CN116794929A - Stepping imprinting composite boss template and preparation method thereof - Google Patents
Stepping imprinting composite boss template and preparation method thereof Download PDFInfo
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- CN116794929A CN116794929A CN202310750584.3A CN202310750584A CN116794929A CN 116794929 A CN116794929 A CN 116794929A CN 202310750584 A CN202310750584 A CN 202310750584A CN 116794929 A CN116794929 A CN 116794929A
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- 238000002360 preparation method Methods 0.000 title abstract description 11
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- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010146 3D printing Methods 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 55
- 229910052710 silicon Inorganic materials 0.000 claims description 55
- 239000010703 silicon Substances 0.000 claims description 55
- 229920002635 polyurethane Polymers 0.000 claims description 54
- 239000004814 polyurethane Substances 0.000 claims description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 41
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- 238000004519 manufacturing process Methods 0.000 claims description 19
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- 238000005516 engineering process Methods 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- -1 acrylic ester Chemical class 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003848 UV Light-Curing Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 20
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 20
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 20
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 20
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- 239000003999 initiator Substances 0.000 description 5
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- General Physics & Mathematics (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
The application provides a stepping imprinting composite boss template and a preparation method thereof; the method is mainly used for step-by-step imprinting lithography, and can flexibly prepare a step-by-step imprinting boss template; the template can be easily replaced to meet the stepping imprinting requirement; the step-by-step imprinting composite boss template can be rapidly prepared by adopting a 3D printing, pouring and adhesive sucking method, and the boss consists of a transparent rigid supporting layer, a transparent elastic buffer layer and a transparent template imprinting layer respectively; the high light transmittance can greatly improve the utilization rate of UV light, and is energy-saving and environment-friendly; meanwhile, the rigid layer of the composite boss template provides support and transmission of imprinting force, the elastic layer provides uniform distribution and buffering of force, and the template layer provides transmission and replication of a structure. Therefore, the application can realize the preparation and replacement of the stepping imprinting composite boss template, has good universality and has important research significance and engineering application value.
Description
Technical Field
The application relates to the technical field of micro-nano processing and manufacturing, in particular to a stepping imprinting composite boss template and a preparation method thereof.
Background
In the field of semiconductors, the size of micro-nano devices is continuously developed towards smaller directions, the processing difficulty is higher, and although optical lithography is the mainstream lithography technology of micro-nano manufacturing, the optical lithography is still limited by the diffraction limit of exposure wavelength, so that the resolution is improved, the wavelength of a light source is shortened, the numerical aperture is improved, the exposure mode is improved, and the like, so that the optical lithography is the main direction of research by researchers in various countries. The nano-imprint technology has the characteristics of high resolution, low cost, few process links, high speed, capability of preparing various nano-scale structures and the like, and becomes a powerful competitor of the photoetching technology. The advantages of nanoimprint technology include relatively simple and efficient process (large-area production, high productivity), low cost, reusable imprint template, and no need of complex optical system such as optical exposure or electromagnetic focusing system such as electron beam exposure. Moreover, since there is no diffraction phenomenon in optical exposure and no scattering phenomenon in electron beam exposure, the nanoimprint technique can produce high-resolution patterns with a resolution of 5nm or less.
The step-by-step imprinting is compatible with a large-size silicon process, the manufacturing cost of the stamp is low, the figure quality is superior to the optical exposure result of the same size, and meanwhile, the equipment cost and the operation cost are greatly reduced compared with the optical exposure. However, since the transfer of the microscopic pattern in the step-by-step imprinting is completed by using a boss template, the manufacture of the high-precision, high-uniformity, high-flatness and high-fidelity imprinting template is one of the core problems of the whole process, and in the boss template manufacturing process, how to select template materials and control the process conditions in the template manufacturing process are important points of the whole boss template manufacturing.
Disclosure of Invention
The application aims to provide a stepping imprinting composite boss template and a preparation method thereof, which are used for overcoming the defects in the prior art.
In order to achieve the above purpose, the present application provides the following technical solutions:
the application discloses a stepping imprinting composite boss template which is formed by compositing a transparent rigid supporting layer, a transparent elastic buffer layer and a transparent template imprinting layer; the transparent elastic buffer layer is positioned between the transparent rigid support layer and the transparent template imprinting layer; the surface of the transparent template imprinting layer is provided with a nano-size structure; the hardness of the transparent rigid supporting layer is 85-95 HD; the hardness of the transparent elastic buffer layer is 7-10 HD; the hardness of the transparent template imprinting layer is 25-30 HD; and the transparent template imprinting layer adopts fluorine-based polyurethane acrylic ester.
Preferably, the transparent rigid supporting layer adopts one of acrylic plate, silica glass and quartz glass; the transparent elastic buffer layer adopts aliphatic polyurethane acrylic ester or aliphatic acrylic ester.
Preferably, the transparent rigid support layer has a light transmittance of greater than 90%; the light transmittance of the transparent elastic buffer layer is more than 85%; the light transmittance of the transparent template imprinting layer is more than 85%.
Preferably, the contact angle of the transparent template imprinting layer is greater than 120 °.
The application also discloses a preparation method of the stepping imprinting composite boss template, which comprises the following steps:
s1, manufacturing a pattern outline for pouring a transparent elastic buffer layer on a silicon wafer through a 3D printing technology;
s2, pouring a transparent elastic buffer layer on the pattern outline in the step S1, covering a transparent rigid support layer after degassing treatment, and performing ultraviolet curing to obtain a preliminary template;
s3, removing the preliminary template, and placing one surface of the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate to adsorb the transparent template imprinting layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template, forming a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
Preferably, the step S1 specifically includes the following sub-steps:
s11, cleaning the silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 15-30 min;
s12, evaporating a layer of silicon dioxide with the thickness of 10-50 nm after finishing the pattern contour by a 3D printing technology;
s13, placing the silicon wafer in a volume ratio of 3: 1-5: 1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 5% -20% into the absolute ethanol/water solution, adjusting the PH to 3.5-5.5, and reacting for 90-120 min at 65-85 ℃ to obtain a hydrophobic silicon wafer;
preferably, in step S2, a pretreatment is required before the transparent rigid support layer is covered: and cleaning the transparent rigid support layer, and then treating the transparent rigid support layer with oxygen plasma for 15-30 min.
Preferably, the step S3 specifically includes the following sub-steps:
s31, spin-coating fluorine-based polyurethane acrylate on a silicon wafer;
s32, removing the preliminary template from the pattern outline in the step S1, and placing one surface of the elastic buffer layer on the silicon wafer in the step S31 for 10-20 min, so that the fluorine-based polyurethane acrylate is adsorbed in the crosslinked network of the elastic buffer layer.
The application has the beneficial effects that:
1. the fluorine-based polyurethane acrylic ester is adopted as the transparent template imprinting layer, and the fluorine-containing surface energy is lower, and the hardness is improved due to double bond crosslinking, so that the imprinting precision can be ensured, and the structure lower than 300 nanometers can be copied; the general PDMS material is softer, and the surface energy is lower than that of fluorine-based polyurethane acrylic ester, so that the structure of more than 300 nanometers can be copied;
2. the application adopts a hard-soft-hard composite form of a transparent rigid supporting layer, a transparent elastic buffer layer and a transparent template imprinting layer; the transparent rigid supporting layer provides support and transmission of imprinting force; the transparent elastic buffer layer provides even distribution and buffering of force; the transparent template imprinting layer provides for transfer and replication of the structure.
3. Through 3D printing technology, can design step-by-step impression boss pattern in a flexible way.
4. Different types of template molds, including metal, nonmetal and silicon rubber, can be duplicated, so that the requirement of stepping lithography is met;
5. the high light transmittance is adopted, so that the utilization rate of UV light can be greatly improved, and the energy conservation and environmental protection are realized;
6. the step imprinting composite boss template can be rapidly prepared by adopting a 3D printing, pouring and adhesive sucking method; the preparation and replacement of the stepping imprinting composite boss template can be realized, the universality is good, and the method has important research significance and engineering application value.
The features and advantages of the present application will be described in detail by way of example with reference to the accompanying drawings.
Drawings
FIG. 1 is a flow chart of a step imprint preparation process;
FIG. 2 is a schematic diagram of a step-by-step imprinting composite boss template imprinting;
FIG. 3 is a contact angle of a transparent template imprinting layer;
FIG. 4 is a schematic diagram of PDMS imprint results for comparison two;
fig. 5 is a schematic diagram of an imprinting result according to the first embodiment.
1-transparent rigid supporting layer, 2-transparent elastic buffer layer and 3-transparent template impression layer.
Detailed Description
The present application will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the detailed description and specific examples, while indicating the application, are intended for purposes of illustration only and are not intended to limit the scope of the application. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present application.
Referring to fig. 2, an embodiment of the present application provides a stepped imprinting composite boss template; is formed by compounding a transparent rigid supporting layer, a transparent elastic buffer layer and a transparent template imprinting layer; the transparent elastic buffer layer is positioned between the transparent rigid support layer and the transparent template imprinting layer; the surface of the transparent template imprinting layer is provided with a nano-size structure; the hardness of the transparent rigid supporting layer is 85-95 HD; the hardness of the transparent elastic buffer layer is 7-10 HD; the hardness of the transparent template imprinting layer is 25-30 HD; and the transparent template imprinting layer adopts fluorine-based polyurethane acrylic ester.
In a possible embodiment, the transparent rigid supporting layer is one of acrylic plate, silica glass and quartz glass; the transparent elastic buffer layer adopts aliphatic polyurethane acrylic ester or aliphatic acrylic ester.
In one possible embodiment, the transparent rigid support layer has a light transmittance of greater than 90%; the light transmittance of the transparent elastic buffer layer is more than 85%; the light transmittance of the transparent template imprinting layer is more than 85%.
Referring to fig. 3, in one possible embodiment, the contact angle of the transparent template imprinting layer is greater than 120 °.
Referring to fig. 1, the preparation method of the step-by-step imprinting composite boss template specifically comprises the following steps:
s1, manufacturing a pattern outline for pouring a transparent elastic buffer layer on a silicon wafer through a 3D printing technology;
s2, pouring a transparent elastic buffer layer on the pattern outline in the step S1, covering a transparent rigid support layer after degassing treatment, and performing ultraviolet curing to obtain a preliminary template;
s3, removing the preliminary template, and placing one surface of the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate to adsorb the transparent template imprinting layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form nano-sized structures (the structures are arranged on the template, the structures are prepared by using EBL, ICP and other processes), the structures can be filled with liquid fluorine-based polyurethane acrylate, and then the structures can be copied by curing and stripping, so that the material is required to have low surface energy and certain mechanical strength), and separating to obtain the stepping imprinting composite boss template after UV curing.
In a possible embodiment, step S1 specifically comprises the following sub-steps:
s11, cleaning the silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 15-30 min;
s12, evaporating a layer of silicon dioxide with the thickness of 10-50 nm after finishing the pattern contour by a 3D printing technology;
s13, placing the silicon wafer in a volume ratio of 3: 1-5: 1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 5% -20% into the absolute ethanol/water solution, adjusting the PH to 3.5-5.5, and reacting for 90-120 min at 65-85 ℃ to obtain a hydrophobic silicon wafer;
in a possible embodiment, in step S2, a pretreatment is required before the transparent rigid support layer is covered: and cleaning the transparent rigid support layer, and then treating the transparent rigid support layer with oxygen plasma for 15-30 min.
In a possible embodiment, step S3 specifically comprises the following sub-steps:
s31, spin-coating fluorine-based polyurethane acrylate on a silicon wafer;
s32, removing the preliminary template from the pattern outline in the step S1, and placing one surface of the elastic buffer layer on the silicon wafer in the step S31 for 10-20 min, so that the fluorine-based polyurethane acrylate is adsorbed in the crosslinked network of the elastic buffer layer.
In one possible embodiment, the preparation of the transparent rigid support layer plus the transparent elastic buffer layer: dissolving 184 initiator in butyl acrylate, then adding 50-70% of aliphatic polyurethane acrylate, and uniformly stirring; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid support layer and the transparent elastic buffer layer are tightly attached together.
Embodiment one:
in the embodiment, the transparent rigid supporting layer adopts silica glass, the light transmittance is 94%, the hardness is 90HD, and the surface energy is 52dynes/cm; the transparent elastic buffer layer adopts 70% aliphatic polyurethane acrylate, the light transmittance is 85%, the hardness is 9HD, and the surface energy is 51dynes/cm; the transparent template imprinting layer adopts 100% fluorine-based polyurethane acrylate, the light transmittance is 86%, the hardness is 30HD, and the surface energy is 15dynes/cm;
s1, cleaning a silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 15min; evaporating a layer of 10 nm-thick silicon dioxide after finishing the pattern contour by a 3D printing technology; placing a silicon wafer in a volume ratio of 3:1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 5%, regulating the PH to 3.5, and reacting for 90min at 65 ℃ to obtain a hydrophobic silicon wafer;
s2, dissolving 184 initiator in butyl acrylate, then adding 70% of aliphatic polyurethane acrylate, and uniformly stirring; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid supporting layer and the transparent elastic buffer layer are tightly attached together; pretreatment is required before the transparent rigid support layer is covered: the transparent rigid support layer was cleaned and then treated with oxygen plasma for 15min.
S3, spin-coating fluorine-based polyurethane acrylate on the silicon wafer; removing the supporting layer and the elastic buffer layer, and placing the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate for 10min to enable the fluorine-based polyurethane acrylate to be adsorbed in the crosslinked network of the elastic buffer layer
S4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
In this embodiment, the transparent rigid support is selected to have rigidity and a high surface energy. The transparent elastic buffer layer can be ultraviolet cured and has high surface energy, and the template layer can be ultraviolet cured and has low surface energy. Referring to FIG. 5, the result of the imprint SEM of this example is that structures below 300 nm can be replicated; it can be seen that the structure is uniform, the structure accuracy is high (the outline is clear), and the residual layer is not substantially visible, or even, the residual layer is present (a typical feature of nanoimprinting is that in order to ensure that the nanostructure on the imprint template is not in contact with the substrate after imprinting, there is a residual nanoimprint layer between the structure of the template and the substrate, so-called residual layer; thus, an additional dry etching step is required to remove the residual layer during imprinting; thus, in this etching step, a thin residual layer of uniform thickness is essential for high fidelity transfer of the imprint pattern, reducing pattern lateral shrinkage and loss of critical dimension control.)
Embodiment two:
in the embodiment, the transparent rigid supporting layer adopts acrylic, the light transmittance is 94%, the hardness is 85HD, and the surface energy is 41dynes/cm; the transparent elastic buffer layer adopts 60% aliphatic acrylic ester, the light transmittance is 87%, the hardness is 8HD, and the surface energy is 48dynes/cm; the transparent template imprinting layer adopts 90% fluorine-based polyurethane acrylate (generally, 10% is volatile solvent such as propylene glycol monomethyl ether and isopropanol, mainly reduces viscosity while saving cost, and even can use 70% fluorine-based polyurethane acrylate; however, the solvent is likely to introduce pores, and pure glue can be used if the cost is not considered); the light transmittance is 87%, the hardness is 28HD, and the surface energy is 16dynes/cm;
s1, cleaning a silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 20min; evaporating a layer of 30 nm-thick silicon dioxide after finishing the pattern contour by a 3D printing technology; placing a silicon wafer in a volume ratio of 4:1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 12%, regulating the PH to 4.5, and reacting at 75 ℃ for 105min to obtain a hydrophobic silicon wafer;
s2, dissolving 184 initiator in butyl acrylate, then adding 60% of aliphatic polyurethane acrylate, and uniformly stirring; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid supporting layer and the transparent elastic buffer layer are tightly attached together; pretreatment is required before the transparent rigid support layer is covered: the transparent rigid support layer was cleaned and then treated with oxygen plasma for 20min.
S3, spin-coating fluorine-based polyurethane acrylate on the silicon wafer; removing the supporting layer and the elastic buffer layer, and placing the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate for 15min, so that the fluorine-based polyurethane acrylate is adsorbed in a crosslinked network of the elastic buffer layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
Embodiment III:
in the embodiment, the transparent rigid supporting layer adopts quartz glass, the light transmittance is 93%, the hardness is 93HD, and the surface energy is 54dynes/cm; the transparent elastic buffer layer adopts 50% aliphatic polyurethane acrylic ester, the light transmittance is 89%, the hardness is 7HD, and the surface energy is 46dynes/cm; the transparent template imprinting layer adopts 80% fluorine-based polyurethane acrylate, the light transmittance is 89%, the hardness is 26HD, and the surface energy is 18dynes/cm;
s1, cleaning a silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 30min; evaporating a layer of silicon dioxide with the thickness of 50nm after finishing the pattern contour by a 3D printing technology; placing a silicon wafer in a volume ratio of 5:1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 20%, regulating the PH to 5.5, and reacting at 75 ℃ for 120min to obtain a hydrophobic silicon wafer;
s2, dissolving 184 initiator in butyl acrylate, then adding 50% of aliphatic polyurethane acrylate, and uniformly stirring; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid supporting layer and the transparent elastic buffer layer are tightly attached together; pretreatment is required before the transparent rigid support layer is covered: the transparent rigid support layer was cleaned and then treated with oxygen plasma for 30min.
S3, spin-coating fluorine-based polyurethane acrylate on the silicon wafer; removing the supporting layer and the elastic buffer layer, and placing the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate for 20min, so that the fluorine-based polyurethane acrylate is adsorbed in a crosslinked network of the elastic buffer layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
Comparative example one:
in the comparative example, the transparent rigid support layer is made of quartz glass, the light transmittance is 93%, the hardness is 93HD, and the surface energy is 54dynes/cm; the transparent elastic buffer layer adopts PDMS, the light transmittance is 86%, the hardness is 10HD, and the surface energy is 23dynes/cm; the transparent template imprinting layer adopts 100% fluorine-based polyurethane acrylate, the light transmittance is 86%, the hardness is 30HD, and the surface energy is 15dynes/cm;
s1, cleaning a silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 30min; evaporating a layer of silicon dioxide with the thickness of 50nm after finishing the pattern contour by a 3D printing technology; placing a silicon wafer in a volume ratio of 5:1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 20%, regulating the PH to 5.5, and reacting at 75 ℃ for 120min to obtain a hydrophobic silicon wafer;
s2, uniformly stirring PDMS; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid supporting layer and the transparent elastic buffer layer are tightly attached together; pretreatment is required before the transparent rigid support layer is covered: the transparent rigid support layer was cleaned and then treated with oxygen plasma for 30min.
S3, spin-coating fluorine-based polyurethane acrylate on the silicon wafer; removing the supporting layer and the elastic buffer layer, and placing the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate for 20min, so that the fluorine-based polyurethane acrylate is adsorbed in a crosslinked network of the elastic buffer layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
According to the embodiment, the surface energy of the adopted aliphatic polyurethane acrylate material is 46-51 dynes/cm (46 in the first embodiment, 48 in the second embodiment, 51 in the third embodiment), and the surface energy of PDMS is 22-24 dynes/cm (23 in the first comparative embodiment), but in the nano-imprinting composite template, the elastic buffer layer needs to be used as a connecting layer between the rigid layer and the imprinting layer, and as the PDMS shows low energy, if the PDMS is used for connection, the phenomenon of loose connection and layer separation is necessarily caused; and the adoption of the aliphatic polyurethane acrylate can ensure the tight connection between the layers. Moreover, the elastic layer of the aliphatic polyurethane acrylate contains acrylate groups which are the same as the template layer, so that strong chemical connection exists; and the PDMS and the template layer can only be connected by physical adsorption.
Therefore, the PDMS material is adopted as the transparent elastic buffer layer, and the PDMS material is easy to separate due to low surface energy and poor adhesiveness; and thus is not suitable for use as an elastic buffer.
Comparative example two:
in the comparative example, the transparent rigid support layer is made of quartz glass, the light transmittance is 93%, the hardness is 93HD, and the surface energy is 54dynes/cm; the transparent elastic buffer layer adopts 50% aliphatic polyurethane acrylic ester, the light transmittance is 89%, the hardness is 7HD, and the surface energy is 46dynes/cm; the transparent template imprinting layer adopts PDMS, the light transmittance is 86%, the hardness is 10HD, and the surface energy is 23dynes/cm.
S1, cleaning a silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 30min; evaporating a layer of silicon dioxide with the thickness of 50nm after finishing the pattern contour by a 3D printing technology; placing a silicon wafer in a volume ratio of 5:1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 20%, regulating the PH to 5.5, and reacting at 75 ℃ for 120min to obtain a hydrophobic silicon wafer;
s2, dissolving 184 initiator in butyl acrylate, then adding 50% of aliphatic polyurethane acrylate, and uniformly stirring; pouring the transparent rigid support layer into a template subjected to hydrophobic treatment, covering the transparent rigid support layer subjected to plasma treatment on a pouring area, and curing by UV; at this time, the transparent rigid supporting layer and the transparent elastic buffer layer are tightly attached together; pretreatment is required before the transparent rigid support layer is covered: the transparent rigid support layer was cleaned and then treated with oxygen plasma for 30min.
S3, spin-coating PDMS on the silicon wafer; removing the supporting layer and the elastic buffer layer which are attached together, and placing the elastic buffer layer on a silicon wafer spin-coated with PDMS for 20min, so that the PDMS is adsorbed in a crosslinked network of the elastic buffer layer;
s4, placing the preliminary template adsorbed with PDMS on a die for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
Referring to fig. 4, in this comparative example, a PDMS material is used as a transparent template imprinting layer, which may result in low template precision due to insufficient hardness, while the template material requires low surface energy and has a certain rigidity to ensure imprinting precision. In nanoimprinting, the template layer requires a low surface energy, indeed, PDMS is useful as a template. However, PDMS is not sufficiently hard (soft), and therefore is easily deformed when the nano-structure is pressed, and thus, the imprint accuracy cannot be ensured, and is generally used only for a micro-structure. The hardness of the fluorine-based polyurethane acrylate adopted by the application is 26-30 HD, the surface energy is 15-18 dynes/cm, the surface energy of PDMS is 22-24 dynes/cm, the hardness is 8-10 HD, and the nano-scale imprinting precision cannot be ensured due to the relatively low hardness of PDMS.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the application.
Claims (8)
1. Step-by-step impression composite boss template: the method is characterized in that: is formed by compounding a transparent rigid supporting layer, a transparent elastic buffer layer and a transparent template imprinting layer; the transparent elastic buffer layer is positioned between the transparent rigid support layer and the transparent template imprinting layer; the surface of the transparent template imprinting layer is provided with a nano-size structure; the hardness of the transparent rigid supporting layer is 85-95 HD; the hardness of the transparent elastic buffer layer is 7-10 HD; the hardness of the transparent template imprinting layer is 25-30 HD; and the transparent template imprinting layer adopts fluorine-based polyurethane acrylic ester.
2. A stepped imprinting composite boss template according to claim 1, wherein: the transparent rigid supporting layer adopts one of an acrylic plate, silica glass and quartz glass; the transparent elastic buffer layer adopts aliphatic polyurethane acrylic ester or aliphatic acrylic ester.
3. A stepped imprinting composite boss template according to claim 1, wherein: the light transmittance of the transparent rigid support layer is more than 90%; the light transmittance of the transparent elastic buffer layer is more than 85%; the light transmittance of the transparent template imprinting layer is more than 85%.
4. A stepped imprinting composite boss template according to claim 1, wherein: the contact angle of the transparent template imprinting layer is larger than 120 degrees.
5. The method for preparing the stepping imprinting composite boss template according to claim 1, which is characterized by comprising the following steps:
s1, manufacturing a pattern outline for pouring a transparent elastic buffer layer on a silicon wafer through a 3D printing technology;
s2, pouring a transparent elastic buffer layer on the pattern outline in the step S1, covering a transparent rigid support layer after degassing treatment, and performing ultraviolet curing to obtain a preliminary template;
s3, removing the preliminary template, and placing one surface of the elastic buffer layer on a silicon wafer spin-coated with fluorine-based polyurethane acrylate to adsorb the transparent template imprinting layer;
s4, placing the initial template adsorbed with the fluorine-based polyurethane acrylate on a mould for manufacturing the template to form a nano-size structure, and separating to obtain the stepping imprinting composite boss template after UV curing.
6. The method for preparing a stepped imprinting composite boss template according to claim 5, wherein the step S1 specifically comprises the following sub-steps:
s11, cleaning the silicon wafer in advance, and then treating the silicon wafer with oxygen plasma for 15-30 min;
s12, evaporating a layer of silicon dioxide with the thickness of 10-50 nm after finishing the pattern contour by a 3D printing technology;
s13, placing the silicon wafer in a volume ratio of 3: 1-5: 1, adding a methacryloxypropyl trimethoxy silane solution with the mass fraction of 5% -20% into the absolute ethanol/water solution, adjusting the PH to 3.5-5.5, and reacting for 90-120 min at 65-85 ℃ to obtain the hydrophobic silicon wafer.
7. The method for preparing the stepping imprinting composite boss template according to claim 5, wherein: in step S2, pretreatment is required before the transparent rigid support layer is covered: and cleaning the transparent rigid support layer, and then treating the transparent rigid support layer with oxygen plasma for 15-30 min.
8. The method for preparing the stepping imprinting composite boss template according to claim 5, wherein: the step S3 specifically comprises the following sub-steps:
s31, spin-coating fluorine-based polyurethane acrylate on a silicon wafer;
s32, removing the preliminary template from the pattern outline in the step S1, and placing one surface of the elastic buffer layer on the silicon wafer in the step S31 for 10-20 min, so that the fluorine-based polyurethane acrylate is adsorbed in the crosslinked network of the elastic buffer layer.
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