A printing device for printing micro-patterns, methods of use and uses

Abstract

This invention relates to a printing apparatus, method of use, and application for printing micro-patterns. The printing apparatus for printing micro-patterns includes at least one writing unit, which comprises a liquid storage slit unit and at least one liquid dispensing guide device. The liquid storage slit unit includes a first side structure having a first side surface and a second side surface structure having a second side surface, the first and second sides being arranged opposite each other to form a liquid storage slit. The liquid dispensing guide device has at least two flexible dispensing beams, each flexible beam including a thicker end and a sharper end. When there is liquid to be printed between corresponding flexible dispensing beams, the corresponding sharpers can approach each other. The printing apparatus can achieve stable liquid supply, stable writing, high precision, adaptability to different writing directions, low risk of clogging, and easy cleaning and / or replacement; it can achieve high-throughput micro-pattern writing.

Description

Technical Field

[0001] This invention belongs to the field of functional material patterning printing technology, specifically relating to a printing apparatus, method of use, and application for printing micro-patterns. Background Technology

[0002] High-throughput micropatterning technology is a manufacturing technology that integrates the characteristics of "high throughput" and "micropatterning". Its core lies in achieving large-area processing on the substrate surface through large-scale processes in multiple regions or batches to prepare micron or nanoscale patterned structures with specific geometric shapes and arrangement rules. The micropatterned structures can endow materials with unique physical, chemical and optical properties.

[0003] In existing technologies, solution-based high-throughput micropatterning methods mainly fall into two categories: one is direct micropattern writing (such as inkjet printing and electrohydraulic jet printing); the other is template-assisted micropatterning techniques (such as photolithography, contact printing, and solution shearing). For direct micropattern writing methods, nozzle clogging and discontinuous solution transport during the micropatterning process limit their wider application, especially in scenarios requiring high-throughput manufacturing. For template-assisted micropatterning techniques, large-area, uniform films need to be prepared in advance; however, this process is difficult to control the film edges, thus limiting high-throughput manufacturing.

[0004] Therefore, there is an urgent need in this field to develop an apparatus and method for producing printed micropatterns that combines precise fluid control with high-throughput fabrication of micropatterned surfaces. Summary of the Invention

[0005] To address the shortcomings of existing technologies, one objective of this invention is to provide a printing apparatus for printing micro-patterns, the printing apparatus comprising at least one writing unit, the writing unit comprising a liquid storage slit unit and at least one liquid dispensing guide device;

[0006] The liquid storage slit unit includes a first side structure having a first side surface and a second side surface structure having a second side surface. The first side surface and the second side surface are arranged opposite to each other and have an adjustable distance for forming a liquid storage slit; the distance is 0.1mm to 4mm.

[0007] The liquid dispensing guide device has at least two liquid dispensing flexible beams, each comprising a thick end and a pointed end; the distance between the liquid storage slits is set such that the thick end is fixed within the liquid storage slit; the pointed end extends out of the liquid storage slit, and when there is liquid to be printed between the corresponding liquid dispensing flexible beams, the corresponding pointed ends can approach each other.

[0008] The printing apparatus provided in this application has a liquid storage slit with a distance of 0.1mm to 4mm for storing the liquid to be printed. The liquid to be printed can be stably present in the liquid storage slit under capillary action. When the liquid outlet guiding device contacts the printing substrate, the liquid is guided to the printing substrate. The liquid storage slit stably supplies liquid to the liquid outlet guiding device for dispensing, improving writing stability. Especially when writing micron- or nano-scale patterns, it can stably supply liquid without blocking or leaking, and the writing accuracy is high. This may be because the liquid storage slit can hold the liquid to be printed by capillary action, and only the liquid outlet guiding device guides the liquid to be printed to flow out. At the same time, the contact state between the liquid outlet guiding device and the substrate controls the dispensing speed to obtain the expected pattern.

[0009] On the other hand, the printing apparatus provided in this application has a two-stage liquid holding configuration. The first stage of liquid holding is a liquid storage slit, and the second stage of liquid holding is a liquid storage space formed by multiple liquid outlet flexible beams with their tips close together. The liquid storage slit can stably store liquid, and the liquid outlet flexible beams are used to guide the liquid to be printed from the liquid storage slit. Since the thick ends of the liquid outlet flexible beams of different liquid outlet guiding devices are fixed in the liquid storage slit, that is, they have similar liquid outlet starting points, it is possible to control multiple sets of liquid outlet guiding devices to simultaneously dispense liquid, thereby achieving high-throughput writing of micro-patterns.

[0010] On the other hand, this application relies mainly on capillary action rather than gravity to hold and guide the flow of printing liquid. Therefore, this application can be adapted to different printing directions. In particular, when the printing substrate is above the printing device, the printing device provided by this application can still print and write stably.

[0011] On the other hand, the liquid storage slit of the printing device provided in this application is an open space, which reduces the risk of clogging and is easy to clean and / or replace.

[0012] This application does not specifically limit the included angle between the first side and the second side, as long as the distance between them is 0.1~4mm. That is, any included angle between 0° and 180° is acceptable. 0° means the first and second sides are parallel, and 180° means the first and second sides are coplanar. When the angle between the first and second sides is not 0°, the liquid to be printed is usually located in a relatively small area. The liquid storage slit between the first and second sides can be wider at the top and narrower at the bottom, or narrower at the top and wider at the bottom.

[0013] Preferably, the included angle between the first side and the second side is 0° to 45°, such as 1°, 5°, 10°, 15°, 23°, 27°, 32°, 37°, 43°, etc.

[0014] Setting the angle between the first and second sides within the range of 0° to 45° allows for more liquid to be stably stored in the slit, increasing the writing volume, especially for printing devices without a continuous liquid supply system, which can increase the number of words written in a single stroke.

[0015] Preferably, the liquid storage slit has an upper opening that communicates with the environment, and more preferably, the upper part of the liquid storage slit is completely in communication with the environment.

[0016] Preferably, the liquid storage slit has a side opening that communicates with the environment, more preferably two opposite side openings, and even more preferably the sides of the liquid storage slit are completely in communication with the environment.

[0017] The connection between the liquid storage slit and the environment can simplify the factors affecting the liquid holding performance of the liquid storage slit, that is, reduce the influence of factors such as atmospheric pressure and edge adsorption force.

[0018] This application does not specify a particular height for the liquid storage slit; the height of the liquid storage slit can be selected as long as it can stably hold the liquid, matching different included angles. Typically, the height of the liquid storage slit is 10mm to 80mm, such as 12mm, 15mm, 18mm, 24mm, 28mm, 34mm, 45mm, 58mm, 67mm, 75mm, etc.

[0019] Preferably, the first and second sides have a hydrophilic relationship with the solution to be printed, and the contact angle of the solution to be printed on both the first and second sides is ≤65°.

[0020] A contact angle of less than 65° allows the writing liquid to be more stably held in the reservoir slit through capillary action.

[0021] Preferably, the materials of the first side and / or the second side are each independently selected from any one or a combination of at least two of glass, metal, polymer materials, ferroelectric composite materials, and ceramic materials.

[0022] The liquid outlet flexible beam is used to export the liquid in the liquid storage slit for writing. Any slender structure that can export the liquid to be printed from the liquid storage slit can be used in this application.

[0023] Preferably, the liquid-discharging flexible beam is either an inverted cone structure or an inverted pyramid structure, with the thick end being the base of the cone and the tip being the apex of the cone.

[0024] Preferably, the length of the liquid outlet flexible beam is 1mm to 30mm, such as 2mm, 5mm, 8mm, 13mm, 17mm, 19mm, 22mm, 26mm, 28mm, etc.

[0025] This application does not specifically limit the cone base size of the liquid outlet flexible beam, as long as it can be placed in the liquid storage slit. Preferably, the cone base size of the liquid outlet flexible beam is less than 1.1 times the minimum distance of the liquid storage slit. The liquid outlet flexible beam can be fixed in the liquid outlet slit by methods known or new in the art, typically but not limitingly including adhesive fixing to the first side or the second side.

[0026] Preferably, the diameter of the cone base is 100μm to 500μm, such as 105μm, 114μm, 148μm, 186μm, 225μm, 247μm, 256μm, 275μm, 297μm, 325μm, 353μm, 378μm, 386μm, 415μm, 432μm, 447μm, 468μm, 485μm, 498μm, etc.

[0027] Preferably, the number of liquid discharge flexible beams in each of the liquid discharge guiding devices is independently selected from 2 to 10, preferably 3.

[0028] Preferably, the horizontal spacing between the thicker ends of different flexible beams of the same liquid discharge guiding device is ≤100μm.

[0029] Setting the number of liquid outlet flexible beams to 2 to 10 and the horizontal spacing between the thick ends of different liquid outlet flexible beams ≤ 100 μm can improve the stability of the second-stage liquid holding.

[0030] Preferably, the arrangement direction of the different flexible beams of the same liquid dispensing guide device is perpendicular to the printing path of the printing device. This design will further improve the stability of the second-stage liquid holding.

[0031] Preferably, the arrangement of the thicker ends of the different liquid discharge flexible beams of the same liquid discharge guiding device includes any one or a combination of at least two of the following: horizontal arrangement, concave arrangement, convex arrangement, and wavy arrangement.

[0032] Preferably, the material of the liquid-discharging flexible beam is any one or a combination of at least two of the following: polymer, animal hair, wood fiber, metal and its compounds, glass fiber, carbon fiber, and silica fiber.

[0033] Preferably, the polymer comprises any one or a combination of at least two of nylon, polybutylene terephthalate (PBT), and polydimethylsiloxane (PDMS).

[0034] Preferably, the animal hair includes any one or a combination of at least two of the following: sheep hair, wolf hair, purple hair, and rabbit hair.

[0035] Preferably, the metal and its compound fibers include any one or a combination of at least two of silver, copper, iron, iron(II,III) oxide, AlNiCo, ironChromiumCo, and aluminum dioxide.

[0036] Preferably, the printing apparatus includes two or more writing units, with the liquid guiding devices of different writing units located on different writing paths. Multiple writing units can increase the writing throughput of the printing apparatus and enable the simultaneous writing of multiple patterns.

[0037] Optionally, the printing device includes two or more writing units, with different writing units arranged side by side, and liquid guiding devices for different writing units disposed in the same liquid storage slit. The first side structure of the writing units arranged side by side is integrated, and / or the second side structure of the writing units arranged side by side is integrated.

[0038] In this configuration, the liquid dispensing guide devices of different writing units are set in the same liquid storage slit, meaning that the first side of different writing units is designed as an integral part, the second side of different writing units is designed as an integral part, forming an integrally designed liquid storage slit. The liquid dispensing guide devices of different writing units are arranged side by side in the liquid storage slit, and the liquid dispensing flexible beams of the same writing unit are arranged close to each other. The liquid dispensing flexible beams of different writing units have a distance greater than the spacing between the liquid dispensing flexible beams of the same writing unit.

[0039] Optionally, the printing device includes two or more writing units, with different writing units arranged alternately, and the liquid dispensing guide devices of different writing units located in different liquid storage slits and arranged alternately along the writing path; adjacent writing units preferably share a side structure, the side structure being defined as a shared side structure, one side of the shared side structure being the second side structure of a writing unit, and the other side of the shared side structure being the first side structure of an adjacent writing unit.

[0040] In this configuration, the liquid dispensing guides of different writing units are arranged in an alternating manner, meaning that the liquid dispensing guides of different writing units are located on different writing paths. The alternating arrangement can further reduce the spacing between the writing paths of different writing units, enabling writing at a lower resolution.

[0041] Optionally, the printing device includes three or more writing units, the different writing units being arranged side by side and / or staggered, and the liquid dispensing guide devices of any two writing units having different writing paths.

[0042] Preferably, the first side and the second side are arranged opposite each other and have an adjustable distance, which is achieved by rotating a screw, by a snap-fit, or by a limiting device.

[0043] The distance between the first and second sides is fixed by a known or novel fixing method in the art, and this application does not specifically limit this method. When screws, clips, or the like are used to fix the first and second sides, the distance between the first and second sides can be adjusted as needed to improve the adaptability of the printing device to different liquids to be printed.

[0044] The second objective of this application is to provide a printing system for printing micro-patterns, comprising:

[0045] The platform is used to place the substrate to be printed.

[0046] The moving device has three-dimensional freedom of movement (XYZ) and can move along the printing path on a surface parallel to the printing substrate.

[0047] One of the objectives is that the printing apparatus is configured to be connected to the moving device and move along the printing path.

[0048] During the operation of the printing system provided in this application, the substrate to be printed is placed on the platform, and the moving device is used to adjust the starting position of the printing device in the XY plane and the height of the Z axis, that is, to adjust the starting point of the writing unit on the substrate to be printed, and the degree of contact between the liquid outlet flexible beam and the substrate to be written.

[0049] Preferably, the printing system further includes a liquid supply device for supplying the liquid to be printed to the liquid storage slit, comprising:

[0050] Solution storage unit for storing the liquid to be printed; and,

[0051] The solution delivery unit includes a delivery pipeline connecting the solution storage unit and the liquid storage slit, and a delivery power unit.

[0052] Exemplary power devices for liquid delivery may be liquid injectors, peristaltic pumps, or other known or new power devices for liquid delivery in the art.

[0053] This application does not specifically limit the liquid supply device; any device capable of stably transmitting a small amount of liquid to the liquid storage slit can be used in this application. This application does not specifically limit the transmission speed of the liquid to be printed; those skilled in the art can select one according to printing needs.

[0054] Preferably, when the printing device moves to print, the distance between the liquid dispensing flexible beam and the substrate to be printed is 0mm to 1mm. 0mm means that the liquid dispensing flexible beam is in direct contact with the substrate to be printed, and greater than 0mm means that the liquid dispensing flexible beam has a distance of a certain size from the substrate to be printed. This distance ensures that the printing solution is written on the substrate. Under normal circumstances, the liquid dispensing flexible beam needs to be in direct contact with the substrate to be printed. The elevation angle of the liquid dispensing flexible beam is, for example, selected from any angle ≤90°.

[0055] The third objective of this application is to provide a printing method for printing micro-patterns, using the printing apparatus for printing micro-patterns described in the first objective or the printing system for printing micro-patterns described in the second objective, comprising the following steps:

[0056] S1 Prepares the liquid to be printed;

[0057] S2 Prepare the substrate to be printed, preferably by placing the substrate to be printed on the platform;

[0058] S3 injects the liquid to be printed into the liquid storage slit, the liquid to be printed is stored in the liquid storage slit and wets the liquid outlet flexible beam, the tips of the liquid outlet flexible beams of the same liquid outlet guiding device are brought close together, and a liquid outlet guiding device capable of writing is obtained.

[0059] S4 adjusts the distance between the liquid outlet flexible beam and the substrate to be printed, so that the tip of the liquid outlet flexible beam contacts the substrate to be printed, and moves the printing device according to the printing path to obtain a micro pattern; preferably, the moving device is adjusted so that the tip of the liquid outlet flexible beam contacts the substrate to be printed, the moving device is started, and the printing device is moved according to the printing path to obtain a micro pattern.

[0060] Preferably, the moving speed of the "driving the printing device to move along the printing path" is ≤100mm / s, preferably 0.5~50mm / s, such as 0.6mm / s, 0.9mm / s, 1.6mm / s, 3.5mm / s, 7.5mm / s, 8.8mm / s, 10.3mm / s, 12.2mm / s, 14.6mm / s, 25.0mm / s, 26.8mm / s, 28.6mm / s, 34.7mm / s, 42.8mm / s, 48.5mm / s, etc.

[0061] Preferably, the printing substrate includes a rigid substrate and / or a flexible substrate.

[0062] Preferably, the printing substrate includes any one or a combination of at least two of the following: glass substrate, polyethylene terephthalate (PET) substrate, polycarbonate (PC) substrate, polyethylene (PE) substrate, silicon substrate, and paper substrate;

[0063] Preferably, the liquid to be printed has a hydrophilic relationship with the first side and / or the second side, and the contact angle of the solution to be printed on both the first side and the second side is ≤65°.

[0064] Preferably, the dispersant of the liquid to be printed includes any one or a combination of at least two of the following: water, alcohol solvents, alkane solvents, benzene solvents, and ester solvents.

[0065] Preferably, the dispersion of the liquid to be printed includes any one or a combination of at least two of quantum dots, nanoparticles, nanowires, nanosheets, polymer molecules, inks, and dyes.

[0066] The dyes include, for example, any one or a combination of at least two of Rhodamine B, fluorescein, and calcein.

[0067] The fourth objective of this application is to provide the use of the printing method for printing micropatterns as described in the third objective, for preparing any one or at least a combination of two of the following: quantum dot light-emitting diode pixel arrays, thin-film transistor circuit patterns, microfluidic chip microchannel structures, or biosensor micropattern films.

[0068] The fifth objective of this application is to provide a micro-pattern obtained by the printing method for printing micro-patterns described in the third objective.

[0069] The micropatterns obtained by this application can have smaller line width resolutions, while patterns with larger line width resolutions can also be achieved. For example, the line width resolutions of the micropatterns in this application are 1 mm, 500 μm, 200 μm, 50 μm, and can even reach below 10 μm or below 5 μm; the printing area can be printed according to requirements without an upper limit, and can be 1 mm for example. 2 100mm 2 500mm 2 800mm 2 1cm 2 10cm 2 50cm 2 100cm 2 300cm 2 600cm 2 1000cm 2 The printing throughput is defined as the printing area divided by the printing line width resolution. The micro-pattern printing throughput obtained in this application is ≥1. Since there is no upper limit to the printing area, the printing throughput of the micro-patterns provided in this application can be printed according to the needs of those skilled in the art. For example, it can be 8000cm, 5000cm, 3000cm, 1000cm, 800cm, 500cm, 300cm, 100cm, 50cm, etc.

[0070] Compared with the prior art, this application has the following beneficial effects:

[0071] (1) The printing device provided in this application can achieve stable liquid supply for printing, stable writing, high precision, and can adapt to different writing directions, especially adaptable to printing on inverted (substrate above the printing device) substrates.

[0072] (2) The printing apparatus provided in this application has a low risk of clogging and is easy to clean and / or replace;

[0073] (3) The printing method provided in this application can achieve high-throughput micro-patterned writing. Attached Figure Description

[0074] Figure 1 A front view structural schematic diagram of a printing apparatus for printing micro-patterns provided for example device 1;

[0075] Figure 2 A side view of the printing apparatus for printing micro-patterns provided for example device 1;

[0076] Figure 3 Different structural options for the liquid outlet flexible beam 210;

[0077] Figure 4 A schematic diagram showing the first side 111 and the second side 121 at different included angles;

[0078] Figure 5 A schematic diagram of the arrangement of the thick ends of different liquid discharge flexible beams 210 of the same liquid discharge guiding device 200;

[0079] Figure 6 A front view structural schematic diagram of a printing apparatus for printing micro-patterns provided for device example 2;

[0080] Figure 7 A schematic diagram of the operation of the printing apparatus for printing micro-patterns provided for example device 2;

[0081] Figure 8 A front view structural schematic diagram of a printing apparatus for printing micro-patterns provided for device example 3;

[0082] Figure 9 A side view of the printing apparatus for printing micro-patterns provided for device example 3;

[0083] Figure 10 A schematic diagram of the operation of the printing apparatus for printing micro-patterns provided for example 3;

[0084] Figure 11 A schematic diagram of the printing system for printing micro-patterns provided for device example 4;

[0085] Figure 12 The large-area Rhodamine B micron-scale linear array pattern obtained in Example 1;

[0086] Figure 13 The pattern of cadmium-based red quantum dot (CdSe / ZnS) micron-line array obtained in Example 2;

[0087] Figure 14 The three sets of cadmium-based red quantum dot micron array patterns were simultaneously printed as shown in Example 3. Detailed Implementation

[0088] The technical solution of the present invention will be further explained and described below with reference to specific embodiments. However, it should be noted that the specific embodiments are only a specific implementation and explanation of the essence of the technical solution of the present invention, and should not be construed as a limitation on the scope of protection of the present invention.

[0089] The reagents and instruments used in the examples are all commercially available, and the detection methods are conventional methods well known in the art.

[0090] Equipment Example 1

[0091] like Figures 1-2 ( Figure 1 A front view structural schematic diagram of a printing apparatus for printing micro-patterns provided for example device 1; Figure 2 As shown in the side view of the printing apparatus for printing micro-patterns provided in Example 1, Example 1 provides a printing apparatus for printing micro-patterns, including a writing unit 10.

[0092] The writing unit 10 includes a liquid storage slit unit 100 and a liquid outlet guiding device 200;

[0093] The liquid storage slit unit 100 includes a first side structure 110 with a first side 111 and a second side structure 120 with a second side 121. The first side 111 and the second side 121 are arranged parallel to each other (with an included angle of 0°), fixed by screws 140, and spaced apart by a distance W to form a liquid storage slit 130. The distance W is any value between 0.1 mm and 4 mm. The height of the liquid storage slit 130 is 10 mm to 80 mm. The liquid storage slit 130 is fixed only by screws 140 and is open to the environment on all sides.

[0094] The liquid dispensing guide device 200 has three liquid dispensing flexible beams 210, each of which is an inverted conical structure, including a thicker end 211 and a sharper end 212. The distance W between the liquid storage slits 130 is set to fix the thicker end 211 within the liquid storage slit 130. The sharper end 212 extends out of the liquid storage slit 130, and when there is liquid 300 to be printed between the corresponding liquid dispensing flexible beams 210, the corresponding sharper ends 212 can approach each other. The length of the liquid dispensing flexible beam 210 is preferably 1mm to 30mm; the diameter of the cone base is preferably 100μm to 500μm.

[0095] The horizontal spacing between the thicker ends of the different liquid discharge flexible beams 210 of the same liquid discharge guiding device 200 is ≤100μm.

[0096] Figure 3 Different structural options for the fluid-ejecting flexible beam 210 are presented, all of which have a thick end 211 and a pointed end 212. From left to right, they are conical, triangular pyramidal, and square pyramidal structures.

[0097] The angle between the first side 111 and the second side 121 in the printing apparatus provided in Example 1 can also be any angle within the range of 0° to 45°, as long as the thick end 211 of the liquid outlet flexible beam 210 can be fixed. Figure 4 A schematic diagram showing the first side 111 and the second side 121 at different included angles is given.

[0098] The arrangement of the thicker ends of the different liquid discharge flexible beams 210 of the same liquid discharge guiding device 200 includes any one or a combination of at least two of the following: horizontal arrangement, concave arrangement, convex arrangement, and wavy arrangement. Figure 5 As shown, Figure 5 The diagram shows the arrangement of the thicker ends of the different liquid discharge flexible beams 210 of the same liquid discharge guiding device 200, which are arranged horizontally, convexly, concavely, and wavyly, respectively.

[0099] The printing device of Example 1 operates in a direction perpendicular to the arrangement direction of the liquid outlet flexible beam 210.

[0100] Equipment Example 2

[0101] like Figures 6-7 ( Figure 6 A front view structural schematic diagram of the printing apparatus for printing micro-patterns provided for Example 2. Figure 7 As shown in the schematic diagram of the operation of the printing apparatus for printing micro-patterns provided for Device Example 2, Device Example 2 provides a printing apparatus for printing micro-patterns, including three writing units arranged side by side, namely a first side-by-side writing unit 11, a second side-by-side writing unit 12, and a third side-by-side writing unit 13; and the first side-by-side writing unit 11, the second side-by-side writing unit 12, and the third side-by-side writing unit 13 all have the same structure as the writing unit 10 of Device Example 1; and each includes a liquid storage slit unit 100 and a liquid discharge guiding device 200;

[0102] The first side structure of the first parallel writing unit 11, the second parallel writing unit 12, and the third parallel writing unit 13 is designed as a single, relatively long plane, with the first side located on this plane; the second side structure of the first parallel writing unit 11, the second parallel writing unit 12, and the third parallel writing unit 13 is designed as another relatively long plane, with the second side located on this plane.

[0103] In device example 2, it is preferable that different writing units use the same solution to be printed and write the same substance.

[0104] In device example 2, a partition can be provided between the liquid storage spaces of adjacent writing units to maintain different printing solutions in different writing units for writing different substances.

[0105] In Device Example 2, the distance between adjacent liquid outlet flexible beams of adjacent writing units needs to be greater than the distance between adjacent liquid outlet flexible beams within the same writing unit. For example, the distance A between the rightmost liquid outlet flexible beam of the first parallel writing unit 11 and the leftmost liquid outlet flexible beam of the second parallel writing unit 12 will be greater than the distance B between liquid outlet flexible beams belonging to either the first parallel writing unit 11 or the second parallel writing unit 12. Therefore, when using Device Example 2 for micro-pattern printing, a larger distance will appear between different writing units compared to the same writing unit.

[0106] Equipment Example 3

[0107] like Figures 8-10 ( Figure 8 A front view structural schematic diagram of a printing apparatus for printing micro-patterns provided for device example 3; Figure 9 A side view of the printing apparatus for printing micro-patterns provided for device example 3; Figure 10 As shown in the schematic diagram of the operation of the printing apparatus for printing micro-patterns provided in Device Example 3, Device Example 3 provides a printing apparatus for printing micro-patterns, including three staggered writing units, namely a first staggered writing unit 14, a second staggered writing unit 15, and a third staggered writing unit 16; and the first staggered writing unit 14, the second staggered writing unit 15, and the third staggered writing unit 16 all have the same structure as the writing unit 10 of Device Example 1; and each includes a liquid storage slit unit 100 and a liquid discharge guiding device 200;

[0108] The liquid storage slit of the first staggered writing unit 14 is formed by the opposing surfaces of the first side plate 161 and the second side plate 162, the liquid storage slit of the second staggered writing unit 15 is formed by the opposing surfaces of the second side plate 162 and the third side plate 163, and the liquid storage slit of the third staggered writing unit 16 is formed by the opposing surfaces of the third side plate 163 and the fourth side plate 164.

[0109] In device example 3, different writing units can hold the same printing solution and write the same substance, or they can hold different printing solutions and write different substances.

[0110] In device example 3, adjacent writing units are located in different liquid storage slits, naturally having a greater distance than the liquid outlet flexible beams within the same writing unit, thus enabling the printing of micro-patterns with narrower spacing.

[0111] Equipment Example 4

[0112] like Figure 11 ( Figure 11 As shown in the schematic diagram of the printing system for printing micro-patterns provided in Example 4, Example 4 provides a printing system for printing micro-patterns, comprising:

[0113] Platform 20 is used to place the substrate 50 to be printed;

[0114] The moving device 30 has three-dimensional freedom of movement (XYZ) and can move along the printing path on a surface parallel to the printing substrate 50.

[0115] The printing apparatus 10 described in any one of Embodiments 1 to 3 is configured to be connected to the moving device 30 and move along the printing path;

[0116] The liquid supply device 40 is used to supply the liquid to be printed 300 to the liquid storage slit 130, and includes: a solution storage unit 41 for storing the liquid to be printed 300; and a solution delivery unit 42, including a delivery pipeline 421 connecting the solution storage unit 41 and the liquid storage slit 130, and a delivery power device (liquid injector) 422.

[0117] Example 1

[0118] A method for printing micro-patterns, using the printing apparatus provided in Example 1, includes the following steps:

[0119] S1 prepares a 1 mg / mL Rhodamine B aqueous solution as the printing liquid 300;

[0120] S2 Prepare the substrate to be printed (PET substrate) and place the substrate on the platform 20;

[0121] S3 injects the liquid to be printed 300 into the liquid storage slit 130. The liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 that can be used for writing. The first side structure 110 and the second side structure 120 are both glass plates. The distance W between the liquid storage slits 130 is 1 mm. The height of the liquid to be printed 300 held by the liquid storage slit 130 is 5 mm. The diameter of the thick end of the liquid outlet flexible beam 210 is 100 μm, the length is 3 mm, and the material is nylon. The glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first side and the second side is 13°.

[0122] S4 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed, and moves the printing device 10 at a speed of 20 mm / s along a predetermined path direction to obtain a Rhodamine B micron linear array pattern. The arrangement direction of the liquid outlet flexible beam 210 is perpendicular to the predetermined path.

[0123] Figure 12 This is the large-area rhodamine B micron-line array pattern obtained in Example 1. From... Figure 12 It can be seen that the Rhodamine B micron-line array has clear boundaries, consistent linewidth (approximately 150 μm), stable spacing between micron-line spacing, and a printing throughput of 907 cm⁻¹.

[0124] Comparative Example 1

[0125] The only difference from Example 1 is that the distance W of the liquid storage slit 130 is adjusted to 4.5 mm. In this case, the solution cannot be stored in the slit, and the continuous printing of micro-patterns cannot be achieved.

[0126] Example 2

[0127] A method for printing micro-patterns, using the printing apparatus provided in Example 1, includes the following steps:

[0128] S1 prepares an aqueous solution of cadmium-based red quantum dots (CdSe / ZnS) with a concentration of 0.5 nmol / ml as the printing liquid 300;

[0129] S2 Prepare the substrate (glass substrate) to be printed and place the printing substrate on the platform 20;

[0130] S3 injects the liquid to be printed 300 into the liquid storage slit 130, the liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 that can be used for writing. The first side structure 110 and the second side structure 120 are both glass plates. The width of the liquid storage slit 130 is 1.5 mm. The height of the liquid to be printed 300 held by the liquid storage slit 130 is 3 mm. The diameter of the thick end of the liquid outlet flexible beam 210 is 150 μm and the length is 4 mm. The material is PBT (polybutylene terephthalate). The glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first side and the second side is 10°.

[0131] S3 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed, and moves the printing device 10 at a speed of 10 mm / s along a predetermined path to obtain a red quantum dot micron-line array pattern. The arrangement direction of the liquid outlet flexible beam 210 is perpendicular to the predetermined path.

[0132] Figure 13 This is the micron-line array pattern of cadmium-based red quantum dots (CdSe / ZnS) obtained in Example 2. From... Figure 13 It can be seen that the printed quantum dot micrometer lines have clear boundaries, are evenly distributed, and have consistent widths, all around 35μm, with a printing throughput of 1248cm.

[0133] Example 3

[0134] A method for printing micro-patterns, using the printing apparatus provided in Example 2, includes the following steps:

[0135] S1 prepares an aqueous solution of cadmium-based red quantum dots (CdSe / ZnS) with a concentration of 2 nmol / ml, as the printing liquid 300;

[0136] S2 Prepare the substrate to be printed (PET substrate) and place the substrate on the platform 20;

[0137] S3 injects the liquid to be printed 300 into the first parallel writing unit 11, the second parallel writing unit 12, and the third parallel writing unit 13 respectively. The liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 that can be used for writing. The first side structure of the first parallel writing unit 11, the second parallel writing unit 12, and the third parallel writing unit 13 is integrated into a long plane, and the material is glass. The second side structure of the first parallel writing unit 11, the second parallel writing unit 12, and the third parallel writing unit 13 is integrated into another longer plane, and the material is glass plate; the width of the liquid storage slit 130 is 1mm; the height of the liquid to be printed 300 held by the liquid storage slit 130 is 4mm; the diameter of the thick end of the liquid outlet flexible beam 210 is 120μm, the length is 3.5mm, and the material is nylon; the glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first and second side surfaces is 10°.

[0138] S4 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed, and moves the printing device 10 at a speed of 10 mm / s along a predetermined path direction, while obtaining three sets of cadmium-based red quantum dot (CdSe / ZnS) micron-line array patterns.

[0139] Figure 14 The images show three sets of cadmium-based red quantum dot micron array patterns simultaneously printed, obtained in Example 3. From... Figure 14 It can be seen that the three sets of micron-line arrays are evenly and continuously distributed, with consistent micron-line widths (approximately 90 μm), which means that the same material can be printed stably at the same time, with a printing throughput of 1027 cm.

[0140] Example 4

[0141] A method for printing micro-patterns, using the printing apparatus provided in Example 3, includes the following steps:

[0142] S1 prepared cadmium-based red quantum dot aqueous solutions with concentrations of 1 nmol / ml, cadmium-based green quantum dot aqueous solutions with concentrations of 1 nmol / ml, and cadmium-based blue quantum dot aqueous solutions with concentrations of 3 nmol / ml (CdSe / ZnS), as the printing liquid 300;

[0143] S2 Prepare the substrate to be printed (PET substrate) and place the substrate on the platform 20;

[0144] S3 injects red quantum dot aqueous solution into the first interleaved writing unit 14, green quantum dot aqueous solution into the second interleaved writing unit 15, and blue quantum dot aqueous solution into the third interleaved writing unit 16 respectively; the liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 capable of writing; the first side plate 161, the second side plate 162, the third side plate 163, and the fourth side plate 164 are all glass plates; the width of the liquid storage slit 130 is 0.8 mm; the height of the liquid to be printed 300 held by the liquid storage slit 130 is 3 mm; the diameter of the thick end of the liquid outlet flexible beam 210 is 100 μm, the length is 2.5 mm, and the material is nylon; the glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first and second side plates is 10°.

[0145] S4 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed. The printing device 10 moves at a speed of 10 mm / s along a predetermined path direction to obtain a 5 cm × 5 cm red, green and blue quantum dot micron line array pattern with a micron line width of about 157 μm and a printing throughput of 1592. If a larger area is required, a solution delivery unit can be set up, and the liquid to be printed in the solution storage unit can be replenished and delivered to the liquid storage slit using a delivery pipeline to continue writing.

[0146] Example 5

[0147] A method for printing micro-patterns, using the printing apparatus provided in Example 1, includes the following steps:

[0148] S1 prepares a 1 mg / mL Rhodamine B aqueous solution as the printing liquid 300;

[0149] S2 Prepare the substrate to be printed (PET substrate) and place the substrate on the platform 20;

[0150] S3 injects the liquid to be printed 300 into the liquid storage slit 130. The liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 that can be used for writing. The first side structure 110 and the second side structure 120 are both glass plates. The distance W of the liquid storage slits 130 is 0.1 mm. The height of the liquid to be printed 300 held by the liquid storage slit 130 is 1 mm. The diameter of the thick end of the liquid outlet flexible beam 210 is 80 μm, the length is 2 mm, and the material is nylon. The glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first and second sides is 60°.

[0151] S4 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed, and moves the printing device 10 at a speed of 5 mm / s along a predetermined path direction to obtain a Rhodamine B micron linear array pattern. The arrangement direction of the liquid outlet flexible beam 210 is perpendicular to the predetermined path.

[0152] The micron-line array pattern of Rhodamine B has a uniform and continuous distribution of micron-line arrays, with a consistent micron-line width of approximately 55 μm and a printing throughput of 10 cm.

[0153] Example 6

[0154] A method for printing micro-patterns, using the printing apparatus provided in Example 1, includes the following steps:

[0155] S1 prepares a 1 mg / mL Rhodamine B aqueous solution as the printing liquid 300;

[0156] S2 Prepare the substrate to be printed (PET substrate) and place the substrate on the platform 20;

[0157] S3 injects the liquid to be printed 300 into the liquid storage slit 130. The liquid to be printed 300 is stored in the liquid storage slit 130 and wets the liquid outlet flexible beam 210. The tips of the liquid outlet flexible beams of the same liquid outlet guiding device 200 are brought close together to obtain a liquid outlet guiding device 200 that can be used for writing. The first side structure 110 and the second side structure 120 are both glass plates. The distance W between the liquid storage slits 130 is 4 mm. The height of the liquid to be printed 300 held by the liquid storage slit 130 is 1 mm. The diameter of the thick end of the liquid outlet flexible beam 210 is 150 μm, the length is 4 mm, and the material is nylon. The glass plate is hydrophilically treated so that the contact angle between the printing liquid 300 and the first side and the second side is 13°.

[0158] S4 adjusts the distance between the liquid outlet flexible beam 210 and the substrate 50 to be printed, so that the tip 212 of the liquid outlet flexible beam 210 contacts the substrate 50 to be printed, and moves the printing device 10 at a speed of 5 mm / s along a predetermined path direction to obtain a Rhodamine B micron linear array pattern. The arrangement direction of the liquid outlet flexible beam 210 is perpendicular to the predetermined path.

[0159] The micron-line array pattern of Rhodamine B has a uniform and continuous distribution of micron-line arrays, with a consistent micron-line width of approximately 138 μm and a printing throughput of 12 cm.

[0160] The micro-patterns printed in Examples 1-6 have uniform line widths due to the stable liquid supply from the liquid storage slits. The micro-patterns are almost free of burrs and defects and have uniform width.

[0161] It should be noted that, in the high-throughput printing method for micro-patterns provided in this embodiment of the invention, functional micron lines with different widths can be prepared by changing the distance between the liquid-ejecting flexible beam and the substrate and the moving speed of the writing tool; functional micron line arrays with different spacings can be obtained by changing the translation distance of the substrate and repeatedly brushing the lines; and micron lines and arrays with different functions can be obtained by changing the type of functional molecular ink.

[0162] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A printing apparatus for printing micro-patterns, characterized in that, The printing apparatus includes at least one writing unit, which includes a liquid storage slit unit and at least one liquid dispensing guide device. The liquid storage slit unit includes a first side structure having a first side surface and a second side surface structure having a second side surface. The first side surface and the second side surface are arranged opposite to each other and have an adjustable distance for forming a liquid storage slit; the distance is 0.1mm to 4mm. The liquid dispensing guide device has at least two liquid dispensing flexible beams, each comprising a thick end and a pointed end; the distance between the liquid storage slits is set such that the thick end is fixed within the liquid storage slit; the pointed end extends out of the liquid storage slit, and when there is liquid to be printed between the corresponding liquid dispensing flexible beams, the corresponding pointed ends can approach each other.

2. The printing apparatus as claimed in claim 1, characterized in that, The included angle between the first side and the second side is 0°~45°; Preferably, the liquid storage slit has an upper opening that communicates with the environment; more preferably, the upper part of the liquid storage slit is completely in communication with the environment. Preferably, the liquid storage slit has a side opening that communicates with the environment; more preferably, it has two opposing side openings; and even more preferably, the sides of the liquid storage slit are completely in communication with the environment. Preferably, the height of the liquid storage slit is 10mm to 80mm; Preferably, the first and second sides have a hydrophilic relationship with the solution to be printed, and the contact angle of the solution to be printed on both the first and second sides is ≤65°. Preferably, the materials of the first side and / or the second side are each independently selected from any one or a combination of at least two of glass, metal, polymer materials, ferroelectric composite materials, and ceramic materials.

3. The printing apparatus as described in claim 1 or 2, characterized in that, The liquid-discharging flexible beam can be either an inverted cone structure or an inverted pyramid structure, with the thick end being the base of the cone and the pointed end being the apex of the cone; Preferably, the length of the liquid outlet flexible beam is 1mm to 30mm; Preferably, the diameter of the cone base is 100μm~500μm; Preferably, the number of liquid discharge flexible beams in each of the liquid discharge guiding devices is independently selected from 2 to 10, preferably 3; Preferably, the horizontal spacing between the thicker ends of different flexible beams of the same liquid discharge guiding device is ≤100μm; Preferably, the arrangement direction of different liquid discharge flexible beams of the same liquid discharge guiding device is perpendicular to the printing path of the printing device; Preferably, the arrangement of the thicker ends of the different liquid discharge flexible beams of the same liquid discharge guiding device includes any one or a combination of at least two of the following: horizontal arrangement, concave arrangement, convex arrangement, and wavy arrangement. Preferably, the material of the liquid-discharging flexible beam is any one or a combination of at least two of the following: polymer, animal hair, wood fiber, metal and its compounds, glass fiber, carbon fiber, and silica fiber. Preferably, the polymer comprises any one or a combination of at least two of nylon, polybutylene terephthalate (PBT), and polydimethylsiloxane (PDMS); Preferably, the animal hair includes any one or a combination of at least two of the following: sheep hair, wolf hair, purple hair, and rabbit hair; Preferably, the metal and its compound fibers include any one or a combination of at least two of silver, copper, iron, iron(II,III) oxide, AlNiCo, ironChromiumCo, and aluminum dioxide.

4. The printing apparatus according to any one of claims 1 to 3, characterized in that, The printing device includes two or more writing units, and the liquid storage and guiding devices of different writing units are located on different writing paths; Optionally, the printing device includes two or more writing units, with different writing units arranged side by side, and liquid guiding devices for different writing units set in the same liquid storage slit. The first side structure of the side-by-side writing units is integrated, and / or the second side structure of the side-by-side writing units is integrated. Optionally, the printing device includes two or more writing units, with different writing units arranged alternately, and the liquid dispensing guide devices of different writing units located in different liquid storage slits and arranged alternately along the writing path; adjacent writing units preferably share a side structure, the side structure is defined as a shared side structure, one side of the shared side structure is the second side structure of a writing unit, and the other side of the shared side structure is the first side structure of an adjacent writing unit. Optionally, the printing device includes three or more writing units, the different writing units being arranged side by side and / or staggered, and the liquid dispensing guide devices of any two writing units having different writing paths.

5. The printing apparatus according to any one of claims 1 to 4, characterized in that, The first and second sides are arranged opposite each other and have an adjustable distance, which is achieved by rotating a screw, by a snap-fit, or by a limit switch.

6. A printing system for printing micro-patterns, characterized in that, The printing system includes: The platform is used to place the substrate to be printed. The moving device has three-dimensional freedom of movement (XYZ) and can move along the printing path on a surface parallel to the printing substrate. The printing apparatus according to any one of claims 1 to 5 is configured to be connected to the moving device and move along the printing path; Preferably, the printing system further includes a liquid supply device for supplying the liquid to be printed to the liquid storage slit, comprising: Solution storage unit for storing the liquid to be printed; and, The solution delivery unit includes a delivery pipeline connecting the solution storage unit and the liquid storage slit, and a delivery power unit; Preferably, when the printing device moves to print, the distance between the liquid outlet flexible beam and the substrate to be printed is 0mm~1mm.

7. A method for printing micro-patterns, characterized in that, The printing method uses the printing apparatus for printing micro-patterns as described in any one of claims 1 to 5 or the printing system for printing micro-patterns as described in claim 6, and includes the following steps: S1 Prepares the liquid to be printed; S2 Prepare the substrate to be printed, preferably by placing the substrate to be printed on the platform; S3 injects the liquid to be printed into the liquid storage slit, the liquid to be printed is stored in the liquid storage slit and wets the liquid outlet flexible beam, the tips of the liquid outlet flexible beams of the same liquid outlet guiding device are brought close together, and a liquid outlet guiding device capable of writing is obtained. S4 adjusts the distance between the liquid outlet flexible beam and the substrate to be printed, so that the tip of the liquid outlet flexible beam contacts the substrate to be printed, and moves the printing device according to the printing path to obtain a micro pattern; preferably, the moving device is adjusted so that the tip of the liquid outlet flexible beam contacts the substrate to be printed, the moving device is started, and the printing device is moved according to the printing path to obtain a micro pattern.

8. The printing method as described in claim 7, characterized in that, The moving speed of "driving the printing device to move along the printing path" is ≤100mm / s, preferably 0.5~50mm / s; Preferably, the printing substrate includes a rigid substrate and / or a flexible substrate; Preferably, the printing substrate includes any one or a combination of at least two of the following: glass substrate, polyethylene terephthalate (PET) substrate, polycarbonate (PC) substrate, polyethylene (PE) substrate, silicon substrate, and paper substrate; Preferably, the liquid to be printed has a hydrophilic relationship with the first side and / or the second side, and the contact angle of the solution to be printed on both the first side and the second side is ≤65°. Preferably, the dispersant of the liquid to be printed includes any one or a combination of at least two of the following: water, alcohol solvents, alkane solvents, benzene solvents, and ester solvents. Preferably, the dispersion of the liquid to be printed includes any one or a combination of at least two of quantum dots, nanoparticles, nanowires, nanosheets, polymer molecules, inks, and dyes.

9. Use of a printing method for printing micro-patterns as described in claim 7 or 8, characterized in that, The printing method is used to prepare any one or a combination of at least two of the following: quantum dot light-emitting diode pixel arrays, thin-film transistor circuit patterns, microfluidic chip microchannel structures, or biosensor micropatterned films.

10. A micropattern, characterized in that, The material of the micropattern is obtained by the printing method of the micropattern as described in claim 7 or 8.

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