WO2022041675A1 - 一种ar衍射光波导压印模具的制备方法及软模具和应用 - Google Patents

一种ar衍射光波导压印模具的制备方法及软模具和应用 Download PDF

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WO2022041675A1
WO2022041675A1 PCT/CN2021/079295 CN2021079295W WO2022041675A1 WO 2022041675 A1 WO2022041675 A1 WO 2022041675A1 CN 2021079295 W CN2021079295 W CN 2021079295W WO 2022041675 A1 WO2022041675 A1 WO 2022041675A1
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mold
electroforming
nickel
mask
pdms
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PCT/CN2021/079295
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English (en)
French (fr)
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郭鹏飞
张厚超
兰红波
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青岛理工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms

Definitions

  • the invention relates to the technical field of augmented reality AR and micro-nano manufacturing, in particular to a preparation method, soft mold and application of an AR diffractive optical waveguide imprint mold.
  • Augmented Reality is a new technology that skillfully integrates virtual information with the real world. After the virtual information is simulated, it can use one or a group of optical couplers to integrate the virtual information and the real scene through the "superposition” method, and the two kinds of information complement each other, so as to realize the "enhancement of the real world”. ". AR glasses (helmet display) are the core functional components of augmented reality systems.
  • the main factor currently limiting the mass production of AR glasses is the design and manufacture of the display system.
  • the display systems used in the current AR glasses on the market are basically a combination of various micro-displays and optical elements such as prisms, free-form surfaces, and optical waveguides.
  • the optical waveguide has the following significant advantages: a large range of eye-moving frames, adapting to more people, good optical effects, similar appearance to glasses, placed next to the imaging system, large field of view, light weight and thin thickness, as well as good accessibility
  • the potential for mass production, etc. is considered to be the most ideal solution for AR glasses to become consumer-grade.
  • AR optical waveguides are divided into two types: Geometric Waveguide and Diffractive Waveguide.
  • the solution adopted by the Israeli company Lumus is the geometric optical waveguide, which realizes the output of the image and the enlargement of the eye-moving frame through many stacked semi-transparent and semi-reflective mirrors at a certain angle.
  • the production process of geometric optical waveguides is cumbersome, requiring multiple layers of different reflectance-transmittance (R/T) to be coated on each mirror in the mirror array, resulting in low overall yields.
  • R/T reflectance-transmittance
  • diffractive optical waveguides have gradually shown better and wider industrial application prospects.
  • the diffraction grating is the core of the diffractive optical waveguide.
  • the diffractive optical waveguides mainly include surface relief gratings and volume holographic gratings.
  • volume holographic grating which is prepared by using the method of holographic interference exposure to form "light and dark interference fringes" formed inside the material. It is complex, difficult to mass-produce, long-term reliability, and material stability is difficult to guarantee.
  • the consensus that has been formed in the industry is: AR glasses want to have the appearance of ordinary glasses and really go to the consumer market, and the surface relief inclined grating is the best solution at present.
  • Microsoft, Rokid, Magic Leap and other companies have released a variety of consumer-grade AR glasses products, proving the superior performance of surface relief inclined grating diffractive optical waveguides.
  • the inventors found that the existing micro-nano fabrication technologies face the problem of difficulty in manufacturing the surface relief inclined grating, especially the challenging problem of low-cost mass production of the inclined grating.
  • Precision micro-electroforming technology is a micro-mold manufacturing technology with high precision and low cost.
  • LIGA and UV-LIGA technology are considered to be effective methods for making high-precision imprinting molds.
  • LIGA technology has outstanding advantages, its process steps are complicated and the cost is high.
  • a complex and expensive high-energy X-ray source, a synchrocyclotron is required, as well as a photolithographic mask.
  • the lithographic mask itself is a microstructure, which needs to be prepared by ion beam lithography and other technologies first, which is time-consuming and complicated, and there are few types of photoresists available, which makes it difficult for LIGA technology to achieve large-area inclined grating imprinting of any shape. Efficient and low-cost preparation of molds.
  • the purpose of the present invention is to provide a preparation method, a soft mold and an application of an AR diffractive optical waveguide imprint mold.
  • the technical scheme of the present invention is:
  • a preparation method of an AR diffraction optical waveguide imprinting mold the specific steps are:
  • Step 1 Print the electroforming template: use a two-photon polymerization micro-nano 3D printer to print an electroforming mask on a nickel substrate;
  • Step 2 Electroforming tilted grating metal mold: using nanosecond pulse micro-electroforming, electroform the nickel substrate with mask obtained in step 1 to obtain tilted grating metal nickel mold;
  • Step 3 Prepare an imprinting composite soft mold: take the inclined grating metal nickel mold manufactured in step 2 as a master mold, coat the graphic layer polymer PDMS on the master mold, stick PET on the PDMS, and imprint the mold, Remove the PET layer by peeling off the mold to obtain a soft mold that is replicated once, repeat the steps of coating PDMS, pasting PET, embossing, and peeling off the mold, and retaining the outermost PET layer to obtain a composite soft mold.
  • the invention combines nanosecond pulse micro-mask electroforming and micro-nano 3D printing technology to realize a high-precision, low-cost and high-efficiency manufacturing method of a large-area AR diffractive optical waveguide (surface relief inclined grating) imprinting mold.
  • Two-photon polymerization micro-nano 3D printing is used to print electroforming masks on metal substrates.
  • photon polymerization micro-nano 3D printing has high precision and meets the accuracy requirements of diffractive optical waveguides.
  • the electroforming masks are directly printed on the substrate, which has the advantages of low manufacturing cost and high production efficiency.
  • nanosecond pulse micro-mask electroforming technology Using nanosecond pulse micro-mask electroforming technology, the problems of localization and process stability of electrochemical deposition are solved, and high-precision and low-cost manufacturing of inclined grating molds is realized.
  • Two-photon polymerization micro-nano 3D printing can design and print microstructures of any shape, aspect ratio, and tilt angle according to needs; nanosecond pulsed micro-electroforming has strong localization and good process stability. Therefore, using two-photon polymerization micro-nano 3D printing technology to print electroforming masks combined with nanosecond pulse micro-mask electroforming technology can easily realize the fabrication of inclined grating mold structures with arbitrary shapes, large aspect ratios, and large inclination angles.
  • the nickel substrate is pretreated, and the pretreatment method is: polishing and polishing the nickel substrate. Remove various macroscopic defects, corrosion marks, scratches, burrs, sand holes, air bubbles, oxide scale and rust on the surface, reduce the surface roughness, improve the corrosion resistance of the metal, and improve the flatness and finish of the metal substrate surface.
  • the thickness of the printed electroform mask is 1 ⁇ m.
  • the thickness of the printing electroforming mask should not be too large. Considering that the precision of two-photon polymerization micro-nano 3D printing is nanoscale, the mask thickness is set to 1 ⁇ m.
  • the electroforming mask printed on the nickel substrate is cured using UV lamp irradiation.
  • the printing materials used in the two-photon polymerization micro-nano 3D printing in step 1 are UV-curable photoresists, hydrogels, nanocomposite resin materials, and the like.
  • the pulse width of nanosecond pulse micro-electroforming in step 2 is 8-12ns, and the duty ratio is 1:8-12.
  • the high frequency, narrow pulse width, and large duty cycle pulse are selected for electroforming because the size of the pulse width T on is the length of the charging time of the electric double layer. If the pulse width is narrow, the charging time is short, and the area with small current density will not be charged in time or will immediately enter the discharging phase, that is, the inter-pulse T off phase. Therefore, the electrochemical reaction is weak or no electrochemical reaction is carried out in the area with small current density, the electrochemically affected area is small, the grain growth is limited to a relatively small area, and the localization is greatly improved.
  • the electroforming solution in step 3 is a mixture of nickel sulfamate, anode activator, buffer, and anti-pinhole agent.
  • the anode activator is nickel chloride; preferably, the buffer is boric acid; preferably, the anti-pinhole agent is sodium dodecyl sulfate;
  • the preferred concentration of nickel sulfamate in the electroforming solution is 300-450g /L; preferably, the concentration of the anode activator in the electroforming solution is 10-15 g/L; preferably, the concentration of the buffer in the electroforming solution is 30-35 g/L; preferably, the anti-pinhole in the electroforming solution
  • the concentration of the agent is 0.1 ⁇ 0.15g/L.
  • Adding the anode activator nickel chloride to the electroforming solution improves the solubility of the anode, improves the conductivity, and improves the dispersion ability of the solution; adding the buffering agent boric acid slows down the increase of the pH value of the solution in the anode area, so that a higher anode current density can be used It does not cause hydroxide to precipitate on the anode, and also has the effect of improving cathodic polarization and improving the properties of the casting layer; adding anti-pinhole agent sodium lauryl sulfate to reduce the surface tension of the solution, making it difficult for hydrogen bubbles to stay on the surface of the cathode. , thereby preventing the formation of pinholes.
  • the thickness of the electroformed deposited layer is 0.5-1.5 cm; preferably 1 cm.
  • the temperature of the electroforming solution during the electroforming process is 50-55°C.
  • the pH of the electroforming solution during electroforming is 3.8-4.4.
  • a circulating pump is used to flush the electroforming liquid during the electroforming process, and the flushing speed is 1-1.5 m/s. Flushing is to suck out the electroforming liquid through the circulating pump and then discharge it into the electroforming cell. It can agitate the plating solution, reduce the concentration polarization, and quickly discharge the bubbles attached to the electrode surface during processing.
  • the current density of electroforming is 0.5-3.0 A/m 2
  • the electroforming time is 80-120 h; preferably, the electroforming time is 100 h.
  • the mold obtained after electroforming is subjected to post-processing of cleaning, specifically: ultrasonic shock washing with deionized water for 5-10 minutes, and then drying.
  • stress relief post-treatment is performed after cleaning, specifically: vacuum annealing is used for treatment; preferably, the annealing temperature is 350-450° C., and the annealing time is 1.5-2.5 h.
  • vacuum annealing is used for treatment; preferably, the annealing temperature is 350-450° C., and the annealing time is 1.5-2.5 h.
  • the metal nickel master mold is cooled to room temperature with the furnace. The internal stress of the annealed nickel template has been greatly reduced, and the template has become flat, which is suitable for subsequent processes.
  • the thickness of the PDMS layer of the soft mold finally obtained in step 3 is 10-50 ⁇ m, and the thickness of the PET layer is 100-400 ⁇ m.
  • the PDMS graphic layer is obtained by multiple coating, and the PET layer is used as the support layer of the PDMS soft mold. Implemented on PET to obtain multiple PDMS graphic layers.
  • the master mold is subjected to anti-adhesion treatment before coating PDMS in step 3, and the specific steps are: ultrasonic treatment and drying with acetone, isopropanol and deionized water respectively;
  • the ultrasonic cleaning time is 15-25min, and the soaking time is 25-35min.
  • the concentration of the isooctane solution of heptadecafluorodecyltrichlorosilane is 0.5-1.5% by mass.
  • the release agent is CF 3 (CF 2 ) 7 CH 2 CH 2 PO 2 (OH) 2 .
  • the release agent is coated by spin coating, the spin coating speed is 1800-2200r/min, and the spin coating time is 35-45s.
  • the operation mode of progressive sequential line contact pressing is adopted during the pasting process of the PET layer. This way of operation can eliminate as much as possible the bubble defects generated during the embossing process.
  • the operating conditions of the embossing are: the embossing force is 50-500N, and the heating temperature is 50-90°C.
  • PDMS is fully cured after embossing. The embossing process ensures that the graphic layer and the support layer are better adhered to each other, ensure that the graphic layer and the master mold are in complete conformal contact, and reduce bubble defects generated during the heating process.
  • the present invention also provides a soft mold prepared by using the above-mentioned method for preparing an AR diffractive optical waveguide imprint mold.
  • the present invention also provides the application of the above-mentioned soft mold in the field of surface relief inclined grating.
  • the two-photon polymerization micro-nano 3D printing technology has high printing accuracy, and can accurately print various structures of sub-microscale, which meets the accuracy requirements of diffractive optical waveguides, and solves the problem of insufficient process accuracy such as LIGA.
  • Two-photon polymerization micro-nano 3D printing is used to manufacture electroforming masks, which can be directly formed on metal substrates, which overcomes the difficulty of traditional LIGA process mask making, and requires a high-energy X-ray source - synchrocyclotron, which is an expensive facility. And the problem of complex mask manufacturing process, which greatly reduces the manufacturing cost and improves the manufacturing efficiency.
  • the method proposed in the present invention adopts the two-photon polymerization micro-nano 3D printing technology to print the electroforming mask, which has no constraints on the design and manufacture of the inclined grating electroforming mask, especially can realize the surface relief inclined grating of any shape and the large aspect ratio Fabrication of the structure of the tilted grating.
  • Nanosecond pulse electroforming has strong localization and high precision.
  • the inclined grating imprinting mold manufactured by the present invention has very high requirements on manufacturing precision.
  • the growth of the localized electrodeposition processing material should be consciously controlled within a certain area.
  • the current density in the electroforming solution varies in size between the two electrodes. The closer to the center of the electrode, the higher the current density. Therefore, in the central region of the electrode, the growth rate of the cast layer is significantly faster than in the region far from the center.
  • a voltage is applied between the anode and cathode, the metal surface in solution forms an electric double layer.
  • the electric double layer (equivalent to a capacitor) is periodically charged and discharged. Where the current density is high, the charging time of the electric double layer capacitor is short, and where the current density is low, the charging time is long.
  • the size of the pulse width T on is the length of the charging time of the electric double layer. If the pulse width is narrow, the charging time is short, and the area with low current density is too late to be charged or is not fully charged. Enter the discharge stage, namely the interpulse T off stage.
  • the electrochemical reaction is weak or no electrochemical reaction is carried out in the area with small current density, the electrochemical influence area is small, the grain growth is limited to a relatively small area, and the localization is greatly improved, so as to achieve sub-microscale High-precision manufacturing of imprinting molds.
  • Nanosecond pulse electroforming can obtain dense and high conductivity deposition layer.
  • the crystal morphology and growth mode of metal deposition are closely related to the cathodic polarization overpotential. With the increase of overpotential, the critical size of electrocrystallization decreases, the probability of crystal nucleus formation increases, and the number of crystallites increases, which makes the crystallites finer. , the cast layer is dense.
  • the polarization includes two parts, concentration polarization and electrochemical polarization. Concentration polarization has disadvantages for metal deposition, while electrochemical polarization makes crystallization fine.
  • the metal ions at the cathode interface are rapidly replenished, reducing the effective thickness of the diffusion layer, reducing the concentration polarization, making it possible to use higher current densities than conventional DC deposition, which can produce more High electrochemical polarization, to achieve the effect of refining grains and improving the density of the cast layer.
  • Nanosecond pulse electroforming is beneficial to reduce concentration polarization and increase cathode current density.
  • the characteristics of the pulse current waveform are: at the moment of switching on, a much higher current density can be obtained at the electrode than DC, which improves the electrochemical polarization of the electrode and produces a fine cast layer; after disconnection, the electrode quickly returns to its original state, and the cathode The metal ions at the interface can be replenished rapidly, reducing the effective thickness of the diffusion layer and reducing the concentration polarization.
  • the particles in the electroforming liquid move and stop uninterruptedly in the high-frequency pulsed electric field, resulting in high-frequency vibration, which plays a role in stirring the electroforming liquid, reduces the concentration polarization and makes the impurities adsorbed on the surface of the cathode, The desorption of hydrogen, etc., is beneficial to reduce defects and improve the purity of the casting layer.
  • the pulse interval provides time for the temperature drop of the electroforming solution and the discharge of the electroforming products, so that the electroforming solution can be rapidly updated, which can improve the flow field characteristics and make the electroforming solution.
  • the concentration polarization of the electrode surface is reduced.
  • FIG. 2 is a schematic diagram of the principle of a two-photon polymerization micro-nano 3D printer provided by an embodiment of the present invention
  • FIG. 3 is a schematic diagram of an electroforming nickel metal mold provided by an embodiment of the present invention.
  • Fig. 4 is the nickel master mold replication schematic diagram that the embodiment of the present invention provides
  • FIG. 5 is a schematic diagram of an imprinting composite soft mold provided by an embodiment of the present invention.
  • FIG. 6 is a flow chart of manufacturing an AR diffractive optical waveguide imprint mold provided by an embodiment of the present invention.
  • Nickel plate 2. Photoresist, 3. Light source, 4. Dichroic mirror, 5. Objective lens, 6. Substrate, 7. XY motion stage, 8. Control and feedback system, 10. Electroformed nickel Mold, 11, PET, 12, PDMS graphic layer.
  • FIG. 1 is a schematic diagram of an electroforming mask to be manufactured by the present invention and the specific parameters of the diffractive optical waveguide (surface relief inclined grating) that can be manufactured, wherein the angle of inclination ⁇ , groove depth (relative depth) h, line width, filling
  • the factor (grating width c/period ⁇ ) is as described in FIG. 1 .
  • a photoresist 2 is arranged on the surface of the nickel plate 1 .
  • the nickel plate is polished and polished to remove various macro defects, corrosion marks, scratches, burrs, sand holes, bubbles, oxide skin and rust on the surface, reduce the surface roughness, improve the corrosion resistance of the metal, and improve the metal corrosion resistance.
  • the data preprocessing software is used to convert it into a processing file; then, the processing file is input into the two-photon polymerization micro-nano 3D printer Photonic Professional GT2, Fill the printer's cartridge with printing material IP-L 780.
  • the nickel metal plate was placed on the printing platform of the printer as the printing substrate, and the two-photon polymerization micro-nano 3D printer PhotonicProfessional GT2 was turned on.
  • Step 2 Electroforming tilted grating metal mold.
  • the metal mold material is nickel.
  • the micro-electroforming equipment is DZY-III dual-slot dual-channel precision electroforming machine, NPG-18/3500N nanosecond pulse power supply, combined with nanosecond pulse Method of manufacturing nickel mold by precision micro-electroforming process:
  • the nickel metal plate with mask obtained in step 1 was connected to the cathode of the electroforming equipment, and the pure nickel plate was connected to the anode, and placed in a 300 g/L nickel sulfamate electroforming solution.
  • the anode activator nickel chloride 10g/L was added to the electroforming solution to improve the solubility of the anode, the electrical conductivity and the dispersion ability of the solution;
  • the buffering agent boric acid was added at 30g/L to slow down the increase of the pH value of the solution in the anode area, making the It can use a higher anode current density without precipitation of hydroxide on the anode, and also has the effect of improving cathodic polarization and improving the properties of the cast layer; adding anti-pinhole agent sodium dodecyl sulfate 0.1g/L, reducing The surface tension of the solution makes it difficult for hydrogen bubbles to stay on the surface of the cathode, thereby preventing the formation of pinholes.
  • Electroforming The micro-electroforming equipment was turned on, and electroforming was performed with a nanosecond pulse power supply with a pulse width of 10 ns and a duty ratio of 1:10, and the thickness of the electroforming deposition layer was 1 cm.
  • the temperature of the electroforming liquid is controlled at 50°C by the constant temperature system, the pH value is controlled at 4 by the pH value monitoring system, and the liquid is flushed by the pump, and the flushing speed is 1.3m/s, which can stir the bath. Reduce concentration polarization and quickly discharge air bubbles adhering to the electrode surface during processing. To avoid excessive surface roughness, the current density is 2.5A/dm 2 .
  • the electroforming time is about 100h.
  • the high frequency, narrow pulse width, and large duty cycle pulse are selected for electroforming because the size of the pulse width T on is the length of the charging time of the electric double layer. Or immediately enter the discharge phase without being fully charged, that is, the interpulse T off phase. Therefore, the electrochemical reaction is weak or no electrochemical reaction is carried out in the area with small current density, the electrochemically affected area is small, the grain growth is limited to a relatively small area, and the localization is greatly improved.
  • the electroforming nickel mold 10 was removed from the nickel plate 1, and ultrasonically washed with deionized water for 10 minutes to completely remove the residual material on the nickel mold, and dried with nitrogen. Then, surface treatment is performed on the mold of the inclined grating structure to reduce the surface roughness and improve the surface quality of the inclined grating.
  • the manufactured metal nickel master mold was subjected to post-stress relief treatment, vacuum annealing, the temperature was 400 ° C, and the time was 2 hours. After annealing, the metal nickel master mold was annealed. The mold is cooled to room temperature with the oven. The internal stress of the annealed nickel template has been greatly reduced, and the template has become flat, which is suitable for subsequent processes.
  • Step 3 Preparation of the imprinted composite soft mold.
  • the graphic layer polymer PDMS is coated on the master mold, the PET is pasted on the PDMS, the mold is imprinted, cured, and then demolded by peeling.
  • the copied PDMS graphic layer is separated from the metal nickel master mold, and a soft mold for one copy is obtained (PDMS is adhered to PET), which is repeatedly coated with PDMS, pasted with PET (applied at different positions on the same PET), imprinted, and cured. 2.
  • the step of peeling off the mold, and finally a composite soft mold in which a plurality of PDMS soft mold arrays are arranged on a piece of PET is obtained.
  • the imprinting composite soft mold manufactured in this example PDMS is a graphic layer, and its thickness is 10-50 ⁇ m; PET is a supporting layer, and its thickness is 100-400 ⁇ m. Based on step 2, a metal nickel master mold is manufactured, and cyclic replication is performed, and the replicated PDMS soft mold arrays are arranged on a 100 ⁇ 100mm PET substrate to make a double-layer composite soft mold. Process:
  • Preprocessing anti-adhesion treatment is performed on the nickel master mold: 1 ultrasonically treat each with acetone, isopropanol and deionized water for 20 minutes, and then place the master mold on a hot plate (or heating box) for drying; 2 use isooctane as a solvent , configure a 1% concentration of heptadecafluorodecyltrichlorosilane solution (FDTS), let stand for 15min, and then put the master mold into it to soak for 30min; Wash for 20min.
  • FDTS heptadecafluorodecyltrichlorosilane solution
  • mold release agent on the surface of the nickel master mold (the material of mold release agent is: CF 3 (CF 2 ) 7 CH 2 CH 2 PO 2 (OH) 2 , spin coating at 2000r/min for 40s, and apply the mold release agent to the master mold for 40s.
  • a layer of anti-adhesion layer is formed on the surface of the pattern to further reduce the surface energy of the master mold.
  • the pattern layer polymer PDMS is coated on the surface of the master mold by precise coating methods such as spin coating or slit coating, and the thickness is 10-50 microns. Vacuum treatment to discharge air bubbles inside PDMS.
  • Oxygen plasma bombardment treatment is performed on the surface of the support layer material PET to improve the adhesion between PET and PDMS, and finally the support layer material PET is applied with "progressive" sequential line contact pressure and cladding. To PDMS, eliminate as much as possible the bubble defects produced by the imprinting process.
  • the double-layer composite soft mold can not only achieve complete conformal contact with a large area of non-flat surface/substrate by its own flexibility, but also ensure the accuracy and quality of the imprinted pattern through small deformation of the characteristic layer structure, and realize large-area nano-pressing.
  • the perfect combination of "soft" and "hard” required for printing; the double-layer composite soft mold (multiple PDMS soft molds arranged on one PET) can realize large-scale production of multiple inclined grating microstructures after one imprint , and the texture is soft, not easy to be damaged, can be used many times, and reduces the manufacturing cost of the mold.

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Abstract

本发明涉及一种AR衍射光波导压印模具的制备方法及软模具和应用。具体步骤为：采用双光子聚合微纳3D打印机在镍基底上打印电铸掩模；利用纳秒脉冲微细电铸，对得到的带有掩模的镍基板进行电铸，得到倾斜光栅金属镍模具；以制造的倾斜光栅金属镍模具作为母模，在母模上涂布图形层聚合物PDMS，将PET贴覆到PDMS上，对模具进行压印，采用揭开式脱模，得到一次复制的软模具，重复涂覆PDMS、贴覆PET、压印、揭开式脱模的步骤，最终制得若干PDMS软模具阵列排布在一张PET上的复合软模具。实现大面积AR衍射光波导压印模具的高精度低成本高效制作。

Description

一种AR衍射光波导压印模具的制备方法及软模具和应用
本申请要求于2020年08月24日提交中国专利局、申请号为202010859275.6、发明名称为“一种AR衍射光波导压印模具的制备方法及软模具和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及增强现实AR和微纳制造技术领域，特别是涉及一种AR衍射光波导压印模具的制备方法及软模具和应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
增强现实(Augmented Reality，简称AR)是一种将虚拟信息与真实世界巧妙融合的新技术。它能够在虚拟信息模拟仿真后，利用一个或一组光学耦合器，通过“叠加”的方式，将虚拟信息和真实场景融为一体，两种信息互为补充，从而实现对真实世界的“增强”。AR眼镜(头盔显示)是增强现实系统的核心功能部件。
目前限制AR眼镜批量化生产的主要因素是显示系统的设计和制造。当前市场上的AR眼镜采用的显示系统基本上都是各种微型显示屏与棱镜、自由曲面、光波导等光学元件的组合。其中光波导具有以下显著的优势：动眼框范围大、适应更多人群、光学效果好、外观形态与眼镜类似、成像系统旁置、具有视场角大、质量轻和厚度薄以及良好的可量产潜能等，被认为是AR眼镜走向消费级的最理想的解决方案。AR光波导分为几何光波导(Geometric Waveguide)和衍射光波导(Diffractive Waveguide)两种。以色列Lumus公司采用的方案就是几何光波导，它是通过许多堆叠在一起的成一定角度的半透半反镜面来实现图像的输出和动眼框的扩大。几何光波导的生产工艺繁冗，需要在镜面阵列中的每个镜面上镀上不同反射透射比(R/T)的多层膜，导致总体良率较低。目前，衍射光波导已经逐渐显示出 更好和更广泛的工业化应用前景。衍射光栅是衍射光波导的核心，根据所使用的衍射光栅的不同，衍射光波导主要有表面浮雕光栅和体全息光栅。国际上，Digilens、苹果的Akonia公司、英国BAE、索尼等公司采用的解决方案是体全息光栅，它是运用全息干涉曝光的方法在材料内部曝光形成的“明暗干涉条纹”来制备，其材料制备复杂、规模量产困难、长期可靠性、材料稳定性难以保证。目前业界已经形成的共识是：AR眼镜想要具备普通眼镜的外观，真正走向消费市场，表面浮雕倾斜光栅是目前最佳方案。目前Microsoft、Rokid、Magic Leap等公司发布了多款消费级AR眼镜产品，证明了表面浮雕倾斜光栅衍射光波导的优越性能。
但是，发明人发现，现有的微纳制造技术(诸如光学光刻、纳米压印等)面临表面浮雕倾斜光栅制造困难的问题，尤其是难以实现倾斜光栅低成本批量化生产的挑战性难题。目前国际AR设备提供商Microsoft、Magic Leap、Vuzix等公司生产表面浮雕光栅的方法：(1)利用电子束光刻和刻蚀工艺制造小母版，通过步进压印工艺制造大母版(压印模具)；(2)随后采用通过纳米压印(平压平工艺)技术，在玻璃基底(即波导片)涂铺可见光波段透明度很高和高折射率指数的树脂材料上压印出倾斜光栅光波导结构。该方案制作母模具面临很大的限制和约束，例如，电子束光刻和刻蚀工艺相结合只能制造非常小面积的母版，而且对于所制造的倾斜光栅只能限定一定几何特征尺寸，尤其还面临制造成本高和生产周期长的问题。此外，还存在压印的面积较小，模具易损坏等问题。因此，AR衍射光波导(表面浮雕倾斜光栅)压印模具的制作面临难以解决的难题。
精密微电铸技术是一种精度高，成本低的微模具制造技术。其中LIGA以及UV-LIGA技术被认为是制作高精度压印模具的有效方法。LIGA技术虽然具有突出的优点，但是它的工艺步骤比较复杂,成本费用昂贵。为了获得光源，需要复杂而又昂贵的高能量X射线源——同步回旋加速器，同时还需要光刻掩模板。光刻的掩模板本身就是微结构，需要先用离子束光刻等技术制备出来，费时又复杂,可用的光刻胶种类又少，这使得LIGA技术难以实现任意形状的大面积倾斜光栅压印模具的高效低成本制备。
发明内容
针对上述现有技术中存在的问题，本发明的目的是提供一种AR衍射光波导压印模具的制备方法及软模具和应用。
为了解决以上技术问题，本发明的技术方案为：
一种AR衍射光波导压印模具的制备方法，具体步骤为：
步骤1：打印电铸模板：采用双光子聚合微纳3D打印机在镍基底上打印电铸掩模；
步骤2：电铸倾斜光栅金属模具：利用纳秒脉冲微细电铸，对步骤1得到的带有掩模的镍基板进行电铸，得到倾斜光栅金属镍模具；
步骤3：制备压印复合软模具：以步骤2制造的倾斜光栅金属镍模具作为母模，在母模上涂布图形层聚合物PDMS，将PET贴覆到PDMS上，对模具进行压印，采用揭开式脱模除去PET层，得到一次复制的软模具，重复涂覆PDMS、贴覆PET、压印、揭开式脱模的步骤，保留最外层的PET层得到复合软模具。
本发明结合纳秒脉冲微细掩模电铸和微纳3D打印技术，实现了大面积AR衍射光波导(表面浮雕倾斜光栅)压印模具的高精度低成本高效制作的方法。
采用双光子聚合微纳3D打印在金属基底上打印电铸掩模，一方面光子聚合微纳3D打印精度高，满足了衍射光波导的精度要求，另一方面相较于传统的LIGA工艺，省去了制作高精度光刻掩模的过程，直接在基底上打印电铸掩模，具有制造成本低和生产效率高的优势。
采用纳秒脉冲微细掩模电铸技术，解决了电化学沉积的定域性和过程的稳定性的难题，实现了倾斜光栅模具高精度低成本制造。
双光子聚合微纳3D打印可以根据需要设计打印任意形状、深宽比、倾斜角的微结构；纳秒脉冲微细电铸的定域性强，过程的稳定性好。因此利用双光子聚合微纳3D打印技术打印电铸掩模并结合纳秒脉冲微细掩模电铸技术能够容易实现任意形状、大深宽比、大倾角倾斜光栅模具结构的制造。
在本发明的一些实施方式中，步骤1打印电铸模板中，在进行打印电 铸掩模之前，对镍基底进行预处理，预处理的方法为：对镍基底进行磨光、抛光处理。去掉表面的各种宏观缺陷、腐蚀痕、划痕、毛刺、砂眼、气泡、氧化皮及锈等，降低表面粗糙度，提高金属的耐蚀性，提高金属基底表面的平整度和光洁度。
在本发明的一些实施方式中，打印电铸掩模的厚度为1μm。为节约成本，同时不大于电铸过程中的初始加工间隙，打印电铸掩膜厚度不宜过大，考虑到双光子聚合微纳3D打印的精度为纳米级，因此掩膜厚度定为1μm。
在本发明的一些实施方式中，对在镍基底打印的电铸掩模使用UV灯照射进行固化处理。
在本发明的一些实施方式中，步骤1中双光子聚合微纳3D打印使用的打印材料为UV固化光刻胶、水凝胶、纳米复合树脂材料等。
在本发明的一些实施方式中，步骤2中纳秒脉冲微细电铸的脉冲宽度为8-12ns，占空比为1:8-12。选择高频、窄脉宽、大占空比脉冲进行电铸是因为脉宽T on的大小就是双电层的充电时间的长短。脉宽窄，则充电时间短，电流密度小的区域来不及充电或者没有完全充电就立即进入放电阶段，即脉间T off阶段。从而电流密度小的区域电化学反应弱或者根本没有进行电化学反应，电化学影响区较小，晶粒成长被限定在相对较小的区域内，定域性极大提高。
在本发明的一些实施方式中，步骤3中电铸液为氨基磺酸镍、阳极活化剂、缓冲剂、防针孔剂的混合物。优选的，阳极活化剂为氯化镍；优选的，缓冲剂为硼酸；优选的，防针孔剂为十二烷基硫酸钠；优选的电铸液中氨基磺酸镍的浓度为300～450g/L；优选的，电铸液中阳极活化剂的浓度为10～15g/L；优选的，电铸液中缓冲剂的浓度为30～35g/L；优选的，电铸液中防针孔剂的浓度为0.1～0.15g/L。
在电铸液中加入阳极活化剂氯化镍改善阳极的溶解性,提高导电率，改善溶液的分散能力；加入缓冲剂硼酸减缓阳极区溶液PH值的增加，使得能够使用较高的阳极电流密度而不致在阳极上析出氢氧化物，同时还具有提高阴极极化和改善铸层性质的作用；加入防针孔剂十二烷基硫酸钠降 低溶液的表面张力,使氢气泡不易在阴极表面停留,从而防止针孔的形成。
在本发明的一些实施方式中，电铸沉积层的厚度为0.5-1.5cm；优选为1cm。
在本发明的一些实施方式中，电铸过程中电铸液的温度50～55℃。
在本发明的一些实施方式中，电铸过程中电铸液的pH为3.8～4.4。
在本发明的一些实施方式中，电铸过程中利用循环泵对电铸液进行冲液，冲液的速度为1-1.5m/s。冲液是将电铸液吸出经过循环泵后再排到电铸池中。能够对镀液起到搅拌作用，降低浓差极化并使加工过程中附着在电极表面的气泡迅速排出。
在本发明的一些实施方式中，电铸的电流密度为0.5～3.0A/m 2，电铸时间为80-120h；优选的，电铸时间为100h。采用较小的电流密度可以降低表面粗糙度，控制电铸时间在上述范围内，可以更好的避免表面粗糙度过大。
在本发明的一些实施方式中，电铸之后得到的模具进行清洗的后处理，具体为：利用去离子水进行超声震洗，处理的时间为5-10min，然后进行干燥。
在本发明的一些实施方式中，清洗之后进行去应力后处理，具体为：采用真空退火的方法进行处理；优选的，退火的温度为350-450℃，退火的时间为1.5-2.5h。退火后金属镍母模随炉冷却至室温。退火后的镍模板内应力有了很大的减少，模板变得平整，适合后续工艺。
在本发明的一些实施方式中，步骤3中最后得到的软模具的PDMS层的厚度为10～50μm，PET层厚度100～400μm。在制备得到的复合软模具中PDMS图形层是通过多次涂覆得到，PET层作为PDMS软模具的支撑层。在PET上实现得到多个PDMS图形层。
在本发明的一些实施方式中，步骤3涂布PDMS之前对母模进行抗黏附处理，具体步骤为：利用丙酮、异丙醇及去离子水分别进行超声处理、干燥；
然后将母模放在十七氟癸基三氯硅烷的异辛烷溶液中进行浸泡；
浸泡后分别用异辛烷、丙酮、异丙醇进行超声清洗；
然后在镍母模表面涂覆脱模剂。
优选的，超声清洗的时间为15-25min，浸泡的时间为25-35min。
优选的，十七氟癸基三氯硅烷的异辛烷溶液的浓度为质量分数0.5-1.5％。
优选的，脱模剂为CF 3(CF 2) 7CH 2CH 2PO 2(OH) 2。优选的，脱模剂的涂覆采用旋涂的方式，旋涂的速度为1800-2200r/min，旋涂的时间为35-45s。
在本发明的一些实施方式中，PET层的贴覆的过程中采用渐进式顺序线接触施压的操作方式。这种操作方式可以尽可能消除压印过程中产生的气泡缺陷。
在本发明的一些实施方式中，压印的操作条件为：压印力为50-500N，加热温度为50～90℃。压印后PDMS完全固化。压印的过程确保图形层和支撑层更好的粘附在一起，保证图形层和母模之间是完全共形接触，减少加热过程中产生的气泡缺陷。
第二方面，本发明还提供了利用上述AR衍射光波导压印模具的制备方法制备得到的软模具。
第三方面，本发明还提供了上述软模具在表面浮雕倾斜光栅领域中的应用。
本发明一个或多个技术方案具有以下有益效果：
(1)双光子聚合微纳3D打印技术的打印精度高，能够精确打印亚微尺度的各种结构，满足了衍射光波导的精度要求，解决了LIGA等工艺精度不足的问题。
(2)生产成本低、效率高。运用双光子聚合微纳3D打印制造电铸掩模，能够在金属基底上直接成型，克服了传统LIGA工艺掩模版制作困难，需要用高能量X射线源——同步回旋加速器，这一昂贵的设施和复杂的掩模制造工艺的问题，极大地降低了制造成本，提高了制造效率。
(3)能够实现任意形状、大深宽比、大倾角倾斜光栅模具结构的制造。传统的制作模具的方法对于制作衍射光波导倾斜光栅电铸掩模存在很多 不足，例如LIGA技术需要昂贵的同步辐射射线和特制的掩模版，UV-LIGA技术制作掩模的精度受限，很难实现任意形状、大深宽比、大倾角微结构的制作。本发明提出的方法，采用双光子聚合微纳3D打印技术打印电铸掩模，对于倾斜光栅电铸掩模的设计和制造都没有约束，尤其能实现任意形状表面浮雕倾斜光栅和大深宽比倾斜光栅的结构的制造。
(4)纳秒脉冲电铸定域性强、精度高。本发明所制造的倾斜光栅压印模具对制造精度要求非常高，为了获得极高的加工精度，定域电沉积加工材料的生长应当有意识的控制在一定的区域内。而在电铸加工过程中，电铸液中电流密度在两极之间的分布是大小不一的，越靠近电极中心，电流密度越高。因此，在电极中心区域内，铸层成长速度要明显快于远离中心的区域。当在阳极和阴极间加上电压时，溶液中的金属表面形成双电层。当两极之间通上脉冲电压时，双电层(相当于一个电容器)即被周期性的充电和放电。电流密度大的地方，双电层电容充电时间短，而电流密度小的地方，需要的充电时间长。而在纳秒脉冲电流电铸加工过程中，脉宽T on的大小就是双电层的充电时间的长短，脉宽窄，则充电时间短，电流密度小的区域来不及充电或者没有完全充电就立即进入放电阶段，即脉间T off阶段。从而电流密度小的区域电化学反应弱或者根本没有进行电化学反应，电化学影响区较小，晶粒成长被限定在相对较小的区域内，定域性极大提高，从而实现亚微尺度高精度制造压印模具。
(5)纳秒脉冲电铸能得到致密的、导电率高的沉积层。金属沉积时的结晶形态和生长方式与阴极极化过电位密切相关，随着过电位的增长，电结晶的临界尺寸减小，晶核形成的几率增长，晶粒数目增多，使晶粒变细，铸层致密。而极化包括两个部分，浓差极化和电化学极化。浓差极化对金属沉积有弊无利，而电化学极化则使结晶细致。在脉冲电流的脉冲间隔时间内，阴极界面处的金属离子得以迅速补充，降低了扩散层的有效厚度，减小浓差极化，使得可以使用高于常规直流电沉积的电流密度，从而可以产生更高的电化学极化，达到细化晶粒，提高铸层致密度的效果。
(6)纳秒脉冲电铸有利于降低浓差极化,提高阴极电流密度。脉冲电流波形的特点是：在接通瞬间可以在电极处得到较直流高得多的电流密度, 提高电极的电化学极化,产生细致的铸层；断开后,电极迅速恢复至原状,阴极界面处的金属离子得以迅速补充，降低了扩散层的有效厚度，减小浓差极化。电铸液中的粒子在高频脉冲电场中不间断的运动与停止，产生高频振动，对电铸液起到了一个搅拌的作用，减小浓差极化且使吸附在阴极表面的杂质、氢气等脱附,有利于减少缺陷,提高铸层的纯度，同时脉冲间歇为电铸液温度下降和电铸产物的排出提供了时间,使电铸液迅速得到更新，能够改善流场特性，使电极表面的浓差极化减小。
(7)实现大面积(大尺寸)表面浮雕倾斜光栅纳米压印模具高精度低成本快速制造。
(8)工艺简单，设备成本低。
(9)本发明既可用于表面浮雕倾斜光栅衍射光波导纳米压印模具的制造，也适合其它类型衍射光波导(例如纳米柱式衍射光波导)纳米压印模具的制造。
说明书附图
构成本发明的一部分的说明书附图用来提供对本申请的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明实施实例提供的打印的电铸掩模示意图；
图2为本发明实施实例提供的双光子聚合微纳3D打印机原理示意图；
图3为本发明实施实例提供的电铸镍金属模具示意图；
图4为本发明实施实例提供的镍母模复制示意图；
图5为本发明实施实例提供的压印复合软模具示意图；
图6为本发明实施实例提供的制造AR衍射光波导压印模具流程图；
其中，1、镍板，2、光刻胶，3、光源，4、分色镜，5、物镜，6、衬底，7、XY运动台，8、控制与反馈系统，10、电铸镍模具，11、PET，12、PDMS图形层。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的 说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
实施实例
图1是本发明所要制造的一种电铸掩模示意图以及其能够制造的衍射光波导(表面浮雕倾斜光栅)的具体参数，其中倾斜角度Φ、槽深(相对深度)h、线宽、填充因子(光栅宽度c/周期ρ)如图1所述。本实施实例所要制造的金属模具的参数：倾斜角度35°、槽深330nm、线宽220nm、周期405nm、填充因子(系数)55％。镍板1表面设置光刻胶2。
以实施实例所述的倾斜光栅纳米压印模具为例，结合图1-图6，具体说明基于提出方法和设备制造倾斜光栅纳米压印模具的具体过程。
步骤1：打印电铸掩模。
使用双光子聚合微纳3D打印机(Nanoscribe公司的Photonic Professional GT2)在镍板上打印电铸掩模，镍板尺寸为30×20×1mm，打印材料选用IP-L 780。
具体工艺过程：
(1)预处理。首先对镍板磨光、抛光处理，去掉表面的各种宏观缺陷、腐蚀痕、划痕、毛刺、砂眼、气泡、氧化皮及锈等，降低表面粗糙度，提高金属的耐蚀性，提高金属基底表面的平整度和光洁度。然后根据本实施例所确定的倾斜光栅电铸掩模的几何形状和尺寸，利用数据前处理软件将其转换成加工文件；随后，将加工文件输入到双光子聚合微纳3D打印机Photonic Professional GT2，将打印机的料盒中装满打印材料IP-L 780。将镍金属板作为打印基底放在打印机的打印平台上，并开启双光子聚合微纳3D打印机PhotonicProfessional GT2。
(2)打印电铸掩模。根据设置的打印工艺参数，逐层打印，打印1μm厚的电铸掩模，为节约成本，同时不大于电铸过程中的初始加工间隙，打 印电铸掩膜厚度不宜过大，考虑到双光子聚合微纳3D打印的精度为纳米级，因此掩膜厚度定为1μm。其打印原理如图2所示：光源3发出的光通过分色镜4射入物镜5，通过物镜5射入到衬底6上，控制与反馈系统8调控XY运动台7的移动，进而控制衬底6的移动。
(3)后处理。从双光子聚合微纳3D打印机Photonic Professional GT2的打印平台上取下打印好掩模的镍板，去除未固化的聚合物，使用UV灯照射进一步进行后固化处理。制备出带有电铸掩模的镍金属板。
步骤2：电铸倾斜光栅金属模具。
金属模具材料选用镍。基于步骤1在镍金属板上打印的电铸掩模，采用微电铸的设备为DZY-III型双槽双路精密电铸机、NPG-18/3500N型纳秒脉冲电源，结合纳秒脉冲精密微电铸工艺制造镍模具的方法：
(1)预处理。将步骤1制得的带有掩模的镍金属板连接电铸设备的阴极，纯镍板连接阳极，放置在300g/L的氨基磺酸镍电铸液中。在电铸液中加入阳极活化剂氯化镍10g/L，改善阳极的溶解性,提高导电率，改善溶液的分散能力；加入缓冲剂硼酸30g/L，减缓阳极区溶液PH值的增加，使得能够使用较高的阳极电流密度而不致在阳极上析出氢氧化物，同时还具有提高阴极极化和改善铸层性质的作用；加入防针孔剂十二烷基硫酸钠0.1g/L，降低溶液的表面张力，使氢气泡不易在阴极表面停留，从而防止针孔的形成。
(2)电铸。开启微细电铸设备，用脉冲宽度为10ns，占空比1:10的纳秒脉冲电源进行电铸，电铸沉积层厚度为1cm。通过恒温系统将电铸液的温度控制在50℃，利用PH值监测系统将PH值控制在4，并利用泵进行冲液，冲液速度为1.3m/s，对镀液起到搅拌作用，降低浓差极化并使加工过程中附着在电极表面的气泡迅速排出。为了避免表面粗糙度过大，电流密度为2.5A/dm 2。电铸时间约100h。选择高频、窄脉宽、大占空比脉冲进行电铸是因为脉宽T on的大小就是双电层的充电时间的长短，脉宽窄，则充电时间短，电流密度小的区域来不及充电或者没有完全充电就立即进入放电阶段，即脉间T off阶段。从而电流密度小的区域电化学反应弱或者根本没有进行电化学反应，电化学影响区较小，晶粒成长被限定在相对较小的区域内，定域性极大提高。
(3)后处理。如图3所示，将电铸镍模具10从镍板1上取下，用去离子水超声震洗10min，完全去除镍模上残留的材料，并用氮气吹干。随后，对倾斜光栅结构模具进行表面处理，减小表面粗糙度，提高倾斜光栅表面质量。为了减小金属镍母模因残余内应力而存在弯曲的问题，对制造的金属镍母模进行了去应力后处理，采用真空退火，温度为400℃，时间为2小时，退火后金属镍母模随炉冷却至室温。退火后的镍模板内应力有了很大的减少，模板变得平整，适合后续工艺。
步骤3：制备压印复合软模具。
以步骤2制造的倾斜光栅金属镍模具作为母模，在母模上涂布图形层聚合物PDMS，将PET贴覆到PDMS上，对模具进行压印、固化，然后采用揭开式脱模使复制得到的PDMS图形层脱离金属镍母模，得到一次复制的软模具(PDMS粘附在PET上)，重复涂覆PDMS、贴覆PET(在同一张PET不同位置贴覆)、压印、固化、揭开式脱模的步骤，最终制得若干PDMS软模具阵列排布在一张PET上的复合软模具。
本实施例制造的压印复合软模具：PDMS为图形层，其厚度是10～50μm；PET作为支撑层，其厚度100～400μm。基于步骤2制造金属镍母模，进行循环复制，将复制的若干PDMS软模具阵列排布在100×100mmPET基底上，制作一种双层复合软模具的工艺过程：
(1)预处理。首先对镍母模进行抗黏附处理：①用丙酮、异丙醇及去离子水各超声处理20min，然后将母模置于热板(或加热箱)上烘干；②以异辛烷为溶剂，配置1％浓度的十七氟癸基三氯硅烷溶液(FDTS)，静置15min，然后将母模放入其中浸泡30min；③分别用异辛烷、丙酮、异丙醇于超声条件下各清洗20min。然后在镍母模表面滴加2ml脱模剂(脱模剂材料为：CF 3(CF 2) 7CH 2CH 2PO 2(OH) 2，以2000r/min的转速旋涂40s，在母模图形表面形成一层抗黏附层，进一步降低母模表面能。然后采用旋涂或者狭缝涂布等精密涂布方式在母模表面涂布图形层聚合物PDMS，厚度10-50微米，并进行抽真空处理，排出PDMS内部的气泡。对支撑层材料PET表面进行氧等离子轰击处理，提高PET与PDMS之间的黏结力，最后将支撑层材料PET采用“渐进式”顺序线接触施压贴覆到PDMS上，尽可能消除压印过程产生的气泡缺陷。
(2)镍母模的复制。将铺放好PET的模具放到加热板上，施加均匀压印力，压印力是100N，加热温度为90℃，直到PDMS完全固化。为了确保图形层和支撑层更好的粘附在一起，保证图形层和母模之间是完全共形接触，减少加热过程中产生的气泡缺陷。最后采用揭开式脱模，实现镍母模的一次复制(如图4所示)。
(3)压印软模具的制造。不断重复上述两个步骤6次，在上一步骤揭下来的PET11上的不同位置进行镍母模的复制。最终在100×100mmPET上得到阵列排布的6个PDMS软模具，得到PDMS图形层12，如图5所示。该软模具能够实现表面浮雕倾斜光栅高效低成本批量化压印。
双层复合软模具既能依靠自身的柔性实现与非平整表面/衬底大面积完全共形接触，又能通过特征层结构的小变形来确保压印图形的精度和质量，实现大面积纳米压印所需“软”与“硬”的完美结合；所制作的双层复合软模具(一张PET上排布多个PDMS软模具)能够实现一次压印后大面积制作多个倾斜光栅微结构，并且质地柔软，不易被破坏，能够被多次使用，降低模具的制造成本。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种AR衍射光波导压印模具的制备方法，其特征在于：具体步骤为：
    步骤1：打印电铸模板：采用双光子聚合微纳3D打印机在镍基底上打印电铸掩模；
    步骤2：电铸倾斜光栅金属模具：利用纳秒脉冲微细电铸，对步骤1得到的带有掩模的镍基板进行电铸，得到倾斜光栅金属镍模具；
    步骤3：制备压印复合软模具：以步骤2制造的倾斜光栅金属镍模具作为母模，在母模上涂布图形层聚合物PDMS，将PET贴覆到PDMS上，对模具进行压印，采用揭开式脱模除去PET层，得到一次复制的软模具，重复涂覆PDMS、贴覆PET、压印、揭开式脱模的步骤，保留最外层的PET层得到复合软模具。
  2. 如权利要求1所述的AR衍射光波导压印模具的制备方法，其特征在于：在所述打印电铸掩模之前，还包括对镍基底进行预处理，所述预处理的方法包括：对镍基底进行磨光、抛光处理。
  3. 如权利要求1所述的AR衍射光波导压印模具的制备方法，其特征在于，所述打印电铸模板具体包括：
    利用UV固化光刻胶、水凝胶或纳米复合树脂材料在镍基底上打印电铸掩膜，所述电铸掩模的厚度为1μm；
    对打印电铸掩模后的镍基底进行固化处理。
  4. 如权利要求1所述的AR衍射光波导压印模具的制备方法，其特征在于，所述电铸倾斜光栅金属模具包括：
    将所述带有掩模的镍基板置入电铸液中，所述电铸液为氨基磺酸镍、阳极活化剂、缓冲剂、防针孔剂的混合物；所述阳极活化剂为氯化镍，所述缓冲剂为硼酸，所述防针孔剂为十二烷基硫酸钠；所述电铸液中氨基磺酸镍的浓度为300～450g/L；所述电铸液中阳极活化剂的浓度为10～15g/L；所述电铸液中缓冲剂的浓度为30～35g/L；所述电铸液中防针孔剂的浓度为0.1～0.15g/L；
    利用微细电铸设备对所述带有掩模的镍基板进行电铸，得到倾斜光栅 金属镍模具。
  5. 如权利要求4所述的AR衍射光波导压印模具的制备方法，其特征在于，在利用微细电铸设备对所述带有掩模的镍基板进行电铸时，
    电铸沉积层的厚度为0.5-1.5cm；
    或，电铸过程中电铸液的温度50～55℃；
    或，电铸过程中电铸液的pH为3.8～4.4；
    或，电铸过程中利用泵对电铸液进行冲液，冲液的速度为1-1.5m/s；
    或，电铸的电流密度为0.5～3.0A/m 2，电铸时间为80-120h。
  6. 如权利要求4所述的AR衍射光波导压印模具的制备方法，其特征在于，所述得到倾斜光栅金属镍模具后，还包括进行清洗的后处理：利用去离子水进行5-10min超声震洗后进行干燥；
    干燥后进行去应力后处理，具体为：采用真空退火的方法进行处理，退火的温度为350-450℃，退火的时间为1.5-2.5h。
  7. 如权利要求1所述的AR衍射光波导压印模具的制备方法，其特征在于，所述贴覆PET包括：采用渐进式顺序线接触施压的操作方式进行贴覆操作；
    所述压印的操作条件为：压印力为50-500N，加热温度为50～90℃；
    所述复合软模具的PDMS层的厚度为10～50μm，PET层厚度100～400μm。
  8. 如权利要求1所述的AR衍射光波导压印模具的制备方法，其特征在于，在母模上涂布图形层聚合物PDMS之前，还包括对所述母模进行抗黏附处理，具体包括：利用丙酮、异丙醇及去离子水分别进行超声处理、干燥，所述超声清洗的时间为15-25min；
    将所述母模放在十七氟癸基三氯硅烷的异辛烷溶液中进行浸泡，浸泡的时间为25-35min，所述十七氟癸基三氯硅烷的异辛烷溶液的浓度为质量分数0.5-1.5％；
    浸泡后分别用异辛烷、丙酮、异丙醇进行超声清洗；
    清洗后在所述母模表面涂覆脱模剂，所述脱模剂为 CF 3(CF 2) 7CH 2CH 2PO 2(OH) 2，所述脱模剂的涂覆采用旋涂的方式，旋涂的速度为1800-2200r/min，旋涂的时间为35-45s。
  9. 采用如权利要求1-8任一所述的AR衍射光波导压印模具的制备方法AR衍射光波导压印模具的制备方法制备得到的软模具。
  10. 如权利要求9所述的软模具在表面浮雕倾斜光栅领域中的应用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702249A (zh) * 2022-03-29 2022-07-05 青岛理工大学 基于复合微纳增材制造大尺寸电加热玻璃批量生产系统

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CN113156756B (zh) * 2021-03-18 2022-03-11 苏州莱科光学科技有限公司 一种超短焦抗光幕制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101101441A (zh) * 2007-08-07 2008-01-09 山东大学 大面积周期阵列三维微结构制备方法
US20160161647A1 (en) * 2011-01-14 2016-06-09 Jx Nippon Oil & Energy Corporation Method for producing mold for minute pattern transfer, method for producing diffraction grating using the same, and method for producing organic el element including the diffraction grating
CN110927873A (zh) * 2019-12-25 2020-03-27 青岛五维智造科技有限公司 一种批量化生产ar衍射光波导的方法和设备
CN112026073A (zh) * 2020-08-24 2020-12-04 青岛理工大学 一种ar衍射光波导压印模具的制备方法及软模具和应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675083A (en) * 1986-04-02 1987-06-23 Hewlett-Packard Company Compound bore nozzle for ink jet printhead and method of manufacture
JPH10278281A (ja) * 1997-04-04 1998-10-20 Citizen Watch Co Ltd インクジェットプリンターヘッドの製造方法
CN101205054B (zh) * 2007-12-11 2011-03-30 山东大学 一种微型金属镍模具制作方法
CN101900936A (zh) * 2009-05-26 2010-12-01 鸿富锦精密工业（深圳）有限公司 压印模具及其制作方法
KR101299556B1 (ko) * 2011-08-17 2013-08-23 전유종 스크린 인쇄를 위한 금속제판 제조방법
CN103572341B (zh) * 2013-09-23 2016-01-20 江苏大学 激光光管电极的电化学复合沉积制造方法与装置
CN104181770B (zh) * 2014-09-10 2017-10-20 青岛理工大学 一种基于4d打印和纳米压印制造微纳复合结构的方法
CN105374467B (zh) * 2015-10-23 2017-03-22 苏州大学 纳米转印方法及纳米功能器件
CN108162425B (zh) * 2017-12-22 2020-08-28 青岛理工大学 一种大尺寸无拼接微纳软模具制造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101101441A (zh) * 2007-08-07 2008-01-09 山东大学 大面积周期阵列三维微结构制备方法
US20160161647A1 (en) * 2011-01-14 2016-06-09 Jx Nippon Oil & Energy Corporation Method for producing mold for minute pattern transfer, method for producing diffraction grating using the same, and method for producing organic el element including the diffraction grating
CN110927873A (zh) * 2019-12-25 2020-03-27 青岛五维智造科技有限公司 一种批量化生产ar衍射光波导的方法和设备
CN112026073A (zh) * 2020-08-24 2020-12-04 青岛理工大学 一种ar衍射光波导压印模具的制备方法及软模具和应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702249A (zh) * 2022-03-29 2022-07-05 青岛理工大学 基于复合微纳增材制造大尺寸电加热玻璃批量生产系统
CN114702249B (zh) * 2022-03-29 2024-05-14 青岛理工大学 基于复合微纳增材制造大尺寸电加热玻璃批量生产系统

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