying and laser direct writing.

[0064] Example 2

[0065] (1) Preparation of photocurable slurry

[0066] In 16 ball mill jars, 7.125g of polyurethane acrylate, 1.1875g of 1,6-hexanediol diacrylate, 1.1875g of trimethylolpropane triacrylate, 0.05g of photoinitiator 184 and 25ml of isopropanol were added, and then 10g of SnO2, WO3, In2O3, ZnO, MnO2, TiO2, CuO, Co3O4, NiO, LaFeO3, Zn2SnO4, MoO2, CrO3, SnO2-Ru, SnO2-Pd and Pt@SnO2 powders were added to the 16 ball mill jars respectively, and the photocuring slurry was obtained by ball milling for 4 hours.

[0067] (2) Photocuring slurry atomization spraying

[0068] A total of 16 4×4 array areas were designed on the micro-hotplate, and 1 μL of the 16 different photocurable slurries were sucked up by 16 different micro-syringes and fixed respectively. Electrostatic spraying was used to apply a high-voltage electrostatic field to atomize the liquid at the needle tip into nanoscale droplets that were deposited on 16 areas on the micro-hotplate. The electrostatic field was turned off to obtain 16 different photocurable gas-sensitive slurry films.

[0069] (3) Laser direct writing of photocurable slurry

[0070] The gas-sensitive film pattern designed by the drawing software is imported into the computer, and the laser beam is controlled by the computer to perform high-precision selective scanning and curing on the 16 atomized forming areas of the micro-hotplate to obtain the required gas-sensitive film pattern on the substrate surface.

[0071] (4) Dissolving to remove glue and high temperature sintering to remove organic matter

[0072] The micro-hotplate was ultrasonically cleaned in anhydrous ethanol and deionized water for 2 minutes each, dried at 70°C to remove the anhydrous ethanol and deionized water, and then annealed at 550°C in a muffle furnace to obtain 16 different single-layer gas-sensitive films.

[0073] Figure 4 The figure shows the process flow of preparing array gas-sensitive film by atomizing and spraying photocuring slurry and laser direct writing with high consistency. Figure 5 It can be seen that although the gas-sensitive film materials prepared in each molding area are different, the film thickness is about 2.55um, the film length and width are about 90um, the thickness control error is within 50nm, and the film length and width error is within 2.2um, showing the high consistency and efficiency of the method of preparing array gas-sensitive films by photocuring slurry atomization spraying and laser direct writing molding.

[0074] Example 3

[0075] (1) Preparation of gas-sensitive film photocuring slurry and catalytic film photocuring slurry

[0076] 7.125 g of polyurethane acrylate, 1.1875 g of 1,6-hexanediol diacrylate, 1.1875 g of trimethylolpropane triacrylate, 0.05 g of photoinitiator 184, and 10 g of In2O3-Au and In2O3-Ir were added to two ball mills and ball milled for 4 hours to prepare a photocurable gas-sensitive slurry;

[0077] 7.125 g of polyurethane acrylate, 1.1875 g of 1,6-hexanediol diacrylate, 1.1875 g of trimethylolpropane triacrylate, 0.05 g of photoinitiator 184 and 10 g of ZnS, Pt, Pt-Cu, Al2O3, LaCrO3, ZSM-5, Pt-Al2O3, and Ag@ZSM-5 powders were added to the other 8 ball mill jars and ball milled for 4 hours to obtain a photocurable catalytic slurry.

[0078] (2) Gas-sensitive film photocuring slurry atomization spraying

[0079] A total of 16 4×4 array areas were designed on the micro-hotplate. 1 μL of In2O3-Au and In2O3-Ir photocurable slurries were respectively aspirated and fixed using two micro-syringes. A high-voltage electrostatic field was applied using electrostatic spraying to atomize the liquid at the needle tip into nanoscale droplets that were deposited on 16 areas of the micro-hotplate. Each photocurable slurry was atomized and sprayed on 2 areas. The electrostatic field was turned off to obtain 16 photocurable gas-sensitive slurry films.

[0080] (3) Laser direct writing of gas sensitive film photocuring slurry

[0081] The designed gas-sensitive film pattern is imported into the computer, and the laser beam is controlled by the computer to perform high-precision scanning and curing on the 16 atomized forming areas of the micro-hotplate to obtain the desired gas-sensitive film pattern.

[0082] (4) Dissolving and removing glue

[0083] The micro hot plate was placed in anhydrous ethanol and deionized water for ultrasonic cleaning for 2 minutes each, and dried at 70°C to remove the anhydrous ethanol and deionized water.

[0084] (5) Repeated atomization spraying of catalytic film photocuring slurry

[0085] Use 8 micro-syringes to draw 1 μL of ZnS, Pt, Pt-Cu, Al2O3, LaCrO3, ZSM-5, Pt-Al2O3, and Ag@ZSM-5 photocurable slurry respectively and fix them. Using electrostatic spraying, a high-voltage electrostatic field is applied to atomize the liquid at the needle tip into nanoscale droplets and deposit them on 16 areas of the micro-hotplate. Each photocurable slurry is atomized and sprayed on 2 areas, which are the positions of the previous layer of In2O3-Au and In2O3-Ir photocurable slurry films. Turn off the electrostatic field to obtain 16 photocurable catalytic slurry films.

[0086] (6) Laser direct writing catalytic film photocuring slurry

[0087] The previous gas-sensitive film pattern was changed in the drawing software, and the designed catalytic film pattern was re-imported into the computer. The computer was used to control the laser beam to perform high-precision scanning and curing on the 16 areas that had been atomized on the micro-hotplate to obtain the required catalytic film pattern.

[0088] (7) Dissolving and removing glue, high temperature sintering to remove organic matter

[0089] The micro-hotplate was ultrasonically cleaned in anhydrous ethanol and deionized water for 2 minutes each, dried at 70°C to remove the anhydrous ethanol and deionized water, and then annealed at 550°C in a muffle furnace to obtain 16 gas-sensitive-catalytic laminated membranes.

[0090] Figure 6 The figure shows the process flow chart of the photocuring slurry atomization spraying and the laser direct writing forming laminated film in parallel. Figure 7 It can be seen from a that after adopting the laminated film preparation method of this embodiment, the thickness of the catalyst film is controlled at about 3.6um, and the thickness control error is within 50nm. Figure 7 It can be seen from b that the length and width of the catalytic membrane are controlled at about 150um, and the errors of the length and width are within 1.2um. The length, width and thickness dimensions of the 16 gas-sensitive-catalytic laminated membranes show high consistency.

[0091] Comparative Example 1

[0092] Manufacturing gas sensitive film by piezoelectric film spraying

[0093] (1) Preparation of spray slurry

[0094] Place 3g SnO2 powder in a ball mill, add 100ml alcohol and 0.46g alumina dispersion for ball milling, then take out and dry; then place the dried powder in a beaker, add isopropanol for mechanical stirring, and when the viscosity is appropriate, transfer it to a ball mill and ball mill again to obtain SnO2 gas sensitive slurry.

[0095] (2) Gas-sensitive slurry piezoelectric spraying

[0096] Place the micro-hotplate on the heated adsorption platform and move it under the piezoelectric spraying device, load SnO2 gas-sensitive slurry into the liquid supply system, and move the nozzle to spray SnO2 gas-sensitive slurry in a total of 16 4×4 array areas.

[0097] (3) Heating to remove organic solvent

[0098] After annealing the micro-hotplate at 100 °C for 10 min on a heated adsorption platform, 16 gas-sensitive films were obtained.

[0099] Comparative Example 2

[0100] Electrostatic spraying to manufacture gas sensitive film

[0101] (1) Preparation of spray slurry

[0102] Place 3g SnO2 powder in a ball mill, add 100ml alcohol and 0.46g alumina dispersion for ball milling, then take out and dry; then place the dried powder in an agate mortar and add organic slurry for manual grinding. When the viscosity is appropriate, transfer it to a ball mill and ball mill again to obtain SnO2 gas sensitive slurry.

[0103] (2) Electrostatic spraying of gas-sensitive slurry

[0104] Place the micro hot plate on the adsorption platform and move it under the electrostatic spraying device, load SnO2 gas-sensitive slurry into the syringe, apply a strong voltage between the tip of the syringe and the adsorption platform, and move the adsorption platform to spray SnO2 gas-sensitive slurry in a 4×4 array area with a total of 16 areas.

[0105] (3) High temperature sintering to remove organic matter

[0106] The micro-hotplate was placed in a muffle furnace and annealed at 550 °C for 2 h to obtain 16 gas-sensitive films.

[0107] Table 1 Comparison of the performance of the single-layer gas-sensitive films prepared in Examples 1-3 and Comparative Examples 1-2

[0108]

[0109] from Figure 8 , 9 It is not difficult to see from Table 1 that the thickness error and length and width error of the single-layer gas-sensitive film manufactured in Comparative Example 1-2 are both high, and the consistency is poor. If used for stacking manufacturing, it will only further reduce the consistency.

[0110] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A parallel manufacturing method for an array type gas sensitive film, characterized in that: The steps include: S1: mixing a photocurable component, a gas-sensitive material and a first organic solvent to prepare a photocurable gas-sensitive slurry; S2: atomizing the photocurable gas-sensitive slurry into nano-scale droplets by an atomizing spraying device, and depositing the nano-scale droplets into a plurality of forming areas in an array on the same plane of the substrate surface to form a plurality of photocurable gas-sensitive slurry films with a predetermined thickness; S3: controlling the laser beam to selectively expose and cure the plurality of photocurable gas-sensitive paste films in the plurality of molding areas according to a predetermined program; S4: placing the substrate in a second organic solvent to dissolve the uncured portion, and drying and sintering to remove the organic matter to simultaneously obtain a plurality of array-type gas-sensitive films on the surface of the substrate.

2. The method according to claim 1, characterized in that The gas-sensitive material in step S1 is a metal oxide or a metal oxide doped with another metal.

3. The method according to claim 2, characterized in that The metal oxide is one or more of SnO2, WO3, In2O3, ZnO, MnO2, TiO2, CuO, Co3O4, NiO, LaFeO3, Zn2SnO4, MoO2, CrO3, and the other metal is Ru, Pd or Pt.

4. The method according to claim 1, characterized in that: The photocurable components include photosensitive prepolymer, reactive diluent and photoinitiator.

5. The method according to claim 4, characterized in that The photosensitive prepolymer is one of acrylated epoxy resin, unsaturated polyester or polythiol-polyene system photocurable resin; The active diluent is one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate; The photoinitiator is one of photoinitiator 184, photoinitiator 1173, photoinitiator 907, photoinitiator 819, photoinitiator 369, Irgacure OXE 01, Irgacure OXE02, and photoinitiator ITX.

6. The method according to claim 5, characterized in that The photosensitive prepolymer is one of bisphenol A epoxy resin, phenolic epoxy resin, alicyclic epoxy resin, aliphatic polyurethane acrylate and aromatic polyurethane acrylate.

7. The method according to claim 1, characterized in that The substrate in step S2 is a heatable micro-hotplate.

8. The method according to claim 1, characterized in that The first organic solvent is one of isopropanol, anhydrous ethanol, toluene, dichloromethane, acetonitrile, acetone, pyridine, cyclohexane, n-pentane, and ether; the second organic solvent is one of anhydrous ethanol, isopropanol, toluene, dichloromethane, acetonitrile, acetone, pyridine, cyclohexane, n-pentane, and ether.

9. The method according to claim 1, characterized in that: The method further comprises: S5: Repeat steps S1-S4 to form a plurality of multi-layer gas-sensitive films in an array on the surface of the substrate.

10. The method according to claim 9, characterized in that The step S6 is also included: After forming the plurality of multilayer gas-sensitive films, continue to repeat S1-S4, replace the gas-sensitive material in S1 with a catalytic material, and correspondingly replace the preset pattern contained in the predetermined program in S3, and form a catalytic film on the plurality of multilayer gas-sensitive films to form a plurality of gas-sensitive-catalytic laminated films; Among them, in the predetermined procedure S3 after the replacement, the length, width and thickness of the preset pattern of the photocurable catalytic paste film are all larger than the preset pattern of the photocurable gas-sensitive paste film before the replacement.

11. The method according to claim 10, characterized in that The catalytic material is a metal element catalyst, a metal oxide catalyst, a metal sulfide catalyst, a molecular sieve catalyst, a non-metallic nano catalyst or a combination of the above substances.

12. The method according to claim 11, characterized in that The metal element catalyst, metal oxide catalyst, metal sulfide catalyst, molecular sieve catalyst and non-metal nanocatalyst are Pt, PtCu alloy, Al2O3, TiO2, LaCrO3, ZnS, ZSM-5, MCM-41 and CNTs; the composition is a composite of Ag and TiO2, a composite of Pt and Al2O3, a composite of Al2O3 and ZnS, a composite of Pt and Fe2O3, Ag-modified molecular sieve ZSM-5 or Pd-modified molecular sieve MCM-41.

13. A gas-sensitive film manufactured by the method according to any one of claims 1 to 12.

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