Micro-nano spray needle manufacturing method based on stretching material and spray needle

Abstract

The invention discloses a micro-nano spray needle manufacturing method based on a stretching material, which comprises the following steps: printing photoresist on a substrate I to obtain a line I, obtaining a substrate I with a nano ridge through a stretching method, printing photoresist on the substrate I with the nano ridge to obtain a line II, and curing and hardening the substrate I to obtain a micro-nano spray needle convex mold; a polymer solution is poured into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; and combining and bonding the micro-nano spray needle bottom plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle. The invention discloses a micro-nano spray needle manufacturing method based on a stretching material and a spray needle, an electric jet printing and stretching method and a pouring method are adopted to obtain a micro-nano spray needle substrate, and oxygen plasma is matched to seal a micro-nano channel of the spray needle to obtain a complete micro-nano spray needle; by utilizing the characteristic that the thermoplastic material can be stretched, the manufacturing cost of the micro-nano spray needle is reduced, and the micro-nano spray needle has the characteristics of simple process and easiness in implementation.

Description

Technical Field

[0001] The invention relates to the field of micro-electromechanical systems, and in particular to a method for manufacturing a micro-nano spray needle based on a stretched material and a spray needle. Background Art

[0002] Micro-nano spray needles are widely used in high-precision manufacturing technologies such as electro-hydraulic jet printing. Electro-hydraulic jet printing technology has attracted much attention due to its high resolution, low cost and wide ink compatibility, and has broad application prospects in the fields of flexible electronic device manufacturing. However, micro-nano spray needles are very easy to get clogged during the printing process and become consumables in printing experiments. Therefore, how to prepare nano spray needles at low cost and quickly has become a key issue that needs to be solved urgently.

[0003] The common problems of low-cost micro-nano needle spraying methods in the prior art are that the size is difficult to control and the processing steps are complicated. For example, the Sutter puller stretching in the traditional needle preparation technology is difficult to control the size and easy to break. However, the SU-8 photoresist cracking method in the prior art has poor size controllability and low repeatability. Summary of the invention

[0004] The present invention overcomes the shortcomings of the prior art and provides a micro-nano spray needle manufacturing method and spray needle based on stretchable materials. The micro-nano spray needle substrate is obtained by electrojet printing and stretching method and casting method, and the spray needle micro-nano channel is sealed with oxygen plasma to obtain a complete micro-nano spray needle. By utilizing the stretchable characteristics of thermoplastic materials, the production cost of the micro-nano spray needle is reduced, and the process is simple and easy to implement.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: a method for manufacturing a micro-nano spray needle based on a stretched material, comprising the following steps: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution into a micro-nano spray needle convex mold; The method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, printing photoresist on substrate 1 to obtain line 1, obtaining substrate 1 with nano ridges by stretching method, and printing photoresist on substrate 1 with nano ridges to obtain line 2, obtaining substrate 1 with micro-nano ridges, and curing substrate 1 with micro-nano ridges to obtain a micro-nano needle convex mold; Step 1a2, pouring a polymer solution into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; Step 1b, obtaining a micro-nano spray needle cover plate by pouring a polymer solution into a micro-nano spray needle cover plate mold; Step 2, aligning and bonding the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle.

[0006] In a preferred embodiment of the present invention, line one comprises micron ridge one; The line 2 includes a micron ridge 2 connected to the line 1, and an outer contour pattern arranged around the periphery of the micron ridge 1 and the micron ridge 2; The photoresist used for printing line one and / or line two is positive photoresist or negative photoresist.

[0007] In a preferred embodiment of the present invention, in step 1a1, the stretching method comprises: The substrate 1 on which the line 1 is printed is heated, and then the heated substrate 1 is stretched to drive the line 1 to stretch, until the line 1 on the substrate 1 is stretched into a nano ridge; In step 1a1, curing the hard film comprises the following steps: The substrate with the micro-nano ridges is placed on a horizontal hot plate for pre-baking, photolithography, and hardening to obtain a micro-nano needle convex mold.

[0008] In a preferred embodiment of the present invention, pouring a polymer solution into a micro-nano spray needle convex mold to obtain a micro-nano spray needle base plate comprises the following steps: Step 1a2.1, sealing, drying and hydrophobicizing the micro-nano spray needle convex mold; Step 1a2.2, pouring the polymer solution into the micro-nano spray needle convex mold; Step 1a2.3, placing the micro-nano spray needle convex mold poured with the polymer solution in an oven for curing; Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold cast with the polymer solution, trimming the shape, and obtaining the micro-nano spray needle base plate.

[0009] In a preferred embodiment of the present invention, in step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 1-5 ml trimethylsiloxane atmosphere for sealed drying, and the hydrophobic treatment time is 10-20 minutes; And / or, in step 1a2.2, the polymer solution is prepared by mixing the PDMS base material and the curing agent in a ratio of 4:1 to 8:1, stirring for 5 minutes to mix them evenly, and then placing them in a vacuum box to degas and remove bubbles, and the obtained polymer solution is a PDMS mixed solution; And / or, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution is placed in a vacuum box, the air pressure in the vacuum box is maintained below 10Pa, for 1 to 2 hours, the bubbles in the polymer solution are eliminated, and the micro-nano spray needle convex mold pattern is filled, and then placed on a static table for 20 to 30 minutes; then the micro-nano spray needle convex mold poured with the polymer solution is placed in an oven for curing, the oven temperature is 60 to 80°C, and the baking time is 2 to 4 hours; then the cured micro-nano spray needle convex mold poured with the polymer solution is cooled to room temperature, taken out for demoulding, and the coated tool is used to cut and trim the shape to obtain a micro-nano spray needle base plate.

[0010] In a preferred embodiment of the present invention, the method for preparing the micro-nano spray needle cover plate mold comprises the following steps: Print photoresist on the cleaned substrate 2 by electrojet, then place it on a horizontal hot plate and heat it for 15-30 minutes, control the temperature at 60-100°C, then photolithograph for 5-10 minutes, place it on the hot plate to harden the film for 15-30 minutes, and the temperature is 60-100°C to obtain a micro-nano spray needle cover plate mold.

[0011] In a preferred embodiment of the present invention, the process of pouring a polymer solution into a micro-nano spray needle cover plate mold to obtain a micro-nano spray needle cover plate comprises the following steps: The micro-nano spray needle cover plate mold is placed in a sealed drying tower with 1-5 ml trimethylsiloxane atmosphere for hydrophobic treatment for 10-20 minutes, and the prepared polymer solution is poured on the micro-nano spray needle cover plate mold. Then, the micro-nano spray needle cover plate mold poured with the polymer solution is placed in a vacuum box with an air pressure of less than 10 Pa for 1-2 hours to remove bubbles from the polymer solution in the micro-nano spray needle cover plate mold and fill the pouring cavity of the micro-nano spray needle cover plate mold with the polymer solution; then, it is placed on a static table for 20-30 minutes; then, it is placed in an oven for curing at an oven temperature of 60-80°C and a baking time of 2-4 hours; then, after cooling to room temperature, it is taken out for demoulding, and the shape is corrected with a coated tool to obtain a micro-nano spray needle cover plate.

[0012] In a preferred embodiment of the present invention, in step 2, the micro-nano spray needle base plate and the micro-nano spray needle cover plate are aligned and bonded to obtain the micro-nano spray needle, comprising the following steps: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate were treated with oxygen plasma respectively, with a treatment power of 15-25W and a treatment time of 20-30s; The processed micro-nano spray needle bottom plate is aligned and bonded with the micro-nano spray needle cover plate to seal the micro-nano channel on the micro-nano spray needle bottom plate.

[0013] In a preferred embodiment of the present invention, the micron ridges 2 include micron ridges having a width of 30-50 μm and 70-100 μm printed after the nano ridges; And / or, in step 1a1, the pre-baking time in the curing hardening film is 15-30 minutes, the pre-baking temperature is 60-100° C., the photolithography time is 5-10 minutes, the hardening time of placing the film on a hot plate is 15-30 minutes, and the hardening temperature is 60-100° C.; and / or, in step 1a1, the substrate is heated to a temperature of 110-130° C., the stretching force is 5-30 N, the stretching time is 8-15 s, and the nano-ridges are nano-ridges of less than 100 nm; and / or, in step 1a1, the substrate 1 is stretched at room temperature with a tensile force of 5 to 30 N, a stretching time of 8 to 15 s, and the nano-ridges are nano-ridges of less than 100 nm; And / or, in step 1a1, during the stretching process, the relative direction of the stretching can be adjusted according to the actual required nano-ridge size requirements; wherein the force trajectories between the relative directions of several stretchings can adopt mutually intersecting force trajectories to adjust the nano-ridge size; And / or, the substrate one and / or the substrate two is one of PMMA film, PET film, PVP film, sealing film, PDMS film, PC film, PP film, PE film, PVC film, PS film, SERS film, and hydrogel film; And / or, the photoresist used for printing line one and / or line two is BN photoresist; And / or, the photoresist used for printing line 1 and / or line 2 can be replaced by one of PDMS, PEO, hydrogel, liquid metal, rubber, and graphene; And / or, in step 2, inserting the steel needle into the microchannel of the micro-nano channel formed by the bonded micro-nano spray needle base plate and the micro-nano spray needle cover plate, performing interference fit, and obtaining the micro-nano spray needle; And / or, the parameter requirements of the photoresist of line one include: a viscosity range of 5 to 5000 cP; a surface tension range of 20 to 45 mN / m.

[0014] In a preferred embodiment of the present invention, a micro-nano spray needle is prepared by a micro-nano spray needle manufacturing method based on a stretched material.

[0015] The present invention solves the defects existing in the technical background, and the beneficial technical effects of the present invention are: A micro-nano spray needle manufacturing method and spray needle based on stretchable materials, using electrojet printing and stretching method and casting method to obtain a micro-nano spray needle base, and oxygen plasma to seal the spray needle micro-nano channel to obtain a complete micro-nano spray needle; by utilizing the stretchable characteristics of thermoplastic materials, the production cost of obtaining the micro-nano spray needle is reduced, and the process is simple and easy to implement. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0017] Figure 1 It is a manufacturing flow chart of the micro-nano spray needle convex mold according to the preferred embodiment of the present invention.

[0018] Figure 2 This is a flow chart of the micro-nano spray needle manufacturing process of a preferred embodiment of the present invention; Figure 3 This is a manufacturing flow chart of a micro-nano spray needle cover plate mold according to a preferred embodiment of the present invention; Figure 4 This is a manufacturing flow chart of a micro-nano spray needle cover plate according to a preferred embodiment of the present invention; Figure 5 It is a micro-nano needle bonding and packaging flow chart of a preferred embodiment of the present invention; Figure 6 It is an optical microscope of the micro-nano spray needle convex mold of the preferred embodiment of the present invention. Figure 1 ; Figure 7 It is an optical microscope of the micro-nano spray needle convex mold of the preferred embodiment of the present invention. Figure 2 ; Figure 8 is a partial optical microscope image of a micro-nano spray needle of a preferred embodiment of the present invention; Fig. 9 This is a picture of a preferred embodiment of the present invention in which after printing line one (micrometer line), the printed line one is gradually stretched by a stretching method to become thinner to form a micrometer ridge one; Fig.10 This is a preferred embodiment of the present invention where the lines are thickened by transverse stretching. The left side shows the printed lines, and the right side shows the lines after transverse stretching.

[0019] In the figure: 1, micron ridge one; 21, substrate one; 22-substrate two; 3, printed steel needle; 4, nano ridge; 5, micron ridge two; 7, plastic conical needle; 8, polymer solution; 9, steel needle. DETAILED DESCRIPTION

[0020] The present invention will now be further described in detail with reference to the accompanying drawings and embodiments. These drawings are simplified schematic diagrams that only illustrate the basic structure of the present invention in a schematic manner, and therefore only show the components related to the present invention.

[0021] It should be noted that if there are directional indications (such as up, down, bottom, top, etc.) involved in the embodiments of the present invention, the directional indication is only used to explain the relative position relationship, movement, etc. between the components in a certain specific posture. If the specific posture changes, the directional indication will also change accordingly. The terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Unless otherwise clearly specified and defined, the terms "set", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected, or indirectly connected through an intermediate medium, or it can be the internal connection of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0022] like Figure 1-Figure 5 As shown, a method for manufacturing a micro-nano spray needle based on a stretched material comprises the following steps: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution 8 into a micro-nano spray needle convex mold; The method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, print photoresist on substrate 1 21 to obtain line 1, and obtain substrate 1 21 with nano ridge 4 by stretching method. Specifically, line 1 includes micron ridge 1. The stretching method adopts a heating stretching method, including: heating substrate 1 21 printed with line 1, and then stretching the heated substrate 1 21, driving line 1 to stretch, until line 1 on substrate 1 21 is stretched into nano ridge 4. Further, the heating temperature of substrate 1 21 is 110~130℃, the stretching force is 5~30N, the stretching time is 8~15s, and the nano ridge 4 is a nano ridge below 100nm. But not limited to this, in other embodiments, the stretching method includes: substrate 1 21 is at room temperature, the stretching force is 2~50N, the stretching time is 2~10s, and the nano ridge 4 is a nano ridge below 100nm. Furthermore, in the present invention, by selecting different stretching materials as the preparation materials of the substrate 21, the heating stretching method or the normal temperature stretching method in the stretching method is correspondingly adopted. The stretching materials include: thermoplastics (stretchable by heating, such as PMMA, PET, etc.), characteristics: softening after heating, plastic stretching (irreversible deformation), and shaping after cooling. Alternatively, the stretching materials include: elastomers (elastic stretchable at room temperature, such as PDMS, rubber, TPE / TPU, etc.); characteristics: reversible stretching (elastic deformation) at room temperature, strong resilience. Alternatively, the stretching materials include: flexible thermoplastics (plastic stretchable at room temperature, such as LDPE cling film, PVC sealing film, PC film, etc.); characteristics: ductile and stretchable at room temperature, but irreversible plastic deformation (no rebound). Furthermore, the photoresist itself has a certain viscosity; the adhesion strength of the substrate is increased by subjecting the substrate 21 to oxygen plasma treatment, thereby increasing the bonding strength between the substrate and the printing material; the surface tension mainly affects the width of the line, for example, the spread shape or the three-dimensional cylindrical shape; so for the actual experiment itself, the photoresist can form a nano-ridge 4 under the stretching method. The parameter requirements of the photoresist of the line 1 in the present invention include: the viscosity range includes 5~5000cP; the surface tension range includes: 20~45mN / m.

[0023] Then, a photoresist is printed on the substrate 1 21 with the nano ridge 4 to obtain line 2. Specifically, line 2 includes micron ridge 2 5 connected to line 1, and an outer contour pattern arranged around the periphery of the micron ridge 1 1 and micron ridge 2 5; a substrate 1 21 with micro-nano ridges is obtained. More specifically, micron ridge 2 5 includes micron ridges with a width of 30-50 μm and 70-100 μm printed after the nano ridge 4.

[0024] Then, the substrate 21 with micro-nano ridges is cured to obtain a micro-nano needle convex mold. Specifically, curing the hard film includes the following steps: placing the substrate 21 with micro-nano ridges on a horizontal hot plate for pre-baking, photolithography, and hardening to obtain a micro-nano needle convex mold. Further, in the curing hard film, the pre-baking time is 15-30 minutes, the pre-baking temperature is 60-100°C, the photolithography time is 5-10 minutes, the hardening time of placing on the hot plate for hardening is 15-30 minutes, and the hardening temperature is 60-100°C. Hardening can improve the adhesion of the photoresist to the substrate 21.

[0025] Step 1a2, pouring a polymer solution 8 into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; comprising the following steps: Step 1a2.1, sealing and drying the micro-nano spray needle convex mold and performing a hydrophobic treatment. Specifically, in step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 1-5 ml of trimethylsiloxane (TMCS) atmosphere for sealing and drying, and the hydrophobic treatment time is 10-20 minutes.

[0026] Step 1a2.2, pouring the polymer solution 8 into the micro-nano spray needle convex mold.

[0027] Step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing. Specifically, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in a vacuum box, and the air pressure in the vacuum box is maintained below 10Pa for 1 to 2 hours to eliminate the bubbles in the polymer solution 8, and fill the micro-nano spray needle convex mold pattern, and then placed on a static table for 20 to 30 minutes; then the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing, the oven temperature is 60 to 80°C, and the baking time is 2 to 4 hours.

[0028] Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold cast with the polymer solution 8, trimming the shape, and obtaining the micro-nano spray needle bottom plate. Specifically, after the solidified micro-nano spray needle convex mold cast with the polymer solution 8 is cooled to room temperature, it is taken out for demoulding, and the shape is cut and trimmed with a coated tool to obtain the micro-nano spray needle bottom plate.

[0029] Step 1b, obtaining the micro-nano spray needle cover plate by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold.

[0030] The method for preparing the micro-nano spray needle cover plate mold comprises the following steps: Print photoresist on the cleaned substrate 22 by electrojet, then place it on a horizontal hot plate for heating for 15-30 minutes, control the temperature to 60-100°C, then photolithography for 5-10 minutes, place it on the hot plate for hardening for 15-30 minutes, and place it on the hot plate for hardening at 60-100°C to obtain a micro-nano spray needle cover plate mold. Hardening can improve the adhesion between the photoresist and the substrate 22.

[0031] The micro-nano spray needle cover plate is obtained by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold, comprising the following steps: The micro-nano spray needle cover plate mold is placed in a sealed drying tower with 1-5 ml trimethylsiloxane atmosphere for hydrophobic treatment for 10-20 minutes, and the prepared polymer solution 8 is poured on the micro-nano spray needle cover plate mold. Then, the micro-nano spray needle cover plate mold poured with the polymer solution 8 is placed in a vacuum box with an air pressure of less than 10 Pa for 1-2 hours to remove bubbles in the polymer solution 8 in the micro-nano spray needle cover plate mold, and the polymer solution 8 fills the pouring cavity of the micro-nano spray needle cover plate mold; then, it is placed on a static table for 20-30 minutes; then, it is placed in an oven for curing at an oven temperature of 60-80°C and a baking time of 2-4 hours; then, after cooling to room temperature, it is taken out for demolding, and the shape is corrected with a coated tool to obtain a micro-nano spray needle cover plate.

[0032] Step 2, align and bond the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle. Specifically, the steps include: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate were treated with oxygen plasma respectively, with a treatment power of 15-25W and a treatment time of 20-30s; The processed micro-nano spray needle bottom plate is aligned and bonded with the micro-nano spray needle cover plate to seal the micro-nano channel on the micro-nano spray needle bottom plate.

[0033] More specifically, the substrate 1 21 and / or the substrate 2 22 is made of one of PMMA film, PET film, PVP film, sealing film, PDMS film, PC film, PP film, PE film, PVC film, PS film, SERS film, and hydrogel film.

[0034] More specifically, the photoresist used for printing line one and / or line two is BN photoresist.

[0035] More specifically, the photoresist used to print line one and / or line two can be replaced by one of PDMS, PEO, hydrogel, liquid metal, rubber, and graphene.

[0036] The biggest feature of the present invention is its strong tolerance and flexibility; as long as the base material has strong plasticity and can be stretched infinitely, the target scale pattern can be obtained. However, since the base will break when stretched to the limit, the size also depends on the choice of the base. In the present invention, most of the printing is at the submicron level, which is convenient and quick to obtain nanoscale lines. Embodiment 1

[0037] like Figure 1-Figure 5 As shown, a method for manufacturing a micro-nano spray needle based on a stretched material comprises the following steps: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution 8 into a micro-nano spray needle convex mold; The method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, print photoresist on substrate 1 21 to obtain line 1, and obtain substrate 1 21 with nano ridges 4 by stretching method. Print photoresist on substrate 1 21 with nano ridges 4 to obtain line 2. Curing the substrate 1 21 with micro-nano ridges to obtain a micro-nano needle convex mold.

[0038] Specifically, the substrate 1 21 is a PMMA substrate. Before printing the photoresist on the PMMA substrate to obtain line 1, the substrate 1 21 is first ultrasonically cleaned in deionized water for 15 minutes, wherein the ultrasonic power is 70W; in this embodiment, the deionized water is anhydrous ethanol; finally, the substrate 1 21 is blown dry with a nitrogen air gun, and the substrate 1 21 is placed on a hot plate at 80°C to dry, and excess moisture on the surface of the substrate 1 21 is removed. And placed on a hot plate at 80°C to dry, remove moisture. When printing the photoresist to obtain line 1, the cleaned PMMA substrate is placed on the printing table, and the printing steel needle 3 of the printing mechanism is used to print line 1 on the PMMA substrate. Line 1 includes micron ridges 1, and the arrangement structure of the micron ridges 1 is a 1-2um array of micron ridges 1 of BN photoresist.

[0039] Specifically, in the step of obtaining a substrate 21 with nano ridges 4 by a stretching method, the stretching method specifically includes: placing the substrate 21 printed with lines 1 on a stretching instrument, heating the heating pad to 110°C, and placing the heated heating pad under the substrate 21 (i.e., PMMA substrate) printed with lines 1 (i.e., BN photoresist micron ridges), heating the substrate 21 printed with lines 1, the heating temperature of the substrate 21 is 110°C, and then using a stretching instrument to stretch the heated substrate 21, thereby driving the lines 1 to stretch, the stretching force is 5N, the stretching time is 8s, until the lines 1 on the substrate 21 are stretched into nano ridges 4. Further, the nano ridges 4 are nano ridges below 100nm.

[0040] Specifically, line 2 includes a micron ridge 2 5 connected to line 1, and an outer contour pattern arranged around the micron ridge 1 1 and the micron ridge 2 5; a substrate 21 with micro-nano ridges is obtained. Among them, the micron ridge 2 5 includes micron ridges with a printing width of 30μm, 70μm, and 30μm after the nano ridge 4. Further, in this embodiment, an electrojet printing method is used to print a 30μm BN photoresist micron ridge on the basis of the array nano ridge; the printing parameters are a voltage of 1500V and a working distance of 450μm. The electrojet printing method is used to print a 70μm BN photoresist micron ridge on the basis of a 30μm BN photoresist micron ridge; the printing parameters of the 70μm BN photoresist micron ridge are a voltage of 2100V and a working distance of 600μm. The electrojet printing method is used to print a 30μm BN photoresist micron ridge on the basis of a 70μm BN photoresist micron ridge. The parameters are a voltage of 1500V and a working distance of 450μm. The printing method of the outer contour graphic includes: using a plastic conical needle 7 to print the outer contour graphic on a clean substrate 21, and the printing parameters of the outer contour graphic include: a printing voltage of 2000V, a moving speed of 50mm / min, and a printing working distance of 300μm.

[0041] Specifically, curing the hard film includes the following steps: placing the substrate 21 with micro-nano ridges on a horizontal hot plate for pre-baking, the pre-baking time during the curing hard film is 15 minutes, and the pre-baking temperature is 60°C; then photolithography, the photolithography time is 5 minutes; then placing it on the hot plate for hardening, the hardening time is 15 minutes, and the hardening temperature is 60°C. The hardening can improve the adhesion between the photoresist and the substrate 21; then obtaining the micro-nano spray needle convex mold.

[0042] Step 1a2, pouring a polymer solution 8 into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; comprising the following steps: Step 1a2.1, sealing and drying the micro-nano spray needle convex mold and performing a hydrophobic treatment. Specifically, in step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 1 ml of trimethylsiloxane (TMCS) atmosphere for sealing and drying, and the hydrophobic treatment time is 10 minutes.

[0043] Step 1a2.2, pouring the polymer solution 8 into the micro-nano spray needle convex mold. Specifically, the preparation method of the polymer solution 8 is: mixing the PDMS base material and the curing agent in a ratio of 4:1, stirring for 5 minutes to mix evenly, and then placing in a vacuum box to degas and remove bubbles, and the obtained polymer solution 8 is a PDMS mixed solution.

[0044] Step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing. Specifically, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is first placed in a vacuum box, and the air pressure in the vacuum box is maintained below 10Pa for 1 hour to eliminate the polymer solution 8. In this embodiment, the bubbles in the PDMS mixed solution are eliminated, and the micro-nano spray needle convex mold pattern is filled, and then placed on a static table for 20 minutes; then the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing, and the oven temperature is 60°C and the baking time is 2 hours.

[0045] Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold cast with the polymer solution 8, trimming the shape, and obtaining the micro-nano spray needle bottom plate. Specifically, after the solidified micro-nano spray needle convex mold cast with the polymer solution 8 is cooled to room temperature, it is taken out for demoulding, and the shape is cut and trimmed with a coated tool to obtain the micro-nano spray needle bottom plate.

[0046] Step 1b, obtaining the micro-nano spray needle cover plate by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold.

[0047] The method for preparing the micro-nano spray needle cover plate mold comprises the following steps: Obtain substrate 22. In this embodiment, substrate 22 is a PMMA substrate. Substrate 22 is placed in anhydrous ethanol for ultrasonic cleaning for 30 minutes, wherein the ultrasonic power is 100W; then ultrasonic cleaning is performed in deionized water for 30 minutes, wherein the ultrasonic power is 100W; finally, it is blown dry with a nitrogen air gun and placed on a hot plate at 80°C for drying to remove excess water on substrate 22. The cleaned substrate 22 is placed on a printing table, and photoresist is printed on substrate 22 by electrojet. During printing, a plastic conical needle 7 is used to print a BN photoresist micro-nano spray needle cover plate mold. The printing parameters are a voltage of 2000V, a printing moving speed of 50mm / min, and a printing working distance of 300μm. Then, substrate 22 printed with BN photoresist is placed on a horizontal hot plate for heating for 15 minutes, and the heating temperature is 60°C, and then photolithography is performed for 5 minutes, and the film is placed on the hot plate for 15 minutes at a temperature of 60°C to obtain a micro-nano spray needle cover plate mold. The hard film can improve the adhesion between the photoresist and the substrate 22.

[0048] The micro-nano spray needle cover plate is obtained by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold, comprising the following steps: Place 1 ml of trimethylsiloxane in a sealed drying tower for evaporation for 5 minutes, then vertically place the micro-nano spray needle cover plate mold in a sealed drying tower with trimethylsiloxane atmosphere for atmosphere treatment for 10 minutes, pour the configured polymer solution 8 on the micro-nano spray needle cover plate mold, and then place the micro-nano spray needle cover plate mold poured with the polymer solution 8 in a vacuum box with an air pressure below 10 Pa for 1 to 2 hours to remove bubbles from the polymer solution 8 in the micro-nano spray needle cover plate mold and fill the pouring cavity of the micro-nano spray needle cover plate mold with the polymer solution 8; then place it on a static table for 20 minutes; then place it in an oven for curing at an oven temperature of 60°C and a baking time of 2 hours; then cool to room temperature, take it out for demolding, and use a coated tool to correct the shape to obtain a micro-nano spray needle cover plate.

[0049] Step 2, align and bond the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle. Specifically, the steps include: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate were treated with oxygen plasma respectively, with a treatment power of 15 W and a treatment time of 20 s; The processed micro-nano spray needle bottom plate is aligned and bonded with the micro-nano spray needle cover plate to seal the micro-nano channel on the micro-nano spray needle bottom plate. Embodiment 2

[0050] like Figure 1-Figure 5 As shown, a method for manufacturing a micro-nano spray needle based on a stretched material comprises the following steps: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution 8 into a micro-nano spray needle convex mold; The method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, print photoresist on substrate 1 21 to obtain line 1, and obtain substrate 1 21 with nano ridges 4 by stretching method. Print photoresist on substrate 1 21 with nano ridges 4 to obtain line 2. Curing the substrate 1 21 with micro-nano ridges to obtain a micro-nano needle convex mold.

[0051] Specifically, the substrate 1 21 is a PMMA substrate. Before printing photoresist on the PMMA substrate to obtain line 1, the substrate 1 21 is first ultrasonically cleaned in deionized water for 30 minutes, wherein the ultrasonic power is 120W; in this embodiment, the deionized water is anhydrous ethanol; finally, the substrate 1 21 is blown dry with a nitrogen air gun, and the substrate 1 21 is placed on a hot plate at 80-100°C to dry, removing excess moisture on the surface of the substrate 1 21. When printing photoresist to obtain line 1, the cleaned PMMA substrate is placed on a printing table, and the printing steel needle 3 of the printing mechanism is used to print line 1 on the PMMA substrate. Line 1 includes micron ridges 1, and the arrangement structure of micron ridges 1 is a 2um array of micron ridges 1 of BN photoresist.

[0052] Specifically, in the step of obtaining a substrate 21 with nano ridges 4 by a stretching method, the stretching method specifically includes: placing the substrate 21 printed with lines 1 on a stretching instrument, heating the heating pad to 130°C, and placing the heated heating pad under the substrate 21 (i.e., PMMA substrate) printed with lines 1 (i.e., BN photoresist micron ridges), heating the substrate 21 printed with lines 1, the heating temperature of the substrate 21 is 130°C, and then using a stretching instrument to stretch the heated substrate 21, thereby driving the lines 1 to stretch, the stretching force is 30N, the stretching time is 15s, until the lines 1 on the substrate 21 are stretched into nano ridges 4. Further, the nano ridges 4 are nano ridges below 100nm.

[0053] Specifically, line two includes a micron ridge 2 5 connected to line one, and an outer contour pattern arranged around the micron ridge 1 1 and the micron ridge 2 5; a substrate 21 with micro-nano ridges is obtained. Among them, the micron ridge 2 5 includes micron ridges with a printing width of 50μm, 100μm, and 50μm after the nano ridge 4. Further, in this embodiment, an electrojet printing method is used to print a 50μm BN photoresist micron ridge on the basis of the array nano ridge; the printing parameters are a voltage of 2500V and a working distance of 700μm. The electrojet printing method is used to print a 100μm BN photoresist micron ridge on the basis of a 50μm BN photoresist micron ridge; the printing parameters of the 100μm BN photoresist micron ridge are a voltage of 2600V and a working distance of 900μm. The electrojet printing method is used to print a 50μm BN photoresist micron ridge on the basis of a 100μm BN photoresist micron ridge. The parameters are voltage 2500V, working distance 700μm. The printing method of the outer contour pattern includes: using a plastic conical needle 7 to print the outer contour pattern on a clean substrate 21, and the printing parameters of the outer contour pattern include: printing voltage 2500V, moving speed 100mm / min, and printing working distance 500μm.

[0054] Specifically, curing the hard film includes the following steps: placing the substrate 21 with micro-nano ridges on a horizontal hot plate for pre-baking, the pre-baking time in the curing hard film is 30 minutes, and the pre-baking temperature is 100°C; then photolithography, the photolithography time is 10 minutes; then placing it on the hot plate for hardening, the hardening time is 30 minutes, and the hardening temperature is 100°C. Hardening can improve the adhesion between the photoresist and the substrate 21; then obtaining a micro-nano spray needle convex mold.

[0055] Step 1a2, pouring a polymer solution 8 into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; comprising the following steps: Step 1a2.1, sealing and drying the micro-nano spray needle convex mold and performing a hydrophobic treatment. Specifically, in step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 5 ml of trimethylsiloxane (TMCS) atmosphere for sealing and drying, and the hydrophobic treatment time is 20 minutes.

[0056] Step 1a2.2, pouring the polymer solution 8 into the micro-nano spray needle convex mold. Specifically, the preparation method of the polymer solution 8 is: mixing the PDMS base material and the curing agent in a ratio of 4:1 to 8:1, stirring for 5 to 10 minutes to mix evenly, and then placing in a vacuum box to degas and remove bubbles, and the obtained polymer solution 8 is a PDMS mixed solution.

[0057] Step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing. Specifically, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is first placed in a vacuum box, and the air pressure in the vacuum box is maintained below 10Pa for 2 hours to eliminate the polymer solution 8. In this embodiment, the bubbles in the PDMS mixed solution are eliminated, and the micro-nano spray needle convex mold pattern is filled, and then placed on a static table for 30 minutes; then the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing, and the oven temperature is 80°C and the baking time is 4 hours.

[0058] Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold cast with the polymer solution 8, trimming the shape, and obtaining the micro-nano spray needle bottom plate. Specifically, after the solidified micro-nano spray needle convex mold cast with the polymer solution 8 is cooled to room temperature, it is taken out for demoulding, and the shape is cut and trimmed with a coated tool to obtain the micro-nano spray needle bottom plate.

[0059] Step 1b, obtaining the micro-nano spray needle cover plate by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold.

[0060] The method for preparing the micro-nano spray needle cover plate mold comprises the following steps: Obtain substrate 22. In this embodiment, substrate 22 is a PMMA substrate. Substrate 22 is placed in anhydrous ethanol for ultrasonic cleaning for 30 minutes, wherein the ultrasonic power is 100W; then ultrasonic cleaning is performed in deionized water for 30 minutes, wherein the ultrasonic power is 100W; finally, it is blown dry with a nitrogen air gun and placed on a hot plate at 100°C for drying to remove excess moisture on substrate 22. The cleaned substrate 22 is placed on a printing table, and photoresist is printed on substrate 22 by electrojet. During printing, a plastic conical needle 7 is used to print a BN photoresist micro-nano spray needle cover plate mold. The printing parameters are a voltage of 2500V, a printing moving speed of 100mm / min, and a printing working distance of 500μm. Then, substrate 22 printed with BN photoresist is placed on a horizontal hot plate for heating for 30 minutes, the heating temperature is 100°C, and then photolithography is performed for 10 minutes, and the substrate is placed on a hot plate for hardening for 30 minutes at a temperature of 100°C to obtain a micro-nano spray needle cover plate mold. The hard film can improve the adhesion between the photoresist and the substrate 22.

[0061] The micro-nano spray needle cover plate is obtained by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold, comprising the following steps: Place 5 ml of trimethylsiloxane in a sealed drying tower for evaporation for 10 minutes, then vertically place the micro-nano spray needle cover plate mold in a sealed drying tower with trimethylsiloxane atmosphere for atmosphere treatment for 20 minutes, pour the configured polymer solution 8 on the micro-nano spray needle cover plate mold, and then place the micro-nano spray needle cover plate mold poured with the polymer solution 8 in a vacuum box with an air pressure below 10 Pa for 2 hours to remove bubbles in the polymer solution 8 in the micro-nano spray needle cover plate mold, and the polymer solution 8 fills the pouring cavity of the micro-nano spray needle cover plate mold; then place it on a static table for 30 minutes; then place it in an oven for curing, the oven temperature is 80°C, and the baking time is 4 hours; then cool to room temperature, take it out for demolding, and use a coated tool to correct the shape to obtain a micro-nano spray needle cover plate.

[0062] Step 2, align and bond the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle. Specifically, the steps include: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate were treated with oxygen plasma respectively, with a treatment power of 25 W and a treatment time of 30 s; The processed micro-nano spray needle bottom plate is aligned and bonded with the micro-nano spray needle cover plate to seal the micro-nano channel on the micro-nano spray needle bottom plate. Embodiment 3

[0063] like Figure 1-Figure 5 As shown, a method for manufacturing a micro-nano spray needle based on a stretched material comprises the following steps: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution 8 into a micro-nano spray needle convex mold; Among them, Figure 1 , Figure 2 As shown, the method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, print photoresist on substrate 1 21 to obtain line 1, and obtain substrate 1 21 with nano ridges 4 by stretching method. Print photoresist on substrate 1 21 with nano ridges 4 to obtain line 2. Curing the substrate 1 21 with micro-nano ridges to obtain a micro-nano needle convex mold.

[0064] Specifically, the substrate 1 21 is a PMMA substrate. Before printing the photoresist on the PMMA substrate to obtain line 1, the substrate 1 21 is first ultrasonically cleaned in deionized water for 22 minutes, wherein the ultrasonic power is 95W; in this embodiment, the deionized water used is anhydrous ethanol; finally, the substrate 1 21 is blown dry with a nitrogen air gun, and the substrate 1 21 is placed on a hot plate at 90°C to dry to remove excess moisture on the surface of the substrate 1 21. When printing the photoresist to obtain line 1, the cleaned PMMA substrate is placed on the printing table, and the printing steel needle 3 of the printing mechanism is used to print line 1 on the PMMA substrate (such as Figure 1 In 1a), line 1 includes micron ridge 1, and the arrangement structure of micron ridge 1 is micron ridge 1 of array BN photoresist of 1-2um. In this embodiment, it is micron ridge 1 of array BN photoresist of 1.5um.

[0065] Among them, Fig. 9 The picture shows that after printing line 1 (micrometer line), the printed line 1 is gradually stretched by heating and stretching to form a micrometer ridge 1. The first one in the direction of the arrows is the original image, the second one is stretched by 50%, the third one is stretched by 100%, and the fourth one is stretched by 150%. The size of the fourth one is about 1um, and the unclear local area is about submicron. Because, a single nanometer-level single line cannot be photographed under a microscope unless it is an array. Figure 6 , Figure 7 The optical microscope image of the micro-nano spray needle convex mold is shown; Figure 6 yes Figure 7 An enlarged schematic diagram of the end. In addition, Fig.10 It is a display. Horizontal stretching makes the lines thicker. The left side shows the printed lines, and the right side shows the lines after horizontal stretching.

[0066] Specifically, in the step of obtaining a substrate 21 with nano ridges 4 by a stretching method, the stretching method specifically includes: placing the substrate 21 printed with lines 1 on a stretching instrument, heating the heating pad to 120°C, and placing the heated heating pad under the substrate 21 (i.e., PMMA substrate) printed with lines 1 (i.e., BN photoresist micron ridges), heating the substrate 21 printed with lines 1, the heating temperature of the substrate 21 is 120°C, and then using a stretching instrument to stretch the heated substrate 21, thereby driving the lines 1 to stretch, the stretching force is 17N, the stretching time is 12s, until the lines 1 on the substrate 21 are stretched into nano ridges 4. Further, the nano ridges 4 are nano ridges below 100nm (such as Figure 1 1b in Figure 1).

[0067] Specifically, line 2 includes micron ridge 2 5 connected to line 1, and an outer contour pattern arranged around the micron ridge 1 1 and micron ridge 2 5; a substrate 1 21 with micro-nano ridges is obtained. Among them, micron ridge 2 5 includes a 40μm (such as 40μm) printed in sequence after the nano ridge 4. Figure 1 1c), 85μm (such as Figure 1 1d), 40μm (such as Figure 1 1e in the figure). Further, in this embodiment, an electrojet printing method is used to print 40μm BN photoresist micro-ridges on the basis of the array nano-ridges; the printing parameters are a voltage of 2000V and a working distance of 600μm. An electrojet printing method is used to print 85μm BN photoresist micro-ridges on the basis of 40μm BN photoresist micro-ridges; the printing parameters of the 85μm BN photoresist micro-ridges are a voltage of 2400V and a working distance of 750μm. An electrojet printing method is used to print 40μm BN photoresist micro-ridges on the basis of 85μm BN photoresist micro-ridges. The parameters are a voltage of 2000V and a working distance of 600μm. The method for printing an outer contour graphic comprises: using a plastic conical needle 7 to print an outer contour graphic (such as Figure 1 As shown in 1f in the figure, the printing parameters of the outer contour graphics include: printing voltage of 2000V, moving speed of 75mm / min, and printing working distance of 400μm.

[0068] Specifically, curing the hard film includes the following steps: placing the substrate 21 with micro-nano ridges on a horizontal hot plate for pre-baking, the pre-baking time in the curing hard film is 22 minutes, and the pre-baking temperature is 80°C; then photolithography, the photolithography time is 7.5 minutes; then placing it on a hot plate for hardening, the hardening time is 22 minutes, and the hardening temperature is 80°C. Hardening can improve the adhesion between the photoresist and the substrate 21; then obtaining a micro-nano spray needle convex mold.

[0069] Step 1a2, pouring a polymer solution 8 into the micro-nano spray needle convex mold to obtain a micro-nano spray needle bottom plate; comprising the following steps: Step 1a2.1, sealing and drying the micro-nano spray needle convex mold and performing a hydrophobic treatment. Specifically, in step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 3 ml of trimethylsiloxane (TMCS) atmosphere for sealing and drying, and the hydrophobic treatment time is 15 minutes.

[0070] Step 1a2.2, pouring the polymer solution 8 into the micro-nano spray needle convex mold. Specifically, the preparation method of the polymer solution 8 is: mixing the PDMS base material and the curing agent in a ratio of 6:1, stirring for 7.5 minutes to mix evenly, and then placing in a vacuum box for degassing to remove bubbles, and the obtained polymer solution 8 is a PDMS mixed solution.

[0071] Step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing (eg Figure 2 2a in the figure). Specifically, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution 8 is first placed in a vacuum box, and the air pressure in the vacuum box is maintained below 10Pa for 1.5 hours to eliminate the polymer solution 8. In this embodiment, the bubbles in the PDMS mixed solution are eliminated, and the micro-nano spray needle convex mold pattern is filled, and then placed on a static table for 25 minutes; then the micro-nano spray needle convex mold poured with the polymer solution 8 is placed in an oven for curing, and the oven temperature is 70°C and the baking time is 3 hours.

[0072] Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold with the polymer solution 8 cast therein, trimming the shape, and obtaining a micro-nano spray needle bottom plate. Specifically, after the solidified micro-nano spray needle convex mold with the polymer solution 8 cast therein is cooled to room temperature, it is taken out for demoulding, and the shape is trimmed by cutting with a coated tool to obtain a micro-nano spray needle bottom plate (such as Figure 2 2b).

[0073] Step 1b, obtaining the micro-nano spray needle cover plate by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold.

[0074] The method for preparing the micro-nano spray needle cover plate mold comprises the following steps: Obtain substrate 22. In this embodiment, substrate 22 is a PMMA substrate. Place substrate 22 in anhydrous ethanol for ultrasonic cleaning for 30 minutes, wherein the ultrasonic power is 100 W; then place substrate 22 in deionized water for ultrasonic cleaning for 30 minutes, wherein the ultrasonic power is 100 W; finally, blow dry with a nitrogen air gun, and place on a hot plate at 90°C for drying to remove excess moisture on substrate 22. Place the cleaned substrate 22 on a printing table, and print photoresist on substrate 22 by electrojet. During printing, use a plastic conical needle 7 to print a BN photoresist micro-nano spray needle cover plate mold. The printing parameters are a voltage of 2000 V, a printing moving speed of 75 mm / min, and a printing working distance of 400 μm. Then place substrate 22 printed with BN photoresist on a horizontal hot plate and heat for 22 minutes at a heating temperature of 80°C, then perform photolithography for 7.5 minutes, place on a hot plate to harden the film for 22 minutes at a temperature of 80°C, and obtain a micro-nano spray needle cover plate mold (such as Figure 3 3a). The hard film can improve the adhesion between the photoresist and the substrate 22.

[0075] The micro-nano spray needle cover plate is obtained by pouring the polymer solution 8 into the micro-nano spray needle cover plate mold, comprising the following steps: Place 3 ml of trimethylsiloxane in a sealed drying tower for evaporation for 7.5 min, then vertically place the micro-nano spray needle cover plate mold in a sealed drying tower with trimethylsiloxane atmosphere for atmosphere treatment for 15 min, pour the prepared polymer solution 8 on the micro-nano spray needle cover plate mold, and then place the micro-nano spray needle cover plate mold poured with the polymer solution 8 in a vacuum box with an air pressure of less than 10 Pa for 1.5 h to remove the bubbles in the polymer solution 8 in the micro-nano spray needle cover plate mold, and the polymer solution 8 fills the casting cavity of the micro-nano spray needle cover plate mold (such as Figure 4 4a in the figure); then placed on a static table for 25 minutes; then placed in an oven for curing, the oven temperature is 70°C, and the baking time is 3 hours; then after cooling to room temperature, taken out for demoulding, and the shape is corrected with a coated tool to obtain a micro-nano spray needle cover plate (such as Figure 4 4b).

[0076] Step 2, align and bond the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle. Specifically, the steps include: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate are treated with oxygen plasma (such as Figure 5 5a), the processing power is 20W and the processing time is 25s; Align and bond the treated micro-nano spray needle base plate to the micro-nano spray needle cover plate (such as Figure 5 5b), sealing the micro-nano channel on the bottom plate of the micro-nano nozzle. Embodiment 4

[0077] Based on the first embodiment, the viscosity range of the photoresist for printing the first line, the second line and the outer contour pattern includes 5 cP; the surface tension range includes: 20 mN / m. Embodiment 5

[0078] Based on the second embodiment, the viscosity range of the photoresist for printing the first line, the second line and the outer contour pattern includes 5000 cP; the surface tension range includes: 45 mN / m. Embodiment 6

[0079] Based on the third embodiment, the viscosity range of the photoresist for printing the first line, the second line and the outer contour pattern includes 2500 cP; the surface tension range includes: 40 mN / m. Embodiment 7

[0080] Based on the third embodiment, the viscosity range of the photoresist for printing the first line, the second line and the outer contour pattern includes 300 cP; the surface tension range includes: 25 mN / m. Embodiment 8

[0081] Based on the third embodiment, the viscosity range of the photoresist for printing the first line, the second line and the outer contour pattern includes 400 cP; the surface tension range includes: 30 mN / m. Embodiment 9

[0082] On the basis of Example 1, in step 2, a 50 μm steel needle 9 after hydrophilic treatment is inserted into the microchannel of the micro-nano channel formed by the bonded micro-nano spray needle base plate and the micro-nano spray needle cover plate, and an interference fit is performed (such as Figure 5 5c) to obtain a micro-nano spray needle. Embodiment 10

[0083] On the basis of Example 2, in step 2, a 60 μm steel needle 9 after hydrophilic treatment is inserted into the microchannel of the micro-nano channel formed by the bonded micro-nano spray needle base plate and the micro-nano spray needle cover plate, and an interference fit is performed to obtain a micro-nano spray needle. Embodiment 11

[0084] On the basis of Example 3, in step 2, a 55 μm steel needle 9 after hydrophilic treatment is inserted into the microchannel of the micro-nano channel formed by the bonded micro-nano spray needle base plate and the micro-nano spray needle cover plate, and an interference fit is performed to obtain a micro-nano spray needle. Embodiment 12

[0085] like Figure 1-Figure 5 As shown, a micro-nano spray needle is prepared by using a micro-nano spray needle manufacturing method based on stretched materials in Example 11. Embodiment 13

[0086] On the basis of the third embodiment, in step 1a1, a photoresist is printed on a substrate 21 to obtain line 1, and a substrate 21 with nano ridges 4 is obtained by a stretching method. A photoresist is printed on a substrate 21 with nano ridges 4 to obtain line 2. The substrate 21 with micro-nano ridges is cured to obtain a micro-nano needle convex mold.

[0087] Specifically, the substrate 1 21 is a PC substrate. Before printing the photoresist on the substrate 1 21 to obtain the line 1, the substrate 1 21 is first ultrasonically cleaned in deionized water for 22 minutes, wherein the ultrasonic power is 95W; and the substrate 1 21 is blown dry with a nitrogen air gun. When printing the photoresist to obtain the line 1, the cleaned substrate 1 21 is placed on the printing table, and the printing steel needle 3 of the printing mechanism is used to print the line 1 on the substrate 1 21. The line 1 includes a micron ridge 1, and the arrangement structure of the micron ridge 1 is a micron ridge 1 of an array BN photoresist of 1 to 2 um. In this embodiment, the micron ridge 1 of the array BN photoresist is 1.5 um.

[0088] The stretching method adopts a room temperature stretching method, including: the substrate 21 is at room temperature, the stretching force is 2N, the stretching time is 2s, and the nano ridge 4 is a nano ridge below 100nm. Embodiment 14

[0089] On the basis of the thirteenth embodiment, the stretching method adopts the room temperature stretching method, including: the substrate 21 is at room temperature, the stretching force is 50N, the stretching time is 10s, and the nano ridge 4 is a nano ridge below 100nm. Embodiment 15

[0090] On the basis of the thirteenth embodiment, the stretching method adopts the room temperature stretching method, including: the substrate 21 is at room temperature, the stretching force is 25N, the stretching time is 6s, and the nano ridge 4 is a nano ridge below 100nm.

[0091] Working principle: The present invention provides a micro-nano spray needle manufacturing method and a spray needle based on a stretchable material. The micro-nano spray needle base is obtained by adopting an electrojet printing and stretching method as well as a casting method, and the spray needle micro-nano channel is sealed by oxygen plasma to obtain a complete micro-nano spray needle. By utilizing the stretchability of thermoplastic materials, the production cost of the micro-nano spray needle is reduced, and the process is simple and easy to implement.

[0092] The present invention adopts two processes of stretching and printing to directly obtain the micro-nano spray needle convex mold; finally, the micro-nano spray needle is obtained by casting and replicating the micro-nano spray needle convex mold pattern, and bonding is performed.

[0093] The present invention obtains a micron pattern by printing any material with high ductility onto a thermoplastic or flexible substrate, and obtains a nano pattern by stretching and shrinking the micron pattern; and then uses printing technology to punch out the needle outline to complete the manufacture of the micro-nano needle convex mold.

[0094] The invention has simple steps, environmentally friendly process, low cost, high efficiency, no dangerous experimental links, and low requirements on experimental equipment and experimental environment, and belongs to a flexible and simple micro-nano manufacturing technology.

[0095] Although the present invention is based on a manufacturing method of thermoplastic materials, if the lines are printed on a flexible substrate, the high elasticity of the flexible substrate can still be relied upon to shrink the micron lines to nano lines, with high selectivity and flexible controllability.

[0096] The above specific implementation methods are specific support for the scheme ideas proposed in the present invention, and cannot be used to limit the protection scope of the present invention. Any equivalent changes or equivalent modifications made on the basis of this technical scheme in accordance with the technical ideas proposed in the present invention still fall within the scope of protection of the technical scheme of the present invention.

Claims

1. A method for manufacturing a micro-nano spray needle based on a stretched material, characterized in that: The following steps are involved: Step 1, obtaining a micro-nano spray needle base plate and a micro-nano spray needle cover plate; Step 1a, obtaining a micro-nano spray needle base plate by pouring a polymer solution into a micro-nano spray needle convex mold; The method for preparing the micro-nano spray needle convex mold comprises the following steps: Step 1a1, printing photoresist on substrate 1 to obtain line 1, obtaining substrate 1 with nano ridges by stretching method, and printing photoresist on substrate 1 with nano ridges to obtain line 2, obtaining substrate 1 with micro-nano ridges, and curing substrate 1 with micro-nano ridges to obtain a micro-nano needle convex mold; Step 1a2, pouring a polymer solution into the micro-nano spray needle convex mold to obtain a micro-nano spray needle base plate; Step 1b, obtaining a micro-nano spray needle cover plate by pouring a polymer solution into a micro-nano spray needle cover plate mold; Step 2, aligning and bonding the micro-nano spray needle base plate and the micro-nano spray needle cover plate to obtain the micro-nano spray needle.

2. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 1, characterized in that: The line one includes a micron ridge one; The line 2 includes a micron ridge 2 connected to the line 1, and an outer contour pattern arranged around the periphery of the micron ridge 1 and the micron ridge 2; The photoresist used for printing line one and / or line two is positive photoresist or negative photoresist.

3. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 2, characterized in that: In step 1a1, the stretching method comprises: The substrate 1 on which the line 1 is printed is heated, and then the heated substrate 1 is stretched to drive the line 1 to stretch, until the line 1 on the substrate 1 is stretched into a nano ridge; In step 1a1, curing the hard film comprises the following steps: The substrate with the micro-nano ridges is placed on a horizontal hot plate for pre-baking, photolithography, and hardening to obtain a micro-nano needle convex mold.

4. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 3, characterized in that: The method of pouring a polymer solution into a micro-nano spray needle convex mold to obtain a micro-nano spray needle base plate comprises the following steps: Step 1a2.1, sealing, drying and hydrophobicizing the micro-nano spray needle convex mold; Step 1a2.2, pouring the polymer solution into the micro-nano spray needle convex mold; Step 1a2.3, placing the micro-nano spray needle convex mold poured with the polymer solution in an oven for curing; Step 1a2.4, demoulding the solidified micro-nano spray needle convex mold cast with the polymer solution, trimming the shape, and obtaining the micro-nano spray needle base plate.

5. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 4, characterized in that: In step 1a2.1, the micro-nano spray needle convex mold is placed in a sealed drying tower with 1-5 ml trimethylsiloxane atmosphere for sealed drying, and the hydrophobic treatment time is 10-20 minutes; And / or, in step 1a2.2, the polymer solution is prepared by mixing the PDMS base material and the curing agent in a ratio of 4:1 to 8:1, stirring for 5 minutes to mix them evenly, and then placing them in a vacuum box to degas and remove bubbles, and the obtained polymer solution is a PDMS mixed solution; And / or, in step 1a2.3, the micro-nano spray needle convex mold poured with the polymer solution is placed in a vacuum box, the air pressure in the vacuum box is maintained below 10Pa, for 1 to 2 hours, the bubbles in the polymer solution are eliminated, and the micro-nano spray needle convex mold pattern is filled, and then placed on a static table for 20 to 30 minutes; then the micro-nano spray needle convex mold poured with the polymer solution is placed in an oven for curing, the oven temperature is 60 to 80°C, and the baking time is 2 to 4 hours; then the cured micro-nano spray needle convex mold poured with the polymer solution is cooled to room temperature, taken out for demoulding, and the coated tool is used to cut and trim the shape to obtain a micro-nano spray needle base plate.

6. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 5, characterized in that: The preparation method of the micro-nano spray needle cover plate mold comprises the following steps: Print photoresist on the cleaned substrate 2 by electrojet, then place it on a horizontal hot plate and heat it for 15-30 minutes, control the temperature at 60-100°C, then photolithograph for 5-10 minutes, place it on the hot plate to harden the film for 15-30 minutes, and the temperature is 60-100°C to obtain a micro-nano spray needle cover plate mold.

7. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 6, characterized in that: The process of pouring a polymer solution into a micro-nano spray needle cover plate mold to obtain a micro-nano spray needle cover plate comprises the following steps: The micro-nano spray needle cover plate mold is placed in a sealed drying tower with 1-5 ml trimethylsiloxane atmosphere for hydrophobic treatment for 10-20 minutes, and the prepared polymer solution is poured on the micro-nano spray needle cover plate mold. Then, the micro-nano spray needle cover plate mold poured with the polymer solution is placed in a vacuum box with an air pressure of less than 10 Pa for 1-2 hours to remove bubbles from the polymer solution in the micro-nano spray needle cover plate mold and fill the pouring cavity of the micro-nano spray needle cover plate mold with the polymer solution; then, it is placed on a static table for 20-30 minutes; then, it is placed in an oven for curing at an oven temperature of 60-80°C and a baking time of 2-4 hours; then, after cooling to room temperature, it is taken out for demoulding, and the shape is corrected with a coated tool to obtain a micro-nano spray needle cover plate.

8. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 7, characterized in that: In step 2, the micro-nano spray needle base plate and the micro-nano spray needle cover plate are aligned and bonded to obtain the micro-nano spray needle, which includes the following steps: The micro-nano spray needle bottom plate and the micro-nano spray needle cover plate were treated with oxygen plasma respectively, with a treatment power of 15-25W and a treatment time of 20-30s; The processed micro-nano spray needle bottom plate is aligned and bonded with the micro-nano spray needle cover plate to seal the micro-nano channel on the micro-nano spray needle bottom plate.

9. The method for manufacturing a micro-nano spray needle based on a stretched material according to claim 8, characterized in that: The micron ridge 2 includes printing micron ridges with widths of 30-50 μm and 70-100 μm after the nano ridges; And / or, in step 1a1, the pre-baking time in the curing hardening film is 15-30 minutes, the pre-baking temperature is 60-100° C., the photolithography time is 5-10 minutes, the hardening time of placing the film on a hot plate is 15-30 minutes, and the hardening temperature is 60-100° C.; and / or, in step 1a1, the substrate is heated to a temperature of 110-130° C., the stretching force is 5-30 N, the stretching time is 8-15 s, and the nano-ridges are nano-ridges of less than 100 nm; And / or, in step 1a1, the substrate 1 is stretched at room temperature with a tensile force of 2 to 50 N, a stretching time of 2 to 10 s, and the nano-ridges are nano-ridges of less than 100 nm; And / or, in step 1a1, during the stretching process, the relative direction of the stretching can be adjusted according to the actual required nano-ridge size requirements; wherein the force trajectories between the relative directions of several stretchings can adopt mutually intersecting force trajectories to adjust the nano-ridge size; And / or, the substrate one and / or the substrate two is one of PMMA film, PET film, PVP film, sealing film, PDMS film, PC film, PP film, PE film, PVC film, PS film, SERS film, and hydrogel film; And / or, the photoresist used for printing line one and / or line two is BN photoresist; And / or, the photoresist used for printing line 1 and / or line 2 can be replaced by one of PDMS, PEO, hydrogel, liquid metal, rubber, and graphene; And / or, in step 2, inserting the steel needle into the microchannel of the micro-nano channel formed by the bonded micro-nano spray needle base plate and the micro-nano spray needle cover plate, performing interference fit, and obtaining the micro-nano spray needle; And / or, the parameter requirements of the photoresist of line one include: a viscosity range of 5 to 5000 cP; a surface tension range of 20 to 45 mN / m.

10. A micro-nano spray needle, characterized in that: The micro-nano spray needle is prepared by using the micro-nano spray needle manufacturing method based on stretched materials as described in any one of claims 1 to 9.

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