Three-dimensional micro-nano structure printing system and method for preparing three-dimensional micro-nano structure

Abstract

The invention provides a three-dimensional micro-nano structure printing system and a method for preparing a three-dimensional micro-nano structure, the three-dimensional micro-nano structure printing system comprises a substrate and a mask integrated structure with a micro-nano pattern opening, and the mask integrated structure is placed on a rotary inclined table in a printing track control device; the inclination angle theta, the rotation azimuth angle psi and the site retention time t are adjusted through a printing track control device, so that the paths and the deposition volumes of the material steam reaching the surface of the substrate through different pattern opening positions of the mask are different, and atoms / molecules in the material steam form a complex three-dimensional micro-nano structure on the surface of the substrate; according to the method for preparing the three-dimensional micro-nano structure through the three-dimensional micro-nano structure printing system, all the advantages of mask photoetching are inherited, the diversity and superposition precision of the three-dimensional micro-nano structure are improved to a great extent, and then the complex three-dimensional micro-nano structure can be formed.

Description

Technical Field

[0001] This invention relates to the field of micro-nano patterning technology, and in particular to a three-dimensional micro-nano structure printing system and a method for preparing three-dimensional micro-nano structures. Background Technology

[0002] The development of micro / nano patterning technology has greatly promoted the fabrication of three-dimensional micro / nano structures applicable to fields such as electronics, optics, bioengineering, and sensing. Currently, the most advanced micro / nano patterning technologies can be divided into two main categories: one is based on photolithography, transferring patterns through masks or photoresists, including electron beam lithography, deep ultraviolet lithography, extreme ultraviolet lithography, scanning probe lithography, colloidal lithography, and nanoimprint lithography. The other is bottom-up molecular self-assembly forming micro / nano patterned structures. The latter utilizes the advantages of macromolecular assembly, including modular DNA epitaxy and well-aligned copolymer matrices. However, most existing micro / nano patterning processes still rely on photolithography, requiring multiple steps such as material deposition, etching, and solvent treatment to transfer the pattern to the substrate. This method generally suffers from high process complexity, lengthy processes, residual contamination, and solvent compatibility issues, hindering its further application.

[0003] To address this, researchers have explored direct material writing methods, including mask lithography, anodic aluminum oxide template lithography, transfer printing, and electrosol printing. Mask lithography, a shadow mask technique, integrates a mask with a substrate and places it above a vacuum evaporation source, allowing material to flow through patterned openings on the mask surface, thus forming a pattern on the substrate that matches the mask structure. While this technique can achieve lateral resolution below 50 nm and is suitable for simple structures, it struggles to fabricate complex patterns. Furthermore, in multi-material patterning, the stacking accuracy heavily relies on the mechanical alignment between different nanomasks, making control extremely challenging. Anodic aluminum oxide template lithography suffers from similar limitations. Transfer printing and electrosol printing, on the other hand, have stringent process environment requirements and a relatively limited range of usable materials.

[0004] Therefore, there is an urgent need for a three-dimensional micro / nano structure printing system and a method for preparing three-dimensional micro / nano structures to solve the above-mentioned technical problems. Summary of the Invention

[0005] The purpose of this invention is to provide a three-dimensional micro / nano structure printing system and a method for preparing three-dimensional micro / nano structures, in order to solve the technical problems of simple patterns and low stacking accuracy in the three-dimensional micro / nano structures prepared by existing mask lithography systems.

[0006] To address the aforementioned technical problems, this invention first provides a three-dimensional micro / nano structure printing system, including a vapor phase material source, a printing trajectory control device, a mask integrated structure, a control box, and a computer electrically connected to the control box. The printing trajectory control device has a rotating tilting stage for supporting the mask integrated structure. The mask integrated structure includes a substrate, a mask disposed opposite to the substrate, and a spacing adjustment device. The mask has multiple micro / nano pattern openings, and the spacing adjustment device is used to adjust the spacing between the substrate and the mask. The printing trajectory control device is used to adjust the tilt angle θ, rotation azimuth angle ψ, and site dwell time t, so that the material vapor generated by the gas phase material source is transmitted to the substrate surface through the micro-nano pattern opening and forms a three-dimensional micro-nano structure; the tilt angle θ is the angle between the horizontal plane where the rotating tilt stage is located and the normal direction of the gas phase material source, the rotation azimuth angle ψ is the self-rotation angle of the rotating tilt stage, and the site dwell time t is the dwell time of a single deposition site on the motion trajectory of the material vapor on the substrate surface.

[0007] Preferably, the vapor material source is selected from one or a combination of metals, organic materials, insulators, and semiconductors; the method for generating the vapor material source is selected from one or a combination of physical vapor deposition and chemical vapor deposition.

[0008] Specifically, this section clarifies that the vapor-phase material source can be selected from metals, organic materials, insulators, semiconductors, or a combination thereof. On the one hand, this broadens the range of applicable materials, allowing for flexible material selection based on the different functional requirements of three-dimensional micro / nano structures, such as conductivity, insulation, and photoelectric response, thus solving the problem of limited material availability and functionality in traditional systems. On the other hand, its generation method covers all vapor deposition processes, allowing for targeted matching based on material melting points, compositional sensitivity, and other characteristics, ensuring the purity of material vapor and the uniformity of deposition, and avoiding molding quality problems caused by process and material mismatch. At the same time, it can adapt to the preparation needs from simple single-layer structures to complex multi-layer composite structures without replacing the entire system, which improves process flexibility and reduces equipment investment and process adjustment costs, providing core support for achieving high-quality, multi-scenario three-dimensional micro / nano structure preparation.

[0009] Preferably, the surface of the substrate near the mask is selected from one or a combination of planar and uneven surfaces. Specifically, this design can adapt to the deposition requirements of different three-dimensional micro / nano structures: planar surfaces can meet the preparation of basic flat layer structures, while uneven surfaces can be directly used as pre-formed substrates to achieve accurate replication of irregular structures, avoiding the cumbersome steps of additional pre-formed surface processing required by traditional single planar substrates; on the other hand, it can complete the forming of three-dimensional micro / nano structures with surface morphologies from simple to complex without changing the substrate, which not only improves the adaptability of the substrate to diverse structural designs, but also reduces process interruptions and positioning errors caused by substrate replacement, ensuring the preparation accuracy and efficiency of three-dimensional micro / nano structures with different morphological characteristics.

[0010] Preferably, the mask includes a thin film with micro-nano patterned openings and a support device for supporting the thin film; the material of the thin film is selected from one or a combination of metal, organic matter, insulator and semiconductor, and the thickness of the thin film is 1nm~100μm; the material of the support device is selected from one or a combination of metal, organic matter, insulator and semiconductor; the support structure is located outside the micro-nano patterned openings.

[0011] Specifically, on the one hand, the thin film is responsible for precisely defining the micro-nano pattern openings. Its material can be flexibly selected from metals, organic materials, insulators or semiconductors according to the material vapor properties (such as chemical inertness and thermal conductivity) to avoid pattern corrosion or vapor contamination caused by material incompatibility. On the other hand, the support device independently undertakes the function of supporting the thin film. Its material can also be flexibly matched with the thin film and the deposition environment to avoid deformation of the support structure and the thin film due to material differences (such as different coefficients of thermal expansion). Moreover, the support structure is located outside the opening and does not block the material vapor transport path, ensuring the accuracy of the micro-nano pattern openings. Preferably, the shape of the micro / nano pattern opening includes circular, square, rectangular and polygonal shapes, the characteristic size of the micro / nano pattern opening is 1nm~100μm, and the spacing between two adjacent micro / nano pattern openings is 1nm~100μm.

[0012] Specifically, on the one hand, the selection of multiple shapes such as circles, squares, and rectangles can directly match the patterning requirements of different functional structures (such as circles for micropillar arrays and squares for pixelated structures), avoiding the cumbersome process of customizing masks multiple times for traditional single-shape openings, and improving the adaptability to diverse structural designs; on the other hand, the feature size of 1nm~100μm covers the entire micro-nano scale range, which can not only meet the high-precision molding of nanoscale fine structures, but also adapt to the fabrication of slightly larger micron-scale structures, solving the application limitations caused by the narrow size range of traditional methods; at the same time, the spacing between adjacent openings of 1nm~100μm can be flexibly adjusted according to the structural density requirements, which can not only achieve the compact deposition of high-density array structures (small spacing), but also ensure the precise positioning of low-density independent structures (large spacing), avoiding the problem of single structural density caused by fixed spacing.

[0013] Preferably, the method for preparing micro / nano patterned openings includes one or a combination of photolithography, focused ion beam etching, electron beam exposure, reactive ion etching, colloidal particle self-assembly, ion beam etching, and plasma etching.

[0014] Specifically, on the one hand, different methods can be tailored to match the required pattern precision, fabrication efficiency, and material properties. For example, photolithography is suitable for conventional precision patterns in mass production, while electron beam lithography and focused ion beam etching can achieve ultra-high precision (nanoscale) patterns. Reactive ion etching and plasma etching can adapt to the etching requirements of thin films made of different materials such as metals and insulators, avoiding the limitations of traditional single methods such as insufficient precision, poor material adaptability, or low mass production efficiency. On the other hand, the combination of methods can address complex pattern fabrication scenarios (such as first fabricating basic patterns through photolithography and then optimizing the precision of the opening edges using ion beam etching), achieving the dual goals of "high precision + high efficiency" without relying on a single process. At the same time, the diverse method selection does not require replacing the entire mask fabrication equipment; only the process parameters or combination methods need to be adjusted to adapt to the fabrication requirements from simple regular patterns to complex irregular openings. This reduces equipment investment costs and process adjustment difficulties while ensuring the fabrication quality of masks with different precision and materials, providing key process support for the subsequent precise patterning deposition of three-dimensional micro and nanostructures.

[0015] Preferably, the spacing adjustment device is selected from one of a fixed spacing device and a variable spacing device; wherein, the fixed spacing device is selected from one of an inorganic thin film of a specific thickness, micro / nanospheres, O-rings and organic thin films; and the variable spacing device is selected from one of a manual displacement stage and an automatic displacement stage.

[0016] Specifically, the fixed-spacing device can select components of corresponding thickness according to the deposition accuracy requirements, ensuring stable spacing without dynamic adjustment. It is suitable for batch preparation of three-dimensional micro-nano structures of the same specifications, avoiding spacing deviations caused by vibration in traditional dynamic adjustment devices. At the same time, fixed components of different materials can also adapt to different deposition environments. On the other hand, the variable-spacing device supports real-time adjustment of spacing according to requirements such as the number of structural layers and deposition thickness. The manual displacement stage is suitable for low-cost control of simple processes, while the automatic displacement stage meets the requirements for high-precision and automated preparation of complex multi-layer structures, solving the limitation of traditional fixed-spacing devices that cannot adapt to dynamic spacing requirements.

[0017] Preferably, the printing trajectory control device includes a fixed base, a pitch stage disposed on the fixed base, and a rotary tilt stage disposed on the pitch stage; The printing trajectory control device also includes a first control motor that is rotatably connected to the pitch stage and a second control motor that is rotatably connected to the tilt stage.

[0018] Specifically, the fixed base provides a stable and rigid foundation for the entire device, avoiding angle deviations caused by base wobbling during adjustment. The hierarchical arrangement of the pitch stage and the tilt stage enables independent dimensional control of the tilt angle θ and rotation azimuth angle ψ, accurately covering the multi-angle trajectory requirements for the deposition of three-dimensional micro-nano structures, overcoming the limitations of traditional integrated structures in achieving multi-dimensional independent adjustment. On the other hand, the first control motor independently drives the pitch stage, and the second control motor independently drives the tilt stage, avoiding interference from the linkage of adjustments in different dimensions. The precise transmission of the motors ensures the accuracy of angle adjustment, replacing the operational errors that are prone to occur in traditional manual adjustment. At the same time, the overall structural design is compact and functionally integrated, achieving automated trajectory control without the need for additional adjustment components. This reduces the space occupied by the equipment and improves the response speed and repeatability of angle adjustment, ensuring that material vapor can be accurately deposited on the substrate surface according to the preset trajectory, providing a key guarantee for the molding accuracy and consistency of complex three-dimensional micro-nano structures.

[0019] Preferably, the tilt angle θ is 0°~90° and the rotation azimuth angle ψ is 0°~360°.

[0020] Accordingly, the present invention also provides a method for preparing three-dimensional micro / nanostructures using any of the above-mentioned three-dimensional micro / nanostructure printing systems, the method comprising: A three-dimensional micro-nano structure printing system is provided. Based on a pre-designed three-dimensional micro-nano pattern, parameters such as tilt angle θ, rotation azimuth angle ψ, and site dwell time t are generated in a computer and then converted into control commands and input into the control box. The control box drives the printing trajectory control device to adjust the values ​​of θ, ψ and t according to the control command, so as to ensure that the material vapor introduced through the multiple micro-nano pattern openings can form a three-dimensional micro-nano structure on the substrate surface.

[0021] Specifically, this preparation method replaces traditional manual adjustment with computer-parametric control, avoiding human error. Furthermore, the coordinated control of tilt angle θ (deposition direction), rotation azimuth angle ψ (deposition orientation), and site dwell time t (deposition thickness) can accurately reproduce structural morphologies ranging from simple layered to complex three-dimensional structures, solving the problem of traditional methods struggling to balance trajectory accuracy and thickness uniformity. On the other hand, control commands directly drive the printing trajectory control device, which is highly compatible with the aforementioned rotating tilt stage, control motor, and other hardware, eliminating the need for intermediate manual intervention, reducing process interruptions, and significantly improving preparation efficiency. Simultaneously, different structural designs can be adapted simply by adjusting parameters in the computer, without modifying the entire equipment or replacing process modules. This ensures consistency in the preparation of different batches of structures and lowers the preparation threshold and equipment investment costs for complex three-dimensional micro / nano structures, providing a feasible path for their diversified design and large-scale production.

[0022] The beneficial effects of this invention are as follows: Unlike existing technologies, this invention provides a three-dimensional micro / nanostructure printing system and a method for preparing three-dimensional micro / nanostructures. The three-dimensional micro / nanostructure printing system places an integrated mask structure, including a substrate and openings with micro / nano patterns, on a rotating tilting stage in a printing trajectory control device. By adjusting the tilt angle θ, rotation azimuth angle ψ, and site dwell time t through the printing trajectory control device, the path and deposition volume of material vapor reaching the substrate surface through different micro / nano pattern openings of the mask vary, thereby enabling atoms / molecules within the material vapor to form complex three-dimensional micro / nanostructures on the substrate surface. The method for preparing three-dimensional micro / nanostructures using this printing system not only inherits all the advantages of mask lithography but also significantly improves the diversity and stacking accuracy of three-dimensional micro / nanostructures, thus facilitating the formation of complex three-dimensional micro / nanostructures. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the overall structure of the three-dimensional micro / nano structure printing system provided in Embodiment 1 of the present invention; Figure 2 This is a schematic diagram of the printing trajectory control device in the three-dimensional micro / nano structure printing system provided in Embodiment 1 of the present invention; Figure 3 This is a schematic diagram of a mask structure with micro-nano patterned openings in the three-dimensional micro / nano structure printing system provided in Embodiment 1 of the present invention; Figure 4 This is a schematic diagram of the mask fabrication process with micro-nano patterned openings in the three-dimensional micro-nano structure printing system provided in Embodiment 1 of the present invention; Figure 5 This is a schematic diagram of the mask integrated structure fabrication process in the method for preparing three-dimensional micro / nano structures provided in Embodiment 1 of the present invention; Figure 6 This is a flowchart of the method for preparing three-dimensional micro / nano structures provided in Embodiment 1 of the present invention; Figure 7a This is a schematic diagram of the motion trajectory of the three-dimensional nanostructure of the windmill provided in Embodiment 1 of the present invention; Figure 7b This is a scanning electron microscope image of the three-dimensional nanostructure of the windmill provided in Embodiment 1 of the present invention; Figure 7c An atomic force microscope image of the three-dimensional nanostructure of the windmill provided in Embodiment 1 of the present invention; In the diagram: 100 – Three-dimensional micro / nano structure printing system; 10 – Vapor phase material source cavity; 20 – Printing trajectory control device; 21 – Fixed base; 22 – Pitch stage; 23 – Rotation tilt stage; 24 – First control motor; 25 – Second control motor; 26 – RS-232 interface; 30 – Mask integrated structure; 31 – Mask; 310 – Open area of ​​support structure; 3110 – Micro / nano pattern opening; 311 – First mask film; 312 – Support structure; 313 – Second mask film; 32 – Substrate; 33 – Spacing adjustment device; 40 – Control box; 50 – Computer; 60 – Vapor phase material source; 70 – Motor control line; 80 – Fixed carrier; 91 – First flange interface; 92 – Second flange interface. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] The three-dimensional micro / nano structure printing system and the method for preparing three-dimensional micro / nano structures provided by the present invention will now be further described with reference to specific embodiments.

[0026] Example 1: Please see Figures 1 to 5 , Figure 1 This is a schematic diagram of the overall structure of the three-dimensional micro / nano structure printing system 100 provided in Embodiment 1 of the present invention. The three-dimensional micro / nano structure printing system 100 includes a vapor phase material source cavity 10, a mask integrated structure 30, a control box 40, and a computer 50 electrically connected to the control box 40. The vapor phase material source cavity 10 is provided with a printing trajectory control device 20 and a vapor phase material source 60 electrically connected to the control box 40. The printing trajectory control device 20 has a rotating tilting stage 23 for supporting the mask integrated structure 30. The mask integrated structure 30 includes a substrate 32, a mask 31 disposed opposite to the substrate 32, and a spacing adjustment device 33. The spacing adjustment device is used to adjust the spacing between the substrate 32 and the mask 31. The mask 31 is provided with a plurality of micro / nano pattern openings 3110. The printing trajectory control device 20 is used to adjust the tilt angle θ, the rotation azimuth angle ψ, and the site dwell time t, so that the material vapor emitted by the gas phase material source 60 is transmitted to the surface of the substrate 32 through the micro-nano pattern opening 3110 and forms a three-dimensional micro-nano structure. The tilt angle θ is the angle between the horizontal plane where the rotating tilt stage 23 is located and the normal direction where the gas phase material source 60 is located. The rotation azimuth angle ψ is the self-rotation angle of the rotating tilt stage 23. The site dwell time t is the dwell time of a single deposition site on the motion trajectory of the material vapor on the surface of the substrate 32.

[0027] Specifically, the three-dimensional micro / nano structure printing system 100 provided in this embodiment of the invention first designs a motion trajectory curve, extracts trajectory points and sends control commands to the control box 40. The pitch stage 22 and the tilt stage 23 of the printing trajectory control device 20 drive the mask 31 and the substrate 32 to rotate together according to the trajectory curve. When moving according to the trajectory, the gas phase material reaches the substrate 32 through the mask 31. At the same time, the dwell time of the motion trajectory points can be adjusted to achieve point flux control and height control of each point, and finally form a three-dimensional micro / nano structure.

[0028] In this embodiment of the invention, the gas-phase material source cavity 10 can isolate impurities and ensure the high purity of the three-dimensional micro-nano structure; the micro-nano pattern openings 3110 of the mask 31 can achieve precise controlled deposition of material vapor and avoid disordered diffusion; the printing trajectory control device 20 can adjust the tilt angle θ, rotation azimuth angle ψ and site dwell time t to flexibly customize various complex three-dimensional shapes such as nano dots and nano spirals; the digital linkage between the computer 50 and the control box 40 improves the preparation accuracy and repeatability and reduces human error; at the same time, the three-dimensional micro-nano structure printing system 100 integrates the functions of vapor deposition, control and mask positioning, simplifies the process and adapts to the efficient and precise preparation needs of three-dimensional micro-nano structures in different scenarios.

[0029] In this embodiment of the invention, a printing trajectory control device 20 and a gas phase material source 60, electrically connected to a control box 40, are disposed inside the vapor phase material source cavity 10. The printing trajectory control device 20 is fixedly connected to the top of the vapor phase material source cavity 10 via a fixed carrier 80, and the printing trajectory control device 20 is connected to the first flange interface 91 and the second flange interface 92 respectively via a motor control line 70. The motor control line 70 is electrically connected to the control box 40 via the first flange interface 91 and the second flange interface 92. The above design can ensure the stability of the position of the printing trajectory control device 20 in the vapor phase material source cavity 10, avoid the deposition deviation caused by device shaking during the vapor deposition process, and ensure the accuracy of the vapor deposition position of the material on the surface of the substrate 32. At the same time, its electrical connection with the control box 40 via the motor control line 70 can realize the stable and real-time transmission of control commands, avoid the adjustment error of parameters such as tilt angle θ and rotation azimuth angle ψ caused by signal interference or delay, and further improve the accuracy and repeatability of three-dimensional micro-nano structure preparation.

[0030] Please see Figure 2 , Figure 2 This is a schematic diagram of the printing trajectory control device 20 in the three-dimensional micro / nano structure printing system 100 provided in Embodiment 1 of the present invention. The printing trajectory control device 20 includes a fixed base 21, a pitch stage 22 disposed on the fixed base 21, and a rotating tilt stage 23 disposed on the pitch stage 22. The fixed base 21 is fixedly connected to the top of the gas phase material source cavity 10 through a fixed carrier 80. The printing trajectory control device 20 also includes a first control motor 24 and a second control motor 25. The first control motor 24 is rotatably connected to the pitch stage 22, and the second control motor 25 is rotatably connected to the rotating tilt stage 23. Both the first control motor 24 and the second control motor 25 are provided with RS-232 interfaces 26.

[0031] Specifically, the fixed base 21 is fixed to the top of the vapor material source cavity 10 via the fixed carrier 80, providing stable support for the entire device and avoiding deposition deviation caused by device shaking during the vapor deposition process. The hierarchical layout of the pitch stage 22 and the rotation tilt stage 23, coupled with the first control motor 24 and the second control motor 25 that drive them respectively, can realize independent and precise adjustment of the tilt angle θ and the rotation azimuth angle ψ without interference, providing a flexible control basis for multi-angle deposition and morphology customization of three-dimensional micro-nano structures. The RS-232 interface 26 provided by the first control motor 24 and the second control motor 25 can ensure stable signal transmission with the control box 40 / computer 50, ensure that the angle adjustment command is executed in real time without interference, reduce parameter errors, and ultimately improve the accuracy of the deposition position and morphology of three-dimensional micro-nano structures and the repeatability of the preparation.

[0032] Specifically, after the substrate 32 and mask 31 are fixed, they are placed on the rotating tilt stage 23. The motion trajectory formed by the coupling of the pitch stage 22 and the rotating tilt stage 23 will cause the substrate 32 and mask 31 to form different motion trajectories. The gaseous material source will reach the substrate 32 through the mask 31 according to the motion trajectory. By controlling the motion trajectory, three-dimensional micro-nano structures of different shapes can be formed. By controlling the dwell time t at each site, the flux and height of each site of the nanostructure can be controlled. Different dwell times at different sites correspond to different heights. By jointly controlling the motion trajectory and dwell time, the required three-dimensional micro-nano structures can be printed. For ease of description, the pitch stage 22 controls the tilt angle ψ, the rotating tilt stage 23 controls the rotation azimuth angle θ, and the dwell time t at the site that constitutes the motion trajectory.

[0033] In this embodiment of the invention, the first control motor 24 and the second control motor 25 start and stop synchronously; by simultaneously adjusting the rotation speed of the first control motor 24 (1000~20000 pulses / revolution) and the rotation speed of the second control motor 25 (1000~20000 pulses / revolution), the residence time t at the site can be precisely controlled, so that multiple different deposition sites on the movement trajectory of material vapor on the surface of the substrate 32 have different deposition heights.

[0034] Specifically, the synchronous start and stop of the first control motor 24 and the second control motor 25 can ensure that the adjustment actions of the tilt angle θ and the rotation azimuth angle ψ are coordinated and consistent, avoiding the disorder of the deposition trajectory caused by the deviation of the action timing. By synchronously adjusting the rotation speed of the two, the residence time t of material vapor at different deposition sites on the substrate 32 can be precisely controlled, so that different deposition heights are formed at each site due to the difference in the amount of vapor accumulation. This enables the precise customization of the three-dimensional micro-nano structure in the height dimension, providing a reliable rate-time-height coordinated control mechanism for constructing nanostructures with complex three-dimensional morphology, and further improving the preparation accuracy and morphological diversity of three-dimensional micro-nano structures.

[0035] Please see Figure 3 , Figure 3 This is a schematic diagram of the structure of a mask 31 with micro-nano patterned openings 3110 in a three-dimensional micro-nano structure printing system 100 provided in an embodiment of the present invention; wherein, the mask 31 with micro-nano patterned openings 3110 provided in the present invention includes a wafer body with an open region 310 of a support structure, and a plurality of micro-nano patterned openings 3110 arranged in an array are provided at the bottom of the open region 310 of the support structure.

[0036] Specifically, the wafer body includes a first mask film 311, a support structure 312 disposed on the first mask film 311, and a second mask film 313 disposed on the support structure 312; wherein, the first mask film 311 constitutes a film with micro-nano patterned openings 3110 in the mask 31, and the support structure 312 and the second mask film 313 constitute a support device for the mask 31.

[0037] The sidewall of the open area 310 of the support structure is composed of the support structure 312 and the second mask film 313, and the bottom of the open area 310 of the support structure is composed of the first mask film 311. The opening area of ​​the open area 310 of the support structure is greater than or equal to the bottom area of ​​the open area of ​​the support structure; the micro-nano patterned opening 3110 completely penetrates the first mask film 311.

[0038] In this embodiment of the invention, the open region 310 of the support structure provides a channel for material vapor, allowing vapor to flow orderly from the inlet towards the micro / nano pattern opening 3110. Its specific shape (opening area greater than or equal to the bottom area) guides the vapor to form a specific flow field distribution; simultaneously, it confines the material vapor to a specific area, reducing disordered diffusion of vapor on the mask 31 surface, thereby improving the resolution and precision of the photolithography process. By controlling the size, shape, and layout of the open region 310 of the support structure, the area and manner of contact between the vapor and the substrate 32 can be precisely controlled, achieving precise control of the photolithography pattern.

[0039] In this embodiment of the invention, the micro-nano patterned opening 3110 serves as the final channel for material vapor to reach the substrate 32, and the micro-nano patterned opening 3110 can precisely control the amount and position of the photolithographic material transported.

[0040] Specifically, both the first mask film 311 and the second mask film 313 are made of SiN. x The supporting structure 312 is made of Si. (SiN) x Chemically stable, Si does not readily react with material vapors or other chemicals, maintaining its structural and performance integrity during photolithography. This prevents material degradation or performance decline due to chemical reactions, ensuring the reliability and lifespan of mask 31. Si also exhibits good thermal stability, maintaining its structural and performance stability under the heat generated during photolithography. It does not experience significant expansion, deformation, or changes in electrical properties due to temperature variations, ensuring the reliability and photolithographic accuracy of mask 31 under different operating conditions.

[0041] Specifically, the thickness of the first mask film 311 and the second mask film 313 is 1nm~100μm, and the thickness of the support structure 312 is 100~1000μm.

[0042] In this embodiment of the invention, the feature size of the micro / nano pattern opening 3110 is 1 nm to 50 μm. This feature size range is used to precisely control the transport of the photolithography material. If the feature size is too small, the amount of material vapor passing through may be insufficient, affecting photolithography efficiency and making the opening prone to clogging by the photolithography material, thus reducing the lifespan of the mask 31. If the feature size is too large, high-resolution photolithography pattern transfer may not be possible because larger nanopores will cause the material vapor to diffuse over a large area when reaching the substrate 32, resulting in a decrease in the resolution of the photolithography pattern and failing to meet the requirements of fine photolithography.

[0043] In this embodiment of the invention, the spacing between two adjacent micro / nano pattern openings 3110 is 1 nm to 50 μm. This spacing is set within this range to balance the resolution and efficiency of the lithography pattern. Too small a spacing will cause material vapor from adjacent micro / nano pattern openings 3110 to interfere with each other, leading to overlapping or distortion of the lithography pattern, affecting its accuracy and quality. Too large a spacing reduces the number of micro / nano pattern openings 3110 that can be placed on the same area of ​​the mask 31, decreasing lithography efficiency and increasing lithography cost. A suitable spacing ensures that each micro / nano pattern opening 3110 independently transmits material vapor and transfers the pattern, while achieving a high density of micro / nano pattern openings 3110 per unit area, thus improving lithography efficiency and pattern resolution.

[0044] Please see Figure 4 , Figure 4 This is a schematic diagram of the fabrication process of the mask 31 with micro-nano patterned openings 3110 in the three-dimensional micro-nano structure printing system 100 provided in the embodiment of the present invention. It mainly uses electron beam exposure and silicon-based inductively coupled etching to obtain nano-opening patterns on the front side, and then uses photolithography, deep reactive ion etching and wet etching to open windows on the back side to obtain the mask 31.

[0045] Specifically, the fabrication process of the mask 31 with micro-nano patterned openings 3110 described above will be explained in one embodiment as follows: Step (1): A double-sided polished silicon nitride wafer is provided. The double-sided polished silicon nitride wafer includes a first mask film 311, a support structure 312 disposed on the first mask film 311, and a second mask film 313 disposed on the support structure 312. The first mask film 311 and the second mask film 313 are both preferably 50nm SiN. x The support structure 312 is preferably made of 300 μm Si, such as Figure 4 As shown in part (1).

[0046] Step (2): Electron beam photoresist is coated on the surface of the first mask film 311 away from the support structure 312, and a portion of it is subjected to electron beam exposure treatment to form an electron beam exposure area on the surface of the electron beam photoresist, such as... Figure 4 As shown in section (2).

[0047] Step (3): Use a developer to remove the electron beam photoresist in the electron beam exposed area; perform inductively coupled plasma etching (ICP-etch) on the electron beam exposed area to remove the SiN in the electron beam exposed area. x Afterwards, inductively coupled plasma etching holes (micro / nano patterned openings 3110) are formed, completely penetrating the electron beam photoresist and the first mask film 311, such as... Figure 4 As shown in section (3).

[0048] Step (4): Remove the remaining electron beam photoresist using a wet stripping process; coat the back photoresist on the side of the second mask film 313 away from the support structure 312, and perform ultraviolet lithography exposure on a portion of it to form a back lithography exposure area on the back photoresist surface, such as... Figure 4 As shown in section (4).

[0049] Step (5): Use developing solution to remove the back photoresist in the back photolithography exposure area; perform deep reactive ion etching (DRIE) on the back photolithography exposure area (DRIE process etches away all silicon nitride and part of silicon) to form a DIE hole. The DIE hole completely penetrates the back photoresist, the second mask film 313, and part of the support structure 312. The bottom area of ​​the DIE hole is larger than the bottom area of ​​the inductively coupled plasma etching hole, such as... Figure 4 As shown in section (5).

[0050] Step (6): After removing the remaining back photoresist using a wet stripping process, the deep reactive ion etching (DRIE) area is subjected to wet etching (removal of deep silicon). After wet etching, the DIE holes obtain the open support structure region 310, connecting the inductively coupled plasma etching holes to the bottom of the open support structure region 310, ultimately obtaining a mask 31 with micro / nano patterned openings 3110, such as... Figure 4 As shown in section (6).

[0051] Please see Figure 5 , Figure 5This is a schematic diagram of the fabrication process of the mask integrated structure 30 in the method for preparing three-dimensional micro-nano structures provided in the embodiments of the present invention; wherein, spin-coating photoresist (spacing adjustment device 33) controls the gap between the mask 31 and the substrate, material vapor passes through the mask 31 to form a three-dimensional micro-nano structure on the substrate 32, and the trajectory of the printing trajectory control device 20 can be controlled to form a variety of different three-dimensional micro-nano structures.

[0052] Specifically, the fabrication process of the above-mentioned mask integrated structure 30 will be described in Example 1 of the present invention as follows: First, photoresist is coated onto one side of the substrate 32; then, the photoresist is subjected to ultraviolet exposure; finally, a mask 31 with micro-nano patterned openings 3110 is transferred onto the photoresist surface, so that the SiN on one side of the mask 31 with the micro-nano patterned openings 3110 is formed. x The layer is tightly bonded and fixed to the remaining photoresist after UV exposure, and multiple micro-nano pattern openings 3110 are located in the UV exposure area of ​​the photoresist and are positioned directly opposite the upper surface of the substrate 32.

[0053] Please see Figure 6 , Figure 6 This is a flowchart of a method for preparing three-dimensional micro / nano structures provided in an embodiment of the present invention; specifically, the method includes: S10, Photoresist is coated on substrate 32 and subjected to ultraviolet exposure to form grooves on the photoresist and expose substrate 32, such as... Figure 5 As shown. The photoresist is applied to the substrate 32 to control the gap between the mask and the substrate 32, which facilitates the subsequent use of vapor deposition to obtain different patterns on the substrate 32.

[0054] Specifically, in step S10: the bottom area of ​​the open region 310 of the support structure is less than or equal to the bottom area of ​​the groove; the thickness of the photoresist is 10~50nm.

[0055] S20, the mask 31 is transferred over the photoresist, so that the side surface of the mask 31 with the micro-nano patterned openings 3110 is tightly bonded and fixed to the photoresist, and the multiple micro-nano patterned openings 3110 are aligned with the grooves to obtain the mask integrated structure 30. The fabrication process of the mask 31 with the micro-nano patterned openings 3110 is as follows: Figure 4 As shown, it will not be elaborated further here.

[0056] S30, the mask integrated structure 30 is transferred to the top of the rotating tilt stage 23 in the printing trajectory control device 20, so that the surface of the substrate 32 in the mask integrated structure 30 away from the photoresist is tightly attached and fixed to the rotating tilt stage 23. Specifically, step S30 also includes: First, a printing trajectory control device 20 is provided, such as... Figure 2 As shown: The printing trajectory control device 20 includes a fixed base 21, a pitch stage 22 disposed on the fixed base 21, and a rotating tilt stage 23 disposed on the pitch stage 22; wherein, the printing trajectory control device 20 also includes a first control motor 24 and a second control motor 25, the first control motor 24 being rotatably connected to the pitch stage 22, and the second control motor 25 being rotatably connected to the rotating tilt stage 23.

[0057] Then, the mask integrated structure 30 is transferred to the top of the rotating tilt stage 23 in the printing trajectory control device 20, so that the surface of the substrate 32 in the mask integrated structure 30 away from the photoresist is tightly fixed and attached to the rotating tilt stage 23.

[0058] S40, by adjusting the tilt angle θ, rotation azimuth angle ψ and site dwell time t respectively through the printing trajectory control device 20, material vapor introduced into the groove through multiple micro-nano pattern openings 3110 forms a three-dimensional micro-nano structure on the surface of the substrate 32.

[0059] Specifically, step S40 also includes: S401, based on the pre-designed three-dimensional nanopattern, generates parameters such as tilt angle θ, rotation azimuth angle ψ, and site dwell time t in computer 50, and converts them into control commands and inputs them into control box 40; S402, the control box 40 drives the printing trajectory control device 20 to adjust the values ​​of θ, ψ and t respectively according to the control command, so as to ensure that the material vapor introduced into the groove by the multiple micro-nano pattern openings 3110 can form a three-dimensional micro-nano structure on the surface of the substrate 32.

[0060] In step S40: the tilt angle θ is 0°~90°, and the rotation azimuth angle ψ is 0°~360°.

[0061] In step S40: the three-dimensional micro / nano structure includes any one of the following: nanodot, nanoring, nanosquare ring, nanopetal shape, nanospiral shape, nano windmill shape, and nanowave shape.

[0062] Specifically, step S40 generates parameters such as tilt angle θ (0°~90°), rotation azimuth angle ψ (0°~360°), and site dwell time t based on a pre-designed three-dimensional nanopattern and converts them into control commands, enabling customized setting of deposition parameters. The control box 40 drives the printing trajectory control device 20 to precisely adjust the values ​​of the three parameters. The wide range of θ and ψ adjustment can adapt to multi-angle deposition requirements, and the adjustment of t can match the deposition amount of different sites. The three parameters work together to ensure that the material vapor accurately forms various target three-dimensional micro-nano structures such as nanodots and nano-spirals. This not only ensures the consistency of the structural morphology with the preset pattern, but also realizes the diversified preparation of three-dimensional micro-nano structures, meeting the customized structural morphology requirements of different application scenarios.

[0063] Please see Figure 7a , Figure 7a This is a schematic diagram of the motion trajectory of the three-dimensional nanopattern of the windmill provided in Embodiment 1 (the horizontal axis is ψ, and the vertical axis is θ); by Figure 7a It can be seen that the motion trajectory of the three-dimensional nanopattern of the windmill exhibits a regular windmill-shaped outline. Under the coordinated change of the rotation azimuth angle ψ (range of 0°~360°) and the tilt angle θ, the trajectory lines are continuous and completely match the preset windmill structure design. This indicates that the parameter combination of tilt angle θ and rotation azimuth angle ψ precisely corresponds to the forming trajectory requirements of the three-dimensional nanopattern of the windmill, providing a clear and controllable path for subsequent material vapor deposition along this trajectory to form the target three-dimensional shape, and verifying the rationality and accuracy of the tilt angle, rotation azimuth angle parameter design and coordinated control logic.

[0064] Please see Figure 7b , Figure 7b This is a scanning electron microscope image of the three-dimensional nanopattern of the windmill provided in Embodiment 1; by Figure 7b As can be seen, the three-dimensional windmill nanopattern prepared in Example 1 exhibits a clear and regular windmill-shaped macroscopic morphology. The various parts of the structure (such as the blades) are symmetrical in shape and have smooth contours, without obvious agglomeration or defects. This indicates that by controlling the tilt angle θ, rotation azimuth angle ψ and dwell time t in a coordinated manner, the printing system can accurately deposit and form a three-dimensional windmill nanopattern with complete morphology and excellent regularity on the surface of substrate 32, verifying the effectiveness of the system in macroscopic morphology control.

[0065] Please see Figure 7c , Figure 7c This is an atomic force microscope image of the three-dimensional nanopattern of the windmill provided in Embodiment 1; by Figure 7c As can be seen, the atomic force microscope image clearly shows the three-dimensional morphology of the windmill's three-dimensional nanopattern: the height differences of each part of the structure (such as the blades) are obvious (combined with the color mark on the right, the height change has a clear gradient), and the surface is flat and without significant defects; at the same time, the arrangement of multiple windmill structures on the substrate 32 has good consistency, indicating that the printing system can accurately control the three-dimensional morphology and height distribution of the windmill's three-dimensional nanopattern, and has excellent repeatability and uniformity when preparing multiple structures, further verifying the reliability of achieving high-precision preparation of three-dimensional micro and nanostructures by synergistic control of tilt angle θ, rotation azimuth angle ψ and dwell time t.

[0066] Unlike existing technologies, this invention has the following advantages: First, this invention discloses a three-dimensional micro / nanostructure printing system 100 and a method for preparing three-dimensional micro / nanostructures. The method for preparing three-dimensional micro / nanostructures includes placing and fixing a mask 31 at a certain distance on a substrate 32. Material atoms or molecules generated by a gas-phase material source reach and deposit on the surface of the substrate 32 through the pattern openings on the mask 31. Each pattern can be regarded as composed of a large number of discrete deposition sites. The tilt angle, rotation azimuth angle, and residence time of a single deposition site of the substrate 32 relative to the gas-phase material source are dynamically adjusted by a printing trajectory control device 20 to precisely control the position and deposition flux of the gas-phase material source atoms or molecules reaching the surface of the substrate 32, thereby printing a three-dimensional micro / nanostructure on the surface of the substrate 32.

[0067] Secondly, the three-dimensional micro-nano structure printing system 100 and the method for preparing three-dimensional micro-nano structures provided by the present invention are simple to operate, flexible in structural design, and have high printing precision. They can achieve precise control over the size and height of three-dimensional micro-nano structures and have broad application prospects in advanced nanofabrication fields such as metasurface construction and semiconductor device manufacturing.

[0068] Third, the present invention utilizes an automated printing trajectory control device 20 to drive the mask 31 and the substrate 32 to achieve coupled complex rotation. At the same time, it can also control the dwell time of each point on the motion trajectory, realize the control of the gas phase material flux at the site and the height control of each site, thereby realizing the printing of various three-dimensional micro and nano structures.

[0069] It should be noted that all the above embodiments belong to the same inventive concept, and the descriptions of each embodiment have different focuses. Where the description in a particular embodiment is not detailed, please refer to the description in other embodiments.

[0070] The above embodiments merely illustrate implementation methods of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A three-dimensional micro / nano structure printing system, characterized in that, The device includes a vapor phase material source, a printing trajectory control device, a mask integrated structure, a control box, and a computer electrically connected to the control box. The printing trajectory control device has a rotating tilting stage for supporting the mask integrated structure. The mask integrated structure includes a substrate, a mask disposed opposite to the substrate, and a spacing adjustment device. The mask has multiple micro-nano patterned openings, and the spacing adjustment device is used to adjust the spacing between the substrate and the mask. The printing trajectory control device is used to adjust the tilt angle θ, the rotation azimuth angle ψ, and the site dwell time t, so that the material vapor generated by the gas phase material source is transmitted to the substrate surface through the micro-nano pattern opening and forms a three-dimensional micro-nano structure; the tilt angle θ is the angle between the horizontal plane where the rotating tilt stage is located and the normal direction of the gas phase material source, the rotation azimuth angle ψ is the self-rotation angle of the rotating tilt stage, and the site dwell time t is the dwell time of the material vapor at a single deposition site on the motion trajectory of the material vapor on the substrate surface.

2. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The gaseous material source is selected from one or a combination of metals, organics, insulators, and semiconductors; the method for generating the gaseous material source is selected from one or a combination of physical vapor deposition and chemical vapor deposition.

3. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The surface of the substrate near the mask is selected from one or a combination of a plane and an uneven surface.

4. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The mask includes a thin film having the micro / nano patterned openings and a support device for supporting the thin film; the material of the thin film is selected from one or a combination of metals, organic materials, insulators and semiconductors, and the thickness of the thin film is 1 nm to 100 μm; the material of the support device is selected from one or a combination of metals, organic materials, insulators and semiconductors. The support structure is located outside the opening of the micro / nano pattern.

5. The three-dimensional micro / nano structure printing system according to claim 4, characterized in that, The micro-nano pattern openings include circular, square, rectangular, and polygonal shapes, with a characteristic size of 1 nm to 100 μm and a spacing of 1 nm to 100 μm between adjacent micro-nano pattern openings.

6. The three-dimensional micro / nano structure printing system according to claim 4, characterized in that, The methods for preparing the micro / nano pattern openings include one or a combination of photolithography, focused ion beam etching, electron beam exposure, reactive ion etching, colloidal particle self-assembly, ion beam etching, and plasma etching.

7. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The spacing adjustment device is selected from one of a fixed spacing device and a variable spacing device; wherein, the fixed spacing device is selected from one or a combination of inorganic thin films, micro / nanospheres, O-rings and organic thin films of a specific thickness; the variable spacing device is selected from one or a combination of a manual displacement stage and an automatic displacement stage.

8. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The printing trajectory control device includes a fixed base, a pitching platform disposed on the fixed base, and a rotating tilting platform disposed on the pitching platform; The printing trajectory control device further includes a first control motor rotatably connected to the pitch stage and a second control motor rotatably connected to the tilt stage.

9. The three-dimensional micro / nano structure printing system according to claim 1, characterized in that, The tilt angle θ is 0°~90°, and the rotation azimuth angle ψ is 0°~360°.

10. A method for fabricating three-dimensional micro / nanostructures using the three-dimensional micro / nanostructure printing system as described in any one of claims 1 to 9, characterized in that, The method includes: The three-dimensional micro-nano structure printing system is provided, which generates parameters such as the tilt angle θ, the rotation azimuth angle ψ, and the site dwell time t in the computer according to the pre-designed three-dimensional micro-nano pattern, and converts them into control commands and inputs them into the control box; The control box drives the printing trajectory control device to adjust the values ​​of θ, ψ and t respectively according to the control command, so as to ensure that the material vapor introduced through the multiple micro-nano pattern openings can form the three-dimensional micro-nano structure on the substrate surface.

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