Transferable film-based structured substrate

Abstract

Transferable nanopatterned substrates are disclosed. These substrates contain transfer carriers laminated to the structured surface of a multilayer structure. After transferring the structure, the transfer carriers can be removed without damaging the structured layer. Methods for manufacturing such transferable nanopatterned substrates are also disclosed.

Description

Technical Field

[0001] The present disclosure relates to film-based structured substrates. The design and structure of the structured substrates are configured to be transferable to rigid substrates such as glass. A method for manufacturing such transferable film-based structured substrates is also disclosed.

Summary of the Invention

[0002] Briefly stated, in one aspect, the present disclosure provides an article comprising: a skin layer having a first major skin surface and a second major skin surface; a structured substrate having a flat major surface adjacent to the second major skin surface and having a structured surface including a protruding surface and a recessed surface; wherein the structured substrate includes an anti-fouling layer, an inorganic layer, and a masking layer; and a transfer carrier including a lamination layer having a first lamination surface bonded to the protruding surface and the recessed surface.

[0003] In another aspect, the present disclosure provides a method comprising: on a support structure including a support layer and a skin layer having a first major skin surface bonded to the support layer, fabricating a structured substrate having a flat major surface bonded to a second major skin surface of the skin layer and having a structured surface including a protruding surface, a recessed surface, and a side surface connecting the protruding surface and the recessed surface; wherein the structured substrate includes an anti-fouling layer, an inorganic layer, and a masking layer; bonding a transfer carrier including a lamination layer to the protruding surface and the recessed surface; wherein the lamination layer is bonded to the masking layer; and separating the skin layer from the support layer; wherein the transfer carrier and the structured substrate remain bonded to the skin layer, forming a transferable structured substrate.

Brief Description of the Drawings

[0004] [Figure 1] FIG. 1 shows a structured substrate including protrusions.

[0005] [Figure 2] Figure 2 shows a structured substrate containing wells.

[0006] [Figure 3] Figure 3 shows a transferable structured substrate containing carriers.

[0007] [Figure 4] Figure 4 shows the transferable structured substrate with the support removed.

[0008] [Figure 5] Figure 5 shows a transferable structured substrate having an adhesive layer and an optional liner.

[0009] [Figure 6] Figure 6 shows a transferable structured substrate bonded to a rigid substrate.

[0010] [Figure 7] Figure 7 shows a structured substrate with protrusions bonded to a rigid substrate after the carriers have been removed.

[0011] [Figure 8] Figure 8 shows a structured substrate containing wells bonded to a rigid substrate with the carriers removed. [Modes for carrying out the invention]

[0012] The cost of gene sequencing depends on the disposable consumables required to operate the sequencing equipment. The consumables used for each sequencing run include chemical and biochemical reagents used to probe the unknown sample, and the flow cell on which the sequencing reaction takes place. Typically, these flow cells contain a glass or silicon substrate etched with 250–2000 nanometer (nm) nanowells. These wells are then filled with a hydrogel having a chemical composition selected to bind the target DNA sample.

[0013] Some gene sequencers use fluorescence imaging as a detection method, and nanowells allow for the densest possible arrangement of individual samples (i.e., unique clusters of DNA amplicons in each well) while remaining optically resolvable. Therefore, patterning of hydrogel-functionalized nanowells is necessary to achieve higher throughput per run compared to flow cells where DNA amplicon clusters are randomly seeded.

[0014] Currently, these nanopatterned substrates are manufactured using wafer-based photolithography, a method that involves numerous process steps performed in a batch process to generate nanowells, which are then selectively chemically functionalized to allow for filling of the wells with hydrogels, and a process to deposit an antifouling coating between the wells. These processes include vapor deposition, masking, etching, mask removal, chemical mechanical planarization (CMP), spin coating, and cleaning. As a result, the manufacturing cost of these patterned substrates individually is estimated to reach several thousand dollars per unit, making them a major factor in the overall sequencing kit cost.

[0015] International Publications WO2022 / 058845 A1 and WO2022 / 144626 describe nanopatterned substrates formed on flexible carrier films for use in chemical or biological assays. These carriers can have thicknesses greater than, for example, 15 micrometers to provide the desired mechanical stability for forming and processing nanostructures in a roll-to-roll process. Such films have been bonded to rigid substrates such as glass and silicon. However, depending on the thickness of the carrier film used, the autofluorescence of the carriers may interfere with fluorescence imaging and detection in gene sequencers. Furthermore, variations in the overall thickness of the substrate may necessitate changing the focal plane of the imaging instrument when scanning flow cells with large surface areas.

[0016] Therefore, there remains a need for robust processes for manufacturing film-based nanopatterned substrates, particularly cost-effective roll-to-roll processes. Furthermore, there is a need to provide film-based nanopatterned substrates that reduce or eliminate concerns regarding autofluorescence, thickness uniformity, or flatness. There is also a need for processes and structures that can be handled throughout the entire manufacturing and use process without damaging the nanopatterned features.

[0017] The method of this disclosure begins with the use of a support comprising a flexible support layer and a skin layer peelably bonded to the support layer. Prior art methods required a transparent, non-autofluorescent substrate. In this disclosure, these limitations are unnecessary because the support layer is removed before use, and therefore a wide range of substrate materials can be used. Examples of support layers include paper, metal foil, polymer films, and combinations thereof. Suitable polymer films include, for example, polyester, poly(meth)acrylate, polyamide, polycarbonate, polyolefin, cyclic olefin polymer (COP), cyclic olefin copolymer (COC), poly(meth)acrylate, polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide, polypropylene, polyethylene, high molecular weight fluorinated polymers (e.g., THV or PVDF), and silicone. The thickness of the support layer is not critical as long as the structure remains flexible, and since it is removed, it does not contribute to unwanted autofluorescence.

[0018] The skin layer is detachably bonded to the support layer. The adhesion force between the skin layer and the support layer needs to be low enough to cleanly peel the skin layer from the support layer without damaging the skin layer or the structure built on the skin layer. That is, the skin layer is a peelable skin layer. In some cases, the peeling force between the skin layer and the support layer is 25 g / cm or less, for example 20 or less, 15 or less, or 10 g / cm or less. In another example, the peeling force is at least 0.5 g / cm, for example at least 1, at least 2, or at least 5 g / cm. For example, in some cases, the peeling force is in the range of 0.5 to 25 g / cm, for example 1 to 20, 2 to 15, or 2 to 10 g / cm. The peeling force can be measured by standard test methods including 90-degree or 180-degree peel tests. To obtain the desired peeling force, the surface of the support layer can be treated using known materials and processes.

[0019] Since the skin layer remains as part of the article during use, a thin layer of a material that does not exhibit autofluorescence or has low autofluorescence is preferred. The skin layer may be thermoplastic or thermosetting. Examples of suitable peelable skin layers include polyester, poly(meth)acrylate, polyamide, polycarbonate, polyolefins (such as polyethylene and polypropylene), cyclic olefin polymers (COP), cyclic olefin copolymers (COC), polyurethane, high molecular weight fluorinated polymers (such as THV or PVDF), and those containing silicone.

[0020] While thicker skin layers can be used, in the present invention, thin skin layers can be used because the support layer provides the desired mechanical strength and stability during processing. In some cases, the skin layer may be 15 micrometers or less in thickness, for example, 10 micrometers or less, 5 micrometers or less, 2 micrometers or less, or even 1500 nanometers or less. In some cases, the skin layer may have a thickness of at least 10 nanometers, for example, at least 20, or even at least 50 nanometers. In some cases, the skin layer may have a thickness in the range of 5 nanometers to 15 micrometers, for example, in the range of 50 nanometers to 2 micrometers, 50 to 1500 nanometers, or 50 to 800 nanometers (including both extreme values).

[0021] Support layers having a peelable skin layer can be prepared according to known methods, including coating and film deposition (e.g., sputtering or vapor deposition). For example, the methods described in U.S. Provisional Patent Application No. 63 / 265650 ("Planarized Inorganic Thin Film Transfer Article," Gotrick et al.) or U.S. Patent Publication No. 2020 / 0156355 ("Multi-Layer Isotropic Films Having Toughness, High Temperature Performance, and UV Absorption," Johnson et al.) can be used.

[0022] The functionalized structure (e.g., micro-structure, nano-structure, or both) is constructed on the skin layer of the support. Known methods can be used to fabricate such a structure. For example, the methods described in International Publication WO2022 / 144626 A1 (“Nanopatterned Films with Patterned Surface Chemistry”, Van Lengerich et al.) and International Publication WO2022 / 058845 A1 (“Nanopatterned Films with Patterned Surface Chemistry”, Fishman et al.) can be used to fabricate a structured substrate having recessed well regions with respect to protruding land regions or having protruding posts surrounded by recessed land regions.

[0023] For example, referring to FIG. 1, the structured substrate 100 includes a resin layer 110 having a first major resin surface 111 bonded to a second major skin surface 22 of the skin layer 20. The skin layer 20 is a peelable skin layer having a first major skin surface 21 peelably bonded to the support layer 10. The resin layer 110 includes a plurality of protrusions 130 extending from a second major resin surface 112, each protrusion terminating at a tip 131, and the space between adjacent protrusions is separated by a land region 140 of the second major resin surface 112, and these land regions 140 are recessed with respect to the tips 131 of the protrusions 130.

[0024] The anti-fouling layer 180 is bonded to the second major resin surface 112 in the land region 140. The masking layer 160 is bonded to the anti-fouling layer 180, and the exposed surfaces of the masking layer collectively form a recessed surface 165. In some cases, the anti-fouling layer can cover a portion of the sidewall of the protrusion extending from the second major resin surface 112 to the height of the recessed surface. In this case, this portion of the anti-fouling layer will be located between the masking layer 160 and the sidewall of the protrusion. The inorganic layer 150 is bonded to the tips 131 of the protrusions 130, and the exposed surfaces of the inorganic layer collectively form a protruding surface 155. In some cases, the inorganic layer can cover a portion of the sidewall of the protrusion extending between the tip of the protrusion and the recessed surface.

[0025] One or more additional layers can be included in the structured substrate 100. For example, the additional layers may be located at one or more positions, such as between the skin layer and the resin layer, between the resin layer and the inorganic layer, between the resin layer and the masking layer, on the inorganic layer, or on the masking layer. If one or more additional layers are provided on the inorganic layer 150, the exposed surfaces of the outermost layer at the tip portion 131 of the projection 130 collectively form a protruding surface 155. Similarly, if one or more additional layers are provided on the masking layer 160, the exposed surfaces of the outermost layer in the land region 140 collectively form a recessed surface 165.

[0026] Alternatively, referring to Figure 2, the structured substrate 200 includes an inorganic layer 250 having a first main inorganic surface 251 bonded to a second main skin surface 22 of the skin layer 20. Here again, the skin layer 20 is a peelable skin layer having a first main skin surface 21 peelably bonded to the support layer 10. The antifouling layer 280 has a first main antifouling surface 281 and a second main antifouling surface 282, the first main antifouling surface 281 being bonded to the second main inorganic surface 252 of the inorganic layer 250.

[0027] The antifouling layer 280 includes a plurality of wells 270 extending in the thickness direction of the antifouling layer from the second main antifouling surface 282. Each well 270 terminates at the exposed portion of the second main inorganic surface 252 of the inorganic layer, and the exposed surfaces of the inorganic layer collectively form a recessed surface 265. The masking layer 260 is bonded to the second main antifouling surface 282 in the region surrounding the wells 270, and the exposed surfaces of the masking layer collectively form a protruding surface 255.

[0028] One or more additional layers may be included in the structured substrate 200. For example, the additional layers may be located at one or more positions, such as between the skin layer and the inorganic layer, between the antifouling layer and the inorganic layer, between the antifouling layer and the masking layer, on the inorganic layer, or on the masking layer. If one or more additional layers are provided on the inorganic layer 250, the exposed surfaces of the outermost layer at the bottom of the well 270 collectively form a recessed surface 265. Similarly, if one or more additional layers are provided on the masking layer 260, the exposed surfaces of the outermost layer in the region surrounding the well 270 collectively form a protruding surface 255.

[0029] As used herein, the terms “protruding surface” and “recessed surface” refer to the relative position of the exposed surface of the structured surface layer. Therefore, in the case of a protrusion surrounded by land regions (e.g., a post), the exposed tip of the post is a protruding surface relative to the exposed land regions between the posts. That is, the tip of the post is located further from the skin layer than the land regions. Similarly, in the case of a well, the exposed bottom of the well is a recessed surface relative to the protruding surface of the resin layer surrounding the well (often called a land region).

[0030] As used herein, the term “bonded” includes both direct and indirect bonding when a first layer is bonded to a second layer. Direct bonding of the first layer to the second layer means that the surfaces of the first and second layers are in direct contact. Indirect bonding of the first layer to the second layer means that the surfaces of the first and second layers are separated by one or more intermediate layers that connect their surfaces. For example, the first layer may be indirectly bonded to the second layer by an intermediate layer such as an adhesive layer.

[0031] In some cases, the structure is a nanostructure. For example, in some cases, one or more of the diameter, height, and inter-projection distance of a projection are in the range of 5 to 5000 nanometers, for example, 5 to 1500, 10 to 1500, 50 to 1000 nanometers, or even 50 to 500 nanometers. In some cases, one or more of the diameter, depth, and inter-well distance of a well are in the range of 5 to 5000 nanometers, for example, 5 to 1500, 10 to 1500, 50 to 1000 nanometers, or even 50 to 500 nanometers.

[0032] In another step, the transfer carrier is bonded to the exposed surface of the structured substrate by the lamination layer. Referring to Figure 3, the structured substrate 300 includes a main surface 301 bonded (directly or indirectly) to a second main skin surface 22. The first main skin surface 21 is bonded to the support layer 10. The structured substrate 300 also includes a structured surface 302, which includes a protruding surface 355 and a recessed surface 365.

[0033] The transfer carrier 380 comprises a carrier layer 385 and a lamination layer 390, the lamination layer 390 having a first lamination surface 391 bonded to a structured surface 302 which includes both a protruding surface 355 and a recessed surface 365. A second lamination surface 392 of the lamination layer 390 is bonded to the carrier layer 385 of the transfer carrier 380.

[0034] Since the transfer layer and lamination layer are removed before use, a wide range of materials can be used. Suitable transfer layers include, for example, polymer films (including polyester, polyolefin, polystyrene, and nylon), metal foils, and combinations thereof. Suitable lamination layers include adhesives such as hot melt adhesives and pressure-sensitive adhesives. Examples of suitable lamination layers include those containing thermoplastic resins and acrylates.

[0035] The lamination layer should be selected so that it can bond to the outermost surfaces of both the protruding and recessed surfaces of the structured surface, while being removable without damaging these surfaces. For example, in some cases, the maximum peel force between the lamination layer and the structured substrate is 25 g / cm or less, e.g., 20 or less, 15 or less, or 10 g / cm or less. In some cases, the minimum peel force between the lamination layer and the structured substrate is 0.5 g / cm or more, e.g., 1 or more, 2 or more, or 5 g / cm or more. For example, in some cases, the peel force may be in the range of 0.5 to 25 g / cm, e.g., 1 to 20, 2 to 15, or 2 to 10 g / cm (including both extreme values). The peel force can be measured by standard test methods, including 90-degree or 180-degree peel tests.

[0036] Referring to Figure 4, in the next step, the transfer carrier 380 may be used to separate the skin layer 20 from the support layer 10. By controlling the peeling force between the skin layer and the support layer, the skin layer can be removed from the support layer without damaging the skin layer or distorting the structured substrate 300. At this time, the structured substrate 300 remains bonded to the lamination layer 390 and is supported by the carrier layer 385.

[0037] Referring to Figure 5, in some cases, the adhesive layer 1010 may be bonded to the first main skin surface 21 of the skin layer 20. Optionally, the release liner 1020 may be bonded to the adhesive layer 1010. Referring to Figure 6, after removing the release liner 1020 (if present), the structured substrate 300 may be bonded to the support 1100 using the adhesive layer 1010. Alternatively, the adhesive layer 1010 may be applied to the support 1100. Subsequently, the structured substrate 300 is bonded to the support 1100 by bonding the first main skin surface 21 of the skin layer 20 to the adhesive layer 1010.

[0038] The support is typically a rigid substrate. Suitable substrates include glass and silicon substrates. Suitable adhesives include hot-melt adhesives and pressure-sensitive adhesives. The adhesive layer is typically optically transparent and has low autofluorescence or non-autofluorescence. Suitable adhesives include block copolymers, polyisobutylene, acrylate and methacrylate adhesives, polyamides, polyurethanes, and silicones. In some cases, optically transparent adhesives available from 3M are preferred. A thin adhesive layer may also be preferred. In some cases, the adhesive layer may be 1000 nanometers or less, for example, 500 nanometers or less or 200 nanometers or less. In some cases, the adhesive layer may be in the range of 5 to 1000 nanometers, for example, 5 to 500 or 10 to 200 nanometers.

[0039] After lamination to a support (e.g., a rigid substrate), the transfer carrier is removed, exposing the structured substrate. The material used, or the exposed surfaces of both the lamination layer and the protruding and recessed surfaces, may be selected to allow for clean removal of the lamination layer and minimize or eliminate distortion of the structured substrate (including the masking layer). However, if removal of the masking layer is also desired, additional processing steps, such as washing with a suitable solvent (e.g., water), may be required. Therefore, it may be desirable to select a material that allows the masking layer to be removed along with the transfer carrier. For example, a material may be selected such that the bond strength between the lamination layer and the masking layer is greater than the bond strength between the masking layer and the substrate directly beneath it (e.g., recessed land areas between posts, or protruding surfaces surrounding wells). With such a selection, the masking layer is removed along with the carrier film, exposing the structured layer. If the masking layer is not completely removed, the residue can be removed by washing with a suitable solvent (e.g., water).

[0040] Masking layer The masking layer is a removable layer, such as a washable / peelable material, that can be applied to any position within the nanopattern. In some cases, the material can be cured. Suitable materials include polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacrylamide and its copolymers, poly(hydroxyethyl methacrylate) and its copolymers, and other water-soluble polymers. The masking layer protects the underlying area during various process steps. After exposure to these conditions, the masking layer is removed, exposing the underlying material. In some cases, the masking layer can minimize or eliminate the effect of plasma treatment on the protected area of ​​the underlying layer.

[0041] resin layer The resin layer is any polymer material, preferably one suitable for or applicable to a roll-to-roll process. Preferably, it is required to have low autofluorescence to provide a low-noise background. In some cases, cyclic olefin copolymers (COPs) or biaxially oriented polypropylene (BOPPs) having low autofluorescence over a broad wavelength range can be used to provide low autofluorescence for detecting a wide range of biodetectable molecules. Other examples of suitable low-autofluorescence polymer materials include (meth)acrylates and their copolymers, where (meth)acrylate includes acrylates and methacrylates. Also included are polyamides, polyesters, polycarbonates (e.g., available under the trademark "MAKROLON" from Covestro AG, Pittsburgh, Pennsylvania), and hydrogenated styrene resins (e.g., cyclic block copolymers available from Vivion, Inc., San Carlos, California). Mixtures and combinations of these materials can also be used. In some cases, the (meth)acrylate may be ultraviolet (UV) curable.

[0042] Anti-fouling layer The antifouling layer is a hydrophobic and non-reactive layer that inhibits or prevents the accumulation or formation of biological species such as microorganisms, or biomolecules such as nucleic acids and proteins. Such materials are resistant to nonspecific binding of target analytes and other reagents used in sequencing, are chemically resistant to silanes, and are etchable to allow patterning. The exposed surface of the antifouling layer prevents nonspecific adsorption of target analytes, sequencing reagents, or phosphors. As an example, but not limited to, methyl groups are formed by plasma-enhanced chemical vapor deposition (PECVD) of hexamethyldisiloxane, resulting in thin surfaces with thicknesses of approximately 1 nanometer to 10 nanometers, or approximately 2 nanometers to 8 nanometers. In some examples, the methyl-terminated surface of the antifouling layer is methyl-rich and has a sufficient methyl group concentration to exhibit a water contact angle greater than 100 degrees.

[0043] In one example, methyl groups can be formed by molecular fragmentation via plasma dissociation of hexamethyldisiloxane, but similar functionality can be obtained by any method of forming methyl-terminated surfaces on metals, metalloids, metal oxides, or metalloid oxides.

[0044] Another example of forming an antifouling surface on an inorganic layer is the reaction with a silane having a hydrolysis-sensitive center containing a methyl group in its organic substituent. Examples of hydrolyzable reactive groups include chloro, methoxy, ethoxy, propoxy, methoxyalkoxy, acetoxy, and amines such as dimethylamine, silazane, and oxime. Examples of organic substituents include methyl, linear alkyl, branched alkyl, aryl, and dipodal structures. In various examples, silanes can be applied by vapor deposition, spraying, or solvent coating. Other chemical species include tetraethyl orthosilicate, tetramethylsilane, hexamethyldisilane, bis(trimethylsilyl)amine, trimethylamine, tetramethyltin, and other similar metal alkyl compounds, which can form methyl-terminated surfaces using plasma-enhanced chemical vapor deposition (PECVD). Furthermore, precursors such as trimethylamine can form monolayers of methyl groups on suitable surfaces using atomic layer growth (ALD). In addition, some antifouling materials include thermoplastic resins such as fluoropolymers, polyolefins, polyesters, silicones, polyacrylates (e.g., C18) having long-chain linear alkyl chains that can crystallize, and silicon (meth)acrylate as constituent elements.

[0045] inorganic layer The inorganic layer contains metals, metalloids, metal oxides, or metalloid oxides. It can be functionalized with adhesion promoters and vapor-depositable materials can be used for growing or binding DNA binding media. In some cases, the thickness of the inorganic layer is less than approximately 200 nanometers, or less than approximately 100 nanometers, less than 50 nanometers, or less than 20 nanometers. The composition of the inorganic layer can vary widely, but is not limited to silicon oxides (SiO2, SiC). x O γ or SiAl x O γ ), TiO, aluminum oxide (AlO xExamples include oxides of other metals such as gold, tin, germanium, gallium, zinc, and indium, as well as mixtures and combinations thereof. In contrast to conventional wafer processes, amorphous silicon oxide deposited by roll-to-roll processes may contain impurities such as aluminum and carbon. This allows for more efficient deposition rates on flexible and temperature-sensitive surfaces, for example, by using sputtering or plasma-enhanced chemical vapor deposition (PECVD) techniques.

[0046] example Table 1: Summary of materials used in the preparation of the examples [Table 1]

[0047] Autofluorescence Measurement Procedure ( The sample was measured using a Perkin Elmer Lambda1050 spectrophotometer (equipped with the integrating sphere accessory PELA1002), with the sample positioned independently at the front of the spectrophotometer (the sample was tilted 30 degrees to the right and 10 degrees to the right of the normal to the incident and detection optics, respectively). The scanning speed was set to 102 nm / min, the UV-Vis integration time to 0.56 seconds / point, the data interval to 1 nm, and the slit width to 5 nm. The instrument was set to "% Transmission" and "% Reflectance" modes.

[0048] For comparison with known reference substances, a 10 ppm quinine solution in 0.5 N sulfuric acid was prepared from quinine hemisulfate monohydrate and measured in a 10 mm quartz cell.

[0049] Example 1: Post structure

[0050] Step 1 (Preparation of Skin Layer): A support having a peelable skin layer was prepared according to the method described in U.S. Patent Publication No. 2020 / 0156355 ("Multi-Layer Isotropic Films Having Toughness, High Temperature Performance, and UV Absorption," Johnson et al.). The support layer was a 50-micron thick polyethylene terephthalate (PET) film, and the peelable skin layer was a 15-micron thick polyethylene terephthalate glycol (PETg) layer.

[0051] Step 2 (Preparation of Structured Resin Layer): A resin layer having a nanostructured surface was prepared by die-coating acrylate resin B onto the peelable skin layer of the support formed in Step 1. The resin-coated skin layer was pressed onto the nanostructured nickel surface attached to a steel roller controlled at a speed of 15.2 meters / min and a temperature of 60°C using a rubber-coated roller. The nanostructured nickel tool had a pattern area of ​​approximately 10 cm × 10 cm and contained pore shapes with a diameter of approximately 1500 nm. The resin thickness was sufficient to completely wet the nickel surface and to form a rolling bead of resin when the coating film was pressed onto the nanostructured nickel surface. The resin layer was exposed to radiation from two Fusion UV lamp systems (equipped with D bulbs and operating at 142 W / cm) from Fusion UV Systems (Gaythersburg, Maryland, USA, trademark “F600”). During this time, the resin layer was in contact with the nanostructured nickel surface. After exfoliating the structure from the nanostructured nickel surface, the structural surface of the resin layer was again exposed to radiation from a Fusion UV lamp system. The resulting post-form had a height of approximately 300 nm and a sidewall angle of approximately 4 degrees.

[0052] Step 3 (Formation of Antifouling Layer): A release film containing hexamethyldisiloxane (HMDSO), assembled according to the methods described in U.S. Patent No. 6,696,157 (David et al.), No. 8,664,323 (Iyer et al.), and U.S. Patent Publication No. 2013 / 0229378 (Iyer et al.), was applied to a resin layer having a nanostructured surface prepared in Step 2 within a parallel-plate capacitively coupled plasma reactor. The reactor chamber was equipped with a central cylindrical electrode with a surface area of ​​1.7 square meters. After placing the nanostructured resin layer, supported by the skin layer and support, together with the release film on the electrode, the chamber was reduced to a base pressure of less than 1.3 Pa. Oxygen gas was introduced into the chamber at a flow rate of 1000 SCCM. The process was carried out by plasma-enhanced chemical vapor deposition (PECVD) coupled to the reactor with radio frequency (RF) power at a frequency of 13.56 MHz and an applied power of 2000 watts. The processing time was controlled by passing the nanostructured tooling film through the reaction zone at a speed of 9.1 meters / minute, resulting in an exposure time of approximately 10 seconds. Afterward, the RF power was shut off and the gas in the chamber was evacuated.

[0053] Following this first treatment, a second plasma treatment was performed in the same reactor without returning the chamber to atmospheric pressure. HMDSO gas was introduced into the chamber at a flow rate of approximately 1750 SCCM to achieve a pressure of 1.2 Pa. Then, RF power (13.56 MHz, applied power 1000 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 9.1 meters / minute to obtain an exposure time of approximately 10 seconds. After the treatment time was completed, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure.

[0054] Step 4 (Deposition of Masking Layer): A solution containing 4% by weight of PVB in isopropyl alcohol (IPA) (Coating Solution 1) was die-coated onto the Step 3 film having an antifouling layer at a speed of 0.0254 meters / second using a slot die in a roll-to-roll process. The coating width was 15.24 centimeters and was supplied at a flow rate of 3.6 SCCM using a Harvard syringe pump. The coating was dried at room temperature for 4 minutes to form a PVB masking layer over the entire structured surface, resulting in a substantially flat surface. As a result, the masking layer was significantly thicker in the recessed areas between posts compared to the areas above the posts.

[0055] Step 5 (Removal of masking layer on top of post and formation of bonding inorganic layer): The masked film was subjected to reactive ion etching (RIE) in the reactor chamber to produce an etched film. After placing the masked film on the electrode, the chamber pressure was reduced to less than 1.3 Pa. Oxygen gas was introduced at a flow rate of 100 SCCM, and RF power (13.56 MHz, applied power 7500 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 3.7 meters / min, obtaining an exposure time of approximately 25 seconds. After the processing was completed, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure. This step removed the masking layer on top of the post, and the underlying methylated surface became inorganic (SiO x The surface was converted. In the recessed areas between posts, the masking layer was not completely removed, and the underlying region was shielded due to the effects of reactive ion etching.

[0056] The structure obtained by steps 1 to 5 corresponds to the structure in Figure 1. As shown in Figure 1, the antifouling layer 180 is bonded to the land region 140 of the second main surface of the resin layer 112. In the structure fabricated in this embodiment, the antifouling layer also extends to the side surface of the post in the area covered by the masking layer. As shown in Figure 1, the masking layer 160 is bonded to the antifouling layer 180, and the exposed surfaces of the masking layer collectively form a recessed surface 165. The inorganic layer 150 is bonded to the top end 131 of the post 130, and its exposed surfaces collectively form a convex surface 155. In the structure fabricated in this embodiment, the inorganic layer extends downward along the side wall of the post and terminates before reaching the recessed surface.

[0057] Step 6 (Addition of Lamination Layer and Transfer Carrier): A transfer carrier was laminated onto the upper surface of the etched structure obtained in Step 5. Specifically, acrylate resin A was supplied to the nip just before laminating a 1.5 mil thick PET carrier film onto the structured surface. The acrylate adhesive resin was supplied to the nip by syringe, maintaining a coating width of 10-12 centimeters. The nip consisted of a 90 durometer rubber roll and a steel roll, set to a temperature of 54°C. The nip was pressurized by two cylinders with an air pressure of 0.27 MPa. The film maintained a contact length of approximately 1.5 meters and underwent curing treatment using a Fusion D valve.

[0058] Step 7 (Removal of support film): After the curing process in Step 6, the support film was peeled off from the skin layer, exposing the skin layer.

[0059] Step 8 (Adhesive Application): A toluene solution containing 6% by weight of Kraton block copolymer thermal adhesive (Kraton FG1901, A) was prepared, and this solution was die-coated onto the exposed skin layer surface using a slot die in a roll-to-roll process at a speed of 0.0254 meters / second. The coating width was 15.24 centimeters, and it was supplied at a flow rate of 0.8 SCCM using a Harvard syringe pump. The adhesive coating was dried at 65°C for 4 minutes, and a polypropylene liner was introduced during winding.

[0060] Step 9 (Lamination to Glass): The film was cut to the size of a 100mm diameter, 1mm thick H-K9L glass wafer manufactured by University Wafer in Boston, Massachusetts, USA. The polypropylene liner was peeled off the adhesive, and the final structure was placed on the wafer. Vacuum lamination was then performed using a NILT CNI apparatus.

[0061] Step 10 (Removal of Transfer Carrier and Lamination Layer): After lamination to the wafer, the transfer carrier and lamination layer were removed from the structure. During this process, the masking layer that remained in the recessed areas after Step 5 was removed, exposing the antifouling layer (deposited in Step 3). If any masking layer remained, it was washed with an appropriate solvent (e.g., water) to expose the antifouling layer.

[0062] The resulting structure is shown in Figure 7. The skin layer 420 is bonded to the glass wafer 1400 via an adhesive layer 1410. The structured substrate includes a resin layer 410, an antifouling layer 480, and an inorganic layer 450. The resin layer 410 is bonded to the skin layer 420 and includes a plurality of posts 430, each post terminated at a apical end 431 and separated from adjacent posts by land regions (these land regions are located below the antifouling layer and are therefore not shown). The antifouling layer 480 is bonded to the land regions of the resin layer. In some cases, the antifouling layer may also cover at least a portion of the sides of the posts. The inorganic layer 450 is bonded to the apical ends 431 of the posts 430.

[0063] Example 2: Well structure

[0064] Step 1 (Template Film Preparation): A template film with a nanostructure was prepared by die-coating acrylate resin B onto a polycarbonate film. The coated film was pressed onto a nanostructured nickel surface using a rubber-coated roller, mounted on a steel roller controlled at a speed of 15.2 meters / min and a temperature of 60°C. The nanostructured nickel tool had a pattern area of ​​10 cm × 10 cm and a pore shape with a diameter of 1500 nm on a pitch of 3000 nm. The thickness of the acrylate resin B coating on the film was sufficient to completely wet the nickel surface and form a rolling bead of resin when the coated film was pressed onto the nanostructured nickel surface. The film was exposed to radiation from two Fusion UV lamp systems (equipped with D bulbs, both operating at 142 W / cm) from Fusion UV Systems (Gaythersburg, Maryland, USA, trademark “F600”). During this time, the film was in contact with the nanostructured nickel surface. After peeling the template film from the nanostructured nickel surface, the nanostructured side of the template film was again exposed to radiation from the Fusion UV lamp system. The resulting post-shaped structure formed on the acrylate resin layer had a height of approximately 250 nm and a sidewall angle of approximately 4 degrees.

[0065] Step 2 (Release Treatment of Template Film): A release film containing hexamethyldisiloxane (HMDSO) was assembled according to the methods described in U.S. Patent No. 6,696,157 (David et al.), No. 8,664,323 (Iyer et al.), and U.S. Patent Publication No. 2013 / 0229378 (Iyer et al.), and applied to the nanostructured template film obtained in Step 1 in a parallel-plate capacitively coupled plasma reactor. The chamber was equipped with a central cylindrical electrode with a surface area of ​​1.7 square meters. After placing the nanostructured template film on the electrode, the reactor chamber was reduced to a base pressure of less than 1.3 Pa. O2 gas was introduced into the chamber at a flow rate of 1000 SCCM. The process was carried out by plasma-enhanced chemical vapor deposition (PECVD) with RF power coupled to the reactor at a frequency of 13.56 MHz and an applied power of 2000 watts. The processing time was controlled by passing the nanostructured template film through the reaction zone at a speed of 9.1 meters / minute, obtaining an exposure time of approximately 10 seconds. After the deposition process was complete, the RF power was shut off and the gas was discharged from the chamber. Following the first treatment, a second plasma treatment was performed in the same reactor without returning the chamber to atmospheric pressure. HMDSO gas was introduced into the chamber at a flow rate of approximately 1750 SCCM, achieving a pressure of 1.2 Pa. RF power (13.56 MHz, applied power 1000 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 9.1 meters / minute, obtaining an exposure time of approximately 10 seconds. After the end of the processing time, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure.

[0066] Step 3 (Skin Layer Preparation): A 400 nm thick peelable acrylate skin layer was prepared on the PET support layer using the method described in international patent application PCT / IB2022 / 061266 ("Planarized Inorganic Thin Film Transfer Article").

[0067] Step 4 (Inorganic Layer Deposition): A silicon-containing etch resist (inorganic layer) with a random nanostructure was deposited on the peelable acrylate layer prepared in Step 3 using a self-made parallel-plate capacitively coupled plasma reactor, according to the method described in U.S. Patent No. 6,696,157 (David et al.). The chamber was equipped with a central cylindrical electrode with a surface area of ​​1.7 square meters. After placing the film on the electrode, the reactor chamber was reduced to a base pressure of less than 1.3 Pa. O2 and HMDSO gases were introduced into the chamber at flow rates of 18 SCCM and 750 SCCM, respectively. The process was carried out by plasma-enhanced chemical vapor deposition (PECVD) with RF power coupled to the reactor at a frequency of 13.56 MHz and an applied power of 7500 watts. The processing time was controlled by passing the film through the reaction zone at a speed of 6.7 meters / minute, resulting in an exposure time of approximately 13 seconds. After the deposition process was complete, the RF power was shut off and the gas in the chamber was discharged.

[0068] Following the first treatment, a second plasma treatment was performed in the same reactor without returning the chamber to atmospheric pressure. Tetramethylsilane and O2 gas were introduced into the chamber at flow rates of approximately 500 SCCM and 2000 SCCM, respectively. RF power (13.56 MHz, applied power 2000 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 9.1 meters / minute, resulting in an exposure time of approximately 10 seconds.

[0069] After the second treatment, a third plasma treatment was performed in the same reactor without returning the chamber to atmospheric pressure. O2 gas was introduced into the chamber at a flow rate of approximately 2000 SCCM. RF power (13.56 MHz, applied power 2000 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 9.1 meters / minute, obtaining an exposure time of approximately 10 seconds. At the end of the treatment time, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure.

[0070] Step 5 (Application of antifouling layer): As the antifouling layer, fluoropolymer solution 1 is applied using a slot die in a roll-to-roll process, and the inorganic (SiO2) obtained in Step 4 is applied.x The surface was die-coated at a speed of 0.0508 meters / second. The coating width was 15.24 centimeters and was supplied at a flow rate of 2.78 SCCM using a Harvard syringe pump. The coating was dried at 65°C for 4 minutes.

[0071] Step 6 (Addition of Masking Layer and Pattern Formation): The release-treated template film prepared in Step 2 was slot-die coated with coating solution 2 (PVA) at a speed of 0.0508 meters / second. The web tension was set to approximately 0.0057 N / mm. The PVA solution was applied in a width of 15.24 centimeters and supplied at a flow rate of 5.8 SCCM using a Harvard syringe pump. The coating was dried at 66°C for 3 minutes. Approximately 15 meters after coating, the film entered the nip. In the nip, the film prepared in Step 5 was laminated so that the antifouling layer was in contact with the PVA-coated surface. The nip consisted of a 90-durometer rubber roll and a steel roll and was set to a temperature of 76.7°C. The nip was pressurized at 0.55 MPa using two Bimba air cylinders. Upon peeling of the resulting laminated structure, the PVA masking layer separated from the HMDSO release surface. The resulting multilayer film included a PET support layer, a peelable acrylate skin layer, an inorganic layer, an antifouling layer, and a masking layer having a well pattern, the well pattern corresponding to the inverted shape of the post-structure of the template film.

[0072] Step 7 (Re-exposure of the inorganic layer): The film obtained in Step 6 was subjected to reactive ion etching (RIE) in the same homemade reactor chamber used for depositing the PECVD release layer to produce an etched film. After placing the coated film on the electrodes, the chamber pressure was reduced to less than 1.06 Pa. O2 gas was introduced into the chamber at a flow rate of 1000 SCCM. RF power (13.56 MHz, applied power 4000 watts) was coupled to the reactor. The film was passed through the reaction zone at a speed of 4.6 meters / minute to obtain an exposure time of approximately 20 seconds. After the processing was completed, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure. In this step, both the masking layer and the antifouling layer were removed, a well was formed, and the inorganic layer was exposed at the bottom of the well. In the region above the antifouling layer on the land area, the masking layer was not completely removed and shielded the lower layer region due to the effects of reactive ion etching.

[0073] The structure obtained by steps 1-7 is similar to the structure shown in Figure 2.

[0074] Step 8 (Addition of Lamination Layer and Transfer Carrier): A transfer carrier was laminated onto the upper surface of the etched structure prepared in Step 7. Specifically, acrylate resin A was supplied to the nip just before laminating a 1.5 mil thick PET carrier film. The acrylate adhesive resin was supplied to the nip by syringe and adjusted to a coating width of 10-12 centimeters. The nip consisted of a 90 durometer rubber roll and a steel roll, and was set to a temperature of 54°C. The nip was pressurized at 0.27 MPa by two Bimba air cylinders. The film maintained a contact length of approximately 1.5 meters, during which time it underwent curing treatment with a Fusion D valve. Subsequently, the support film was peeled from the skin layer, exposing the skin layer.

[0075] Step 9 (Adhesive Application): A toluene solution containing 6% by weight of Kraton block copolymer thermal adhesive (Kraton FG1901, A) was prepared, and this solution was die-coated onto the exposed skin layer surface at a speed of 0.0254 meters / second using a slot die in a roll-to-roll process. The coating width was 15.24 centimeters, and it was supplied at a flow rate of 0.8 SCCM using a Harvard syringe pump. The adhesive coating was dried at 65°C for 4 minutes, and a polypropylene liner was introduced during winding.

[0076] Step 10 (Lamination to Glass): The film was cut to the size of a 100mm diameter, 1mm thick H-K9L glass wafer manufactured by University Wafer in Boston, Massachusetts, USA. The polypropylene liner was peeled off the adhesive, and the final structure was placed on the wafer. Vacuum lamination was then performed using a NILT CNI apparatus.

[0077] Step 11 (Removal of Transfer Carrier and Lamination Layer): After lamination to the wafer, the transfer carrier and lamination layer were removed from the structure. This removed the masking layer that remained on the land area after Step 7, exposing the antifouling layer deposited in Step 5. If any masking layer remained, it was washed with an appropriate solvent (e.g., water) to expose the antifouling layer.

[0078] The resulting structure is shown in Figure 8. The skin layer 520 is bonded to the glass wafer 1500 via an adhesive layer 1510. The structured substrate 500 includes an inorganic layer 550 and an antifouling layer 580. The inorganic layer 550 is bonded to the skin layer 520. The antifouling layer 580 is bonded to the inorganic layer 550 and includes a plurality of wells 570 that extend from the surface of the antifouling layer and terminate at the exposed portion of the inorganic layer.

[0079] Autofluorescence spectra were measured for the following samples: (A) a 15-micron thick PETg skin layer from Example 1, (B) a 400 nm thick acrylate skin layer from Example 2, and (C) a 30-micron thick PET layer commonly used in prior art. The samples were analyzed at three excitation wavelengths, and the resulting autofluorescence spectra were collected using a 5 nm bandpass filter covering three emission wavelength ranges. A summary is shown in Table 3. The values ​​shown in Table 2 are the peak autofluorescence emission intensities in each wavelength range. The 400 nm thick acrylate film was fixed to a borosilicate glass slide for handling. The results of the autofluorescence measurements for the acrylate film-adhesive-glass combination and the glass alone are shown in Table 3. Table 2: Autofluorescence wavelength range [Table 2] Table 3: Peak autofluorescence data [Table 3]

Claims

1. A skin layer having a first main skin surface and a second main skin surface, A structured substrate having a flat main surface adjacent to the second main skin surface and a structured surface including a protruding surface and a recessed surface, wherein the structured substrate includes an antifouling layer, an inorganic layer and a masking layer, A transfer carrier comprising a lamination layer having a first lamination surface bonded to the protruding surface and the recessed surface, An article that is equipped with [something].

2. The inorganic layer has a first main inorganic surface bonded to the second main skin surface, The antifouling layer has a first main antifouling surface bonded to a second main inorganic surface of the inorganic layer, and a second main antifouling surface, and the antifouling layer further includes a plurality of wells extending from the second antifouling surface in the thickness direction of the antifouling layer, each well terminating at an exposed portion of the second main inorganic surface of the inorganic layer, and the exposed portions collectively form the recessed surface. The masking layer is bonded to the second main anti-fouling surface to form the protruding surface. The article according to claim 1, wherein the second lamination surface is bonded to the masking layer and the exposed portion of the second main inorganic surface in the well.

3. The structured substrate further includes a first main resin surface bonded to the second main skin surface and a resin layer having a plurality of protrusions, wherein each protrusion terminates on the second main resin surface at its tip, and adjacent protrusions are separated by land regions of the second main resin surface. The inorganic layer is bonded to the tip of the protrusion, and collectively forms the protruding surface. The antifouling layer is bonded to the second main resin surface in the land region. The masking layer is bonded to the antifouling layer in the land region to form the recessed surface. The article according to claim 1, wherein the second lamination surface is bonded to the inorganic layer at the tip of the protrusion and the masking layer in the land region.

4. The article according to claim 3, wherein the resin layer comprises at least one of a cyclic olefin copolymer, biaxially oriented polypropylene, polyacrylate, polymethacrylate, and copolymer of acrylate and methacrylate.

5. The article according to any one of claims 1 to 4, wherein the masking layer comprises a water-soluble polymer.

6. The article according to any one of claims 1 to 4, wherein the masking layer is selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, and combinations thereof.

7. The article according to any one of claims 1 to 6, wherein the antifouling layer includes a methyl-terminated surface.

8. The article according to any one of claims 1 to 6, wherein the antifouling layer comprises a fluoropolymer.

9. The article according to any one of claims 1 to 8, wherein the inorganic layer comprises silicon, titanium, aluminum oxides, and combinations thereof.

10. The article according to claim 9, wherein the inorganic oxide includes silicon oxide.

11. The article according to any one of claims 1 to 10, wherein the skin layer has a thickness in the range of 5 nanometers to 15 micrometers.

12. The article according to claim 11, wherein the skin layer has a thickness in the range of 5 nanometers to 500 nanometers.

13. The article according to any one of claims 1 to 10, wherein the skin layer comprises at least one of polyester, cyclic olefin polymer, cyclic olefin copolymer, polyacrylate, polycarbonate, and polymethacrylate.

14. The article according to any one of claims 1 to 13, further comprising a support layer having a polymer film peelably attached to the first main skin surface of the skin layer.

15. The article according to any one of claims 1 to 13, further comprising an adhesive layer bonded to the first main skin surface of the skin layer.

16. The article according to claim 15, further comprising a rigid substrate bonded to the adhesive layer and located on the opposite side of the skin layer.

17. The article according to claim 16, wherein the rigid substrate comprises at least one of glass and silicon.

18. A step of forming a structured substrate on a support structure comprising a support layer and a skin layer having a first main skin surface bonded to the support layer, the structured substrate having a flat main surface bonded to a second main skin surface of the skin layer, a protruding surface, a recessed surface, and a structured surface including sides connecting the protruding surface and the recessed surface, wherein the structured substrate includes an antifouling layer, an inorganic layer, and a masking layer, A step of bonding a transfer carrier including a lamination layer to the protruding surface and the recessed surface, wherein at least a portion of the lamination layer is bonded to the masking layer, A step of separating the skin layer from the support layer, wherein the transfer carrier and the structured substrate remain bonded to the skin layer, forming a transferable structured substrate; Methods that include...

19. The method according to claim 18, further comprising the step of applying an adhesive layer to the first main skin surface of the skin layer of the transferable structured substrate.

20. The method according to claim 19, further comprising the step of bonding the transferable structured substrate to a rigid substrate.

21. The method according to any one of claims 18 to 20, further comprising the step of separating the transfer carrier from the structured surface.

22. The method according to claim 21, further comprising the step of removing at least a portion of the masking layer when separating the transfer carrier from the structured surface.

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