Transferable film-based structured substrate

Abstract

The present invention describes a transferable nanopatterned substrate. These substrates include a transfer carrier laminated to a structured surface of a multi-layer construction. After the transfer configuration, the transfer carrier may be removed without damaging the structured layer. Methods of making such transferable nanopatterned substrates are also described.

Description

Technical Field

[0001] This disclosure relates to membrane-based structured substrates. The design and structure of these structured substrates allow them to be transferred onto rigid substrates such as glass. Methods for fabricating such transferable membrane-based structured substrates are also described. Summary of the Invention

[0002] In summary, in one aspect, this disclosure provides an article of articles comprising: a surface layer having a first main surface layer surface and a second main surface layer surface; a structured substrate having a flat main surface adjacent to the second main surface layer surface and a structured surface including a protruding surface and a recessed surface; wherein the structured substrate includes an anti-biofouling layer, an inorganic layer and a masking layer; and a transfer carrier including a laminated layer having a first laminated surface bonded to the protruding surface and the recessed surface.

[0003] In another aspect, this disclosure provides a method comprising: creating a structured substrate on a support structure including a support layer and a surface layer having a first main surface layer surface bonded to the support layer, the structured substrate having a flat main surface layer having a second main surface layer surface bonded to the surface layer and 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-biofouling layer, an inorganic layer and a masking layer; bonding a transfer carrier including a laminated layer to the protruding surface and the recessed surface, wherein the laminated layer is bonded to the masking layer; and separating the surface layer from the support layer, wherein the transfer carrier and the structured substrate remain bonded to the surface layer, thereby forming a transferable structured substrate. Attached Figure Description

[0004] Figure 1 An example of a structured base including protrusions is shown.

[0005] Figure 2 An example of a structured substrate including pores is shown.

[0006] Figure 3 An example of a transferable structured substrate with a carrier is shown.

[0007] Figure 4 An example is shown of a removable structured substrate in which the support members have been removed.

[0008] Figure 5 An example is a transferable structured substrate with adhesive and optional padding.

[0009] Figure 6 An example is a transferable structured substrate bonded to a rigid substrate.

[0010] Figure 7An example is a structured substrate, including protrusions, bonded to a rigid substrate in which the carrier is removed.

[0011] Figure 8 An example is a structured substrate including pores bonded to a rigid substrate in which the carrier is removed. Detailed Implementation

[0012] The cost of gene sequencing is driven by the disposable consumables required to run the sequencing instruments. The consumables for each sequencing run are the chemical and biochemical reagents used to probe unknown samples and the flow cell in which the sequencing reaction occurs. Typically, these flow cells have a glass or silicon substrate with nanopores etched in them, ranging from 250 to 2000 nanometers (nm). The pores are then filled with a hydrogel containing chemical components selected for binding the target DNA sample.

[0013] Some gene sequencers use fluorescence imaging as their detection method, and nanopores allow individual samples (i.e., unique clusters of DNA amplicones in each well) to be packed as tightly as possible while remaining optically resolvable. Therefore, the patterning of hydrogel-functionalized nanopores is necessary to achieve high throughput per run, compared to flow cells in which DNA amplicon clusters are randomly seeded.

[0014] Currently, these nanopatterned substrates are fabricated using a wafer-based photolithography method. This method includes numerous process steps performed in a batch process to generate nanopores that are selectively functionalized by a chemical composition that allows for hydrogel filling of the pores and deposition of an anti-biocontamination coating between them. These steps include vapor deposition, masking, etching, mask removal, chemical mechanical planarization (CMP), spin coating, and washing. Therefore, the fabrication cost of these patterned substrates alone is estimated at several thousand dollars per unit and is a major driver of the overall cost of sequencing kits.

[0015] International Patent Publications WO 2022 / 058845 A1 and WO 2022 / 144626 describe nanopatterned substrates formed on flexible carrier films for chemical or biological assays. The carrier can be relatively thick (e.g., greater than 15 micrometers) to provide the desired mechanical stability for forming and processing nanostructures during roll-to-roll processes. Such films have been bonded to rigid substrates such as glass and silicon. However, in part due to the thickness of the carrier film used, the autofluorescence of the carrier can interfere with fluorescence imaging and detection by gene sequencers. Furthermore, when the imaging apparatus scans across a flow cell with a large surface area, variations in thickness across the substrate may require altering the focal plane of the imaging apparatus.

[0016] Robust processes for producing film-based nanopatterned substrates remain needed, particularly cost-effective roll-to-roll processes. Furthermore, film-based nanopatterned substrates that reduce or eliminate concerns about autofluorescence, thickness uniformity, or flatness are required. Processes and structures that allow handling throughout manufacturing and use without compromising the nanopatterned features are also needed.

[0017] The method disclosed herein begins with a support comprising a flexible support layer and a peelable surface layer releasably bonded to the support layer. In prior art methods, a transparent, non-autofluorescent substrate is required. In this disclosure, the support layer is removed prior to use, and these limitations are not required; therefore, a wide range of substrates can be used. Exemplary support layers include paper, metal foil, polymer films, and combinations thereof. Suitable polymer films include, for example, polyesters, poly(meth)acrylates, polyamides, polycarbonates, polyolefins, cyclic olefin polymers (COP), cyclic olefin copolymers (COC), poly(meth)acrylates, polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide, polypropylene, polyethylene, high molecular weight fluorinated polymers (such as THV or PVDF), and silicone resins. If the structure remains flexible, the thickness of the support layer is not critical, as it will be removed and will not promote any undesirable autofluorescence.

[0018] The surface layer is releasably bonded to the support layer. The adhesion force between the surface layer and the support layer should be low enough to allow the surface layer to peel cleanly from the support layer without damaging the surface layer or distorting the structure built on it; i.e., the surface layer is a peelable surface layer. In some cases, the peel force between the surface layer and the support layer is no greater than 25 g / cm, for example, no greater than 20 g / cm, no greater than 15 g / cm, or even no greater than 10 g / cm. In some cases, the peel force is at least 0.5 g / cm, for example, at least 1 g / cm, at least 2 g / cm, or even at least 5 g / cm. For example, in some cases, the peel force is from 0.5 g / cm to 25 g / cm, for example, from 1 g / cm to 20 g / cm, 2 g / cm to 15 g / cm, or 2 g / cm to 10 g / cm, including end values. The peel force can be determined by standard test methods, including 90-degree or 180-degree peel tests. Known materials and processes can be used to treat the surface of the support layer to obtain the desired peel force.

[0019] Since the surface layer remains part of the article during use, a thinner layer of non-self-fluorescent or low-self-fluorescent material is preferred. The surface layer can be thermoplastic or thermosetting. Examples of suitable peelable surface layers include those comprising polyesters, poly(meth)acrylates, polyamides, polycarbonates, polyolefins (e.g., polyethylene and polypropylene), cyclic olefin polymers (COPs), cyclic olefin copolymers (COCs), polyurethanes, high molecular weight fluorinated polymers (such as THV or PVDF), and silicone resins.

[0020] While thicker surface layers can be used, thin surface layers can be used in this invention because the support layer provides the desired mechanical strength and stability during processing. In some cases, the thickness of the surface layer may be no greater than 15 micrometers, for example, no greater than 10 micrometers, no greater than 5 micrometers, no greater than 2 micrometers, or even no greater than 1500 nm. In some cases, the thickness of the surface layer is at least 10 nm, for example, at least 20 nanometers or even at least 50 nanometers. In some cases, the thickness of the surface layer is from 5 nm to 15 micrometers, for example, 50 nm to 2 micrometers, 50 nm to 1500 nm or even 50 nm to 800 nm, including the extreme values.

[0021] A support layer with a peelable surface can be prepared using known methods, including coating and deposition (e.g., sputtering or vapor deposition). For example, the methods of U.S. Provisional Patent Application 63 / 265650 (“Planarized Inorganic Thin Film Transfer Article”, Johnson et al.) or US 2020 / 0156355 A1 (“Multi-Layer Isotropic Films Having Toughness, High Temperature Performance, and UV Absorption”, Gotrick et al.) can be used.

[0022] Functionalized structures (e.g., microstructures, nanostructures, or both) are constructed on the surface of the support. Known methods for creating such structures can be used. For example, the methods of International Patent Publication WO 2022 / 144626 A1 (“Nanopatterned Films with Patterned Surface Chemistry”, Van Lengerich et al.) and International Patent Publication WO 2022 / 058845 A1 (“Nanopatterned Films with Patterned Surface Chemistry”, Fishman et al.) can be used to create a structured substrate comprising raised pillars surrounded by recessed shore regions or recessed holes relative to the raised shore region.

[0023] For example, refer to Figure 1 The structured substrate 100 includes a resin layer 110 having a first primary resin surface 111 bonded to a second primary surface surface 22 of the surface layer 20. The surface layer 20 is a peelable surface layer having a first primary surface surface 21 releasably bonded to the support layer 10. The resin layer 110 includes a plurality of protrusions 130 extending from the second primary resin surface 112, wherein each protrusion terminates at a distal end 131 and is separated from an adjacent protrusion by a shore region 140 of the second primary resin surface 112, the shore region being recessed relative to the distal end 131 of the protrusion 130.

[0024] An antifouling layer 180 is bonded to a second primary resin surface 112 in the shore plate region 140. A masking layer 160 is bonded to the antifouling layer 180, wherein the exposed surfaces of the masking layer collectively form a recessed surface 165. In some cases, the antifouling layer may cover a portion of the wall of the protrusion extending from the second primary resin surface 112 to the height of the recessed surface. If present, this portion of the antifouling layer will be located between the masking layer 160 and the sidewall of the protrusion. An inorganic layer 150 is bonded to the distal end 131 of the protrusion 130, wherein the exposed surfaces of the inorganic layer collectively form the protrusion surface 155. In some cases, the inorganic layer may cover a portion of the wall of the protrusion extending between the distal end of the protrusion and the recessed surface.

[0025] One or more additional layers may be included in the structured substrate 100. For example, the additional layers may be present at one or more locations, including between the surface 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, and 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 distal end 131 of the protrusion 130 will collectively form the 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 shore region 140 will collectively form the recessed surface 165.

[0026] Alternatively, consider the following locations. Figure 2 The structured substrate 200 includes an inorganic layer 250 having a first primary inorganic surface 251 bonded to a second primary surface surface 22 of the surface layer 20. Similarly, the surface layer 20 is a peelable surface layer having a first primary surface surface 21 releasably bonded to the support layer 10. The biofouling-resistant layer 280 has a first primary biofouling-resistant surface 281 and a second primary biofouling-resistant surface 282. The first primary biofouling-resistant surface 281 is bonded to the second primary inorganic surface 252 of the inorganic layer 250.

[0027] The anti-biofouling layer 280 includes a plurality of holes 270 extending from the second primary anti-biofouling surface 212 through the thickness of the anti-biofouling layer. Each hole 270 terminates in an exposed portion of the second primary inorganic surface 252 of the inorganic layer, wherein the exposed surfaces of the inorganic layer collectively form a recessed surface 265. A masking layer 260 is bonded to the second primary anti-biofouling surface 282 in the region surrounding the holes 270, wherein 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 present at one or more locations, including between the surface layer and the inorganic layer, between the anti-biofouling layer and the inorganic layer, between the anti-biofouling layer and the masking layer, on the inorganic layer, and on the masking layer. If one or more additional layers are provided on the inorganic layer 250, the outermost exposed surfaces at the base of the aperture 270 will collectively form a recessed surface 265. Similarly, if one or more additional layers are provided on the masking layer 260, the outermost exposed surfaces in the region surrounding the aperture 270 will collectively form a protruding surface 255.

[0029] As used herein, the terms "protruding surface" and "recessed surface" refer to the relative positions of the exposed surfaces of a structured surface layer. Thus, in the case of a protrusion (e.g., a post) surrounded by a shore region, the exposed distal end of the post is the protruding surface relative to the recessed exposed shore region between the posts. That is, the distal end of the post is further away from the surface layer than the shore region. Similarly, in the case of a hole, the exposed base of the hole is the recessed surface relative to the protruding surface of the resin layer surrounding the hole, sometimes referred to as the shore region.

[0030] As used herein, when referring to the bonding of a first layer to a second layer, the term "bonding" includes both direct bonding and indirect bonding. If the surfaces of the first and second layers are in direct contact, the first layer is directly bonded to the second layer. If the surfaces of the first and second layers are separated by one or more intermediate layers connecting their surfaces, the first layer is indirectly bonded to the second layer. For example, the first layer may be indirectly bonded to the second layer via 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 spacing between the protrusions are 5 nanometers to 5000 nanometers, such as 5 nm to 1500 nm, 10 nm to 1500 nm, 50 nm to 1000 nm, or even 50 nm to 500 nm. In some cases, one or more of the diameter, depth, and spacing between the pores are 5 nanometers to 5000 nanometers, such as 5 nm to 1500 nm, 10 nm to 1500 nm, 50 nm to 1000 nm, or even 50 nm to 500 nm.

[0032] In another step, the transfer carrier is bonded to the exposed surface of the structured substrate using a laminate. (Reference) Figure 3 The structured substrate 300 includes a primary surface 301 that is (directly or indirectly) bonded to a second primary surface surface 22 of the surface layer 20. A first primary surface surface 21 is bonded to a support layer 10. The structured substrate 300 also includes a structured surface 302 that includes a protruding surface 355 and a recessed surface 365.

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

[0034] Because the transfer layer and laminate are removed before use, a variety of materials can be used. Suitable transfer layers include, for example, polymer films (including polyesters, polyolefins, polystyrene, and nylon), metal foils, and combinations thereof. Suitable laminates include adhesives, such as hot melt adhesives and pressure-sensitive adhesives. Exemplary laminates may comprise thermoplastics and acrylates.

[0035] The laminate should be selected such that it bonds to both the raised and recessed surfaces of the structured surface, but can be removed from these surfaces without damaging the desired structured surface. For example, in some cases, the maximum peel force between the laminate and the structured substrate is no greater than 25 g / cm, such as no greater than 20 g / cm, no greater than 15 g / cm, or even no greater than 10 g / cm. In some cases, the minimum peel force between the laminate and the structured substrate is at least 0.5 g / cm, such as at least 1 g / cm, at least 2 g / cm, or even at least 5 g / cm. For example, in some cases, the peel force is from 0.5 g / cm to 25 g / cm, such as 1 g / cm to 20 g / cm, 2 g / cm to 15 g / cm, or 2 g / cm to 10 g / cm, including end values. The peel force can be determined by standard test methods, including 90-degree or 180-degree peel tests.

[0036] refer to Figure 4 In subsequent steps, the transfer carrier 380 can be used to separate the surface layer 20 from the support layer 10. By controlling the peel force between the surface layer and the support layer, the surface layer can be removed from the support layer without damaging the surface layer and without distorting the structured substrate 300, which remains bonded to the laminate 390 supported by the carrier layer 385.

[0037] refer to Figure 5 In some cases, the adhesive layer 1010 may be bonded to the first surface 21 of the surface layer 20. Optionally, the release liner 1020 may be bonded to the adhesive layer 1010. (See reference) Figure 6 After removing the release liner 1020 (if present), the adhesive layer 1010 can be used to bond the structured substrate 300 to the support 1100. Alternatively, the adhesive layer 1010 can be applied to the support 1100. Subsequently, the first surface 21 of the surface layer 20 can be bonded to the adhesive layer 1010, thereby causing the structured substrate 300 to bond to the support 1100.

[0038] The support is typically a rigid substrate. Exemplary substrates include glass and silicon substrates. Exemplary adhesives include hot melt adhesives or pressure-sensitive adhesives. The adhesive layer is typically optically transparent and has low or no autofluorescence. Suitable adhesives include block copolymers, polyisobutylene, acrylate and methacrylate adhesives, polyamides, polyurethanes, and silicones. In some cases, optically transparent adhesives, including those available from 3M, may be preferred. A thin adhesive layer may be preferred. In some aspects, the thickness of the adhesive layer is no greater than 1000 nm, for example, no greater than 500 nm or no greater than 200 nm. In some cases, the thickness of the adhesive layer is from 5 nm to 1000 nm, for example, from 5 nm to 500 nm, or even from 10 nm to 200 nm.

[0039] After lamination onto a support (e.g., a rigid substrate), the transfer carrier can be removed, thereby exposing the structured substrate. The material used or the exposed surfaces of both the laminate and the protruding and recessed surfaces can be selected to allow for clean removal of the laminate with minimal or no distortion of the structured substrate, including the masking layer. However, if it is also desired to remove the masking layer, this may require additional processing steps, such as washing with a suitable solvent (e.g., water). Therefore, it may be desirable to select a material that allows the masking layer to be removed along with the transfer carrier. For example, the material can be selected such that the bond strength between the laminate and the masking layer is greater than the bond strength between the masking layer and the substrate immediately beneath it, for example, in the recessed shore region between pillars, or around the protruding surface of a hole. With such selection, the masking layer can be removed while the carrier film exposes the structured layer. If the masking layer is not completely removed, any residual material can be removed, for example, by washing with a suitable solvent (e.g., water).

[0040] Masking layer. A masking layer is a removable layer (e.g., a washable / peelable material) that can be applied anywhere on the entire 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 copolymers, and other water-soluble polymers. During the various process steps, the masking layer protects the area beneath it. The masking layer is then removed after exposure to those conditions to expose the material underneath. In some cases, the masking layer may minimize or eliminate the effects of plasma treatment on the protected area below.

[0041] Resin layer. The resin layer is any polymer material, preferably a polymer material suitable for or applicable to roll-to-roll processes. Preferably, it should have low autofluorescence to provide a low-noise background. In some examples, to provide low autofluorescence for the detection of a variety of biodetectable molecules, cyclic olefin copolymers (COP) or biaxially oriented polypropylene (BOPP) can be used, each having low autofluorescence over a wide spectral range. Other examples of suitable low-autofluorescence polymer materials include, but are not limited to, poly(meth)acrylates and their copolymers (wherein the (meth)acrylate comprises acrylates and methacrylates), polyamides, polyesters, polycarbonates (such as, for example, those obtained under the trade name MAKROLON from Covestro AG (Pittsburgh, PA),) hydrogenated styrene (such as, for example, cyclic block copolymers obtained from Vivion, Inc., San Carlos, CA), and mixtures and compositions thereof. In some cases, (meth)acrylates can be cured by ultraviolet (UV) radiation.

[0042] Anti-biocontamination layers. Anti-biocontamination layers are hydrophobic, non-reactive layers that resist or prevent the accumulation or formation of biological species (such as microorganisms) or biomolecules (such as nucleic acids and proteins). These materials are resistant to non-specific binding of target analytes and other reagents used in sequencing, chemically resistant to silanes, and can be etched to achieve patterning. The exposed surfaces of the anti-biocontamination layer prevent non-specific adsorption of target analytes, sequencing reagents, or fluorophores. In one example, not intended to be limiting, methyl groups are formed by plasma-enhanced chemical vapor deposition (PECVD) of hexamethyldisiloxane, resulting in a thin surface with a thickness of about 1 nm to about 10 nm or about 2 nm to about 8 nm. In some examples, the methyl-capped surfaces of the anti-biocontamination layer are sufficiently enriched with methyl groups to provide a water contact angle greater than 100 degrees.

[0043] In some examples, methyl groups can be formed from molecular fragments of hexamethyldisiloxane via plasma dissociation, although any method of creating methyl-terminated surfaces on metals, metalloids, metal oxides, or metalloids can provide similar functionality.

[0044] Another example of forming biofouling-resistant surfaces on inorganic layers includes the reaction of silanes with hydrolysis-sensitive centers having organic substitutions containing methyl groups. Examples of hydrolysis-reactive groups are chlorine, methoxy, ethoxy, propoxy, methoxyalkoxy, acetoxy, and amines such as, for example, dimethylamine, silazane, or oxime. Examples of organic substitutions include methyl, straight-chain alkyl, branched alkyl, aryl, and biarm. In various examples, silanes can be applied by vapor deposition, spraying, or solvent coating. Other chemical components, such as tetraethyl orthosilicate, tetramethylsilane, hexamethyldisilane, bis(trimethylsilyl)amine, trimethylamine, or tetramethyltin and other similar metallic alkyl compounds, can be deposited using plasma-enhanced chemical vapor deposition to produce methyl-terminated surfaces. Alternatively, precursors such as trimethylamine can be deposited on suitable surfaces using atomic layer deposition to form a monolayer of methyl groups. In addition, biofouling-resistant materials may also include blocks made of thermoplastics such as fluoropolymers, polyolefins, polyesters, silicone resins, polyacrylates and silicone (meth)acrylates having crystallizable long straight-chain alkyl chains (e.g., C18).

[0045] Inorganic layers. Inorganic layers comprise metals, metalloids, metal oxides, or metalloid oxides. Vapor-depositable materials suitable for functionalization with binder promoters can be used, which can be used to grow or conjugate DNA binding media. In some cases, the thickness of the inorganic layer is less than about 200 nm, or less than about 100 nm, less than about 50 nm, or even less than about 20 nm. The composition of the inorganic layer can vary widely, but in some examples not intended to be limiting, it includes silicon oxides such as SiO2, SiCxOy, or SiAlxOy, as well as TiO, aluminum oxides such as AlOx, oxides of other metals (such as Au, Sn, Ge, Ga, Zn, and In), and mixtures and compositions thereof. Compared to conventional wafer processing, amorphous silicon oxides deposited by roll-to-roll processing can contain impurities such as aluminum or carbon, which can achieve more efficient deposition rates on flexible, temperature-sensitive surfaces using techniques such as sputtering or PECVD.

[0046] Example

[0047] Table 1: Summary of materials used in the preparation of the examples .

[0048]

[0049] Autofluorescence procedure. The sample was measured freely in a Perkin Elmer Lambda 1050 spectrophotometer equipped with a PELA 1002 integrating sphere attachment, with the sample positioned at the front (sample perpendicular to the incident direction at a 30-degree angle, detector optics perpendicular to the incident direction at a 10-degree angle). The scan rate was set to 102 nm / min, UV-Vis integration to 0.56 sec / pt, data interval to 1 nm, and slit width to 5 nm. The instrument was set to "% transmittance" and "% reflectance" modes.

[0050] To compare with known references, a 10 ppm quinine solution was prepared from quinine hemisulfate monohydrate in 0.5 N sulfuric acid and placed in a 10 mm quartz cell.

[0051] Example 1: Column .

[0052] Step 1 (Preparation of the Surface Layer): A support with a peelable surface layer was prepared according to the method described in US Patent Publication 2020 / 0156355 A1 (“Multi-Layer Isotropic Films Having Toughness, High Temperature Performance, and UV Absorption”, Johnson et al.). The support layer was a 50-micron-thick PET film, and the peelable surface layer was a 15-micron-thick polyethylene terephthalate (PETg) layer.

[0053] Step 2 (Preparation of the Structured Resin Layer): A resin layer with a nano-characterized structured surface is prepared by applying acrylate resin B-mold to the peelable surface of the support formed in Step 1. The resin-coated surface is pressed onto the nano-structured nickel surface, which is attached to a steel roller controlled at a speed of 15.2 m / min using a rubber-coated roller at 60°C. The nano-structured nickel tool consists of a 10 cm × 10 cm patterned area with pore features of approximately 1500 nm in diameter. The resin thickness is sufficient to completely wet the nickel surface and form rolling beads of resin when the coating is pressed onto the nano-structured nickel surface. The resin layer is exposed to radiation from two Fusion UV lamp systems (trade name "F600" from Fusion UV Systems, Gaithersburg, MD) equipped with D bulbs, both operating at 142 W / cm, in contact with the nano-structured nickel surface. After the structure was peeled off from the nanostructured nickel surface, the structured side of the resin layer was re-exposed to radiation from the Fusion UV lamp system. The resulting column is characterized by a height of approximately 300 nm and a sidewall angle of approximately 4 degrees.

[0054] Step 3 (Forming an Anti-Biofouling Layer): A release membrane containing hexamethyldisiloxane (HMDSO), assembled according to the methods described in U.S. Patent Nos. 6,696,157 (David et al.), 8,664,323 (Iyer et al.), and U.S. Patent Publication No. 2013 / 0229378 (Iyer et al.), is applied to the nanostructured surface of the resin layer prepared in Step 2 in a parallel-plate capacitively coupled plasma reactor. The reaction chamber has a central cylindrical energized electrode with a surface area of ​​1.7 m². After placing the nanostructured resin layer, supported by the surface layer and supports, in combination with the release membrane onto the energized electrode, the reaction chamber is pumped down to a base pressure of less than 1.3 Pa. Oxygen is introduced into the chamber at a rate of 1000 SCCM. The reactor is then processed using plasma-enhanced CVD by coupling RF power into the reactor at a frequency of 13.56 MHz and an applied power of 2000 W. The treatment time was controlled by moving the nanostructured mold membrane through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds. The RF power was then turned off and the gas was vented from the reactor.

[0055] Following the first treatment, a second plasma treatment was performed in the same reactor without returning the reaction chamber to atmospheric pressure. HMDSO gas was introduced into the chamber at approximately 1750 SCCM to achieve a pressure of 1.2 Pa. RF power (13.56 MHz) was then coupled into the reactor at an applied power of 1000 W. The membrane was then transported through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds. At the end of this treatment time, the RF power and gas supply were stopped, and the reaction chamber was returned to atmospheric pressure.

[0056] Step 4 (Deposition of the Masking Layer): A solution of 4% by weight PVB in IPA (coating solution 1) is die-coated onto the anti-biofouling layer of the membrane from Step 3 using a slit die in a roll-to-roll process at a rate of 0.0254 m / s. The solution is coated to a width of 15.24 cm and pumped using a Harvard syringe pump at a rate of 3.6 SCCM. The coating is dried at room temperature for four minutes to form a PVB masking layer across the entire structured surface, resulting in a substantially flat surface. Therefore, the masking layer on the top of the columns is significantly thinner compared to the recessed areas between the columns.

[0057] Step 5 (Removing the Masking Layer from the Top of the Columns and Creating the Inorganic Bonded Layer): The masking membrane is subjected to reactive ion etching in the aforementioned reaction chamber to create an etched film. After placing the masking membrane on the energized electrodes, the reaction chamber is pumped down to a base pressure less than 1.3 Pa. Oxygen is introduced into the chamber at a rate of 100 SCCM. RF power (13.56 MHz) is then coupled into the reactor at an applied power of 7500 W. The membrane is then transported through the reaction zone at a rate of 3.7 m / min to achieve an exposure time of approximately 25 seconds. At the end of this processing time, the RF power and gas supply flow are stopped, and the chamber is returned to atmospheric pressure. This step removes the masking layer on the top of the columns and converts the underlying methylated surface into an inorganic (SiOx) surface. The masking layer is not completely removed in the recessed regions between the columns, thus shielding the underlying regions from the reactive ion etching process.

[0058] The structures generated from steps 1 to 5 correspond to Figure 1 The structure. For example... Figure 1 As shown, the antifouling layer 180 is bonded to the second primary resin surface 112 in the shore platen region 140. In the structure produced in this example, the antifouling layer also extends upward along the side of the protrusion in the area covered by the masking layer. Figure 1As shown, the masking layer 160 is bonded to the biofouling-resistant layer 180, wherein the exposed surfaces of the masking layers collectively form a recessed surface 165. The inorganic layer 150 is bonded to the distal end 131 of the protrusion 130, wherein the exposed surfaces of the inorganic layer collectively form a protrusion surface 155. In the structure produced in this embodiment, the inorganic layer also extends downward along the side of the protrusion, terminating before reaching the recessed surface.

[0059] Step 6 (Adding the Lamination Layer and Transfer Carrier): The transfer carrier is laminated onto the top side of the etched structured surface created in Step 5 by feeding acrylate resin A into the roll gap just before laminating the 1.5 mil PET carrier film onto the etched structured surface. The acrylate adhesive resin is injected into the roll gap using a syringe to maintain a coating width of 10-12 cm. The roll gap consists of a rubber roller with a hardness of 90 and a steel roller set at 54°C. The roll gap is engaged by two cylinders pressurized at 0.27 MPa. The films are held in contact for approximately 1.5 meters while they are cured using a fused D-type lamp.

[0060] Step 7 (Removal of Support Film): After the curing process in Step 6, the support film is peeled off from the surface to expose the surface.

[0061] Step 8 (Adhesive Application): During the roll-to-roll process, a solution of 6% by weight of block copolymer thermal adhesive (Kraton FG1901, A from Kraton) in toluene is applied to the exposed surface of the surface layer through a slit die at a rate of 0.0254 m / s. The solution is applied to a width of 15.24 cm and pumped using a Harvard injection pump at a rate of 0.8 SCCM. The adhesive coating is dried at 65°C for 4 minutes, and a polypropylene liner is introduced at the winding machine.

[0062] Step 9 (Lamination to Glass): The film is cut to the dimensions of an H-K9L glass wafer with a diameter of 100 mm and a thickness of 1 mm, sourced from University Wafer (Boston, Massachusetts, USA). The polypropylene liner is then peeled off from the adhesive and the final construction is placed on top of the wafer. The construction is then vacuum-laminated onto the wafer using NILT CNI tools.

[0063] Step 10 (Removal of Transfer Carrier and Laminate): After lamination onto the wafer, the transfer carrier and laminate are stripped from the construction. During this process, the masking layer remaining in the recessed area after step 5 is removed, thereby exposing the anti-biocontamination layer deposited in step 3. If any masking layer remains, it is washed away with a suitable solvent (e.g., water) to expose the anti-biocontamination layer.

[0064] The resulting structure is in Figure 7As shown in the diagram, surface layer 420 is bonded to glass wafer 1400 via adhesive layer 1410. The structured substrate includes resin layer 410, anti-biofouling layer 480, and inorganic layer 450. Resin layer 410, bonded to surface layer 420, includes a plurality of protrusions 430, each protrusion terminating at a distal end 431 and separated from adjacent protrusions by a shore region not visible beneath the anti-biofouling layer. Anti-biofouling layer 480 is bonded to resin layer in the shore region. In some cases, anti-biofouling layer may also cover at least a portion of the sidewalls of the protrusions. Inorganic layer 450 is bonded to the distal end 431 of protrusion 430.

[0065] Example 2: Hole

[0066] Step 1 (Preparation of the Template Film): A nano-characterized template film was prepared by applying acrylate resin B to a polycarbonate film. The coated film was pressed onto a nanostructured nickel surface, which was attached to a steel roller controlled at a speed of 15.2 m / min using a rubber-coated roller at 60°C. The nanostructured nickel tool consisted of a 10 cm × 10 cm patterned area with holes of approximately 1500 nm in diameter and a spacing of 3000 nm. The coating thickness of the acrylate resin B was sufficient to completely wet the nickel surface and form rolling beads 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 (trade name "F600" from Fusion UV Systems, Gaithersburg, MD) equipped with D bulbs, both operating at 142 W / cm, simultaneously in contact with the nanostructured nickel surface. After the template film was peeled off from the nanostructured nickel surface, the nanostructured side of the template film was exposed again to radiation from the Fusion UV lamp system. The resulting column formed in the acrylate resin layer is characterized by a height of approximately 250 nm and a sidewall angle of approximately 4 degrees.

[0067] Step 2 (Release Treatment Template Membrane): A release membrane containing hexamethyldisiloxane (HMDSO), assembled according to the methods described in U.S. Patent Nos. 6,696,157 (David et al.), 8,664,323 (Iyer et al.), and U.S. Patent Publication No. 2013 / 0229378 (Iyer et al.), is applied to the nanostructured template membrane from Step 2 in a parallel-plate capacitively coupled plasma reactor. The chamber has a central cylindrical energized electrode with a surface area of ​​1.7 m². After placing the nanostructured template membrane on the energized electrode, the reaction chamber is pumped down to a base pressure of less than 1.3 Pa. O2 gas is introduced into the chamber at a rate of 1000 SCCM. Treatment is performed using plasma-enhanced CVD by coupling RF power into the reactor at a frequency of 13.56 MHz and an applied power of 2000 W. The treatment time is controlled by moving the nanostructured template membrane through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds. After deposition, the RF power was shut off and the gas was vented from the reactor. Following the first treatment, a second plasma treatment was performed in the same reactor without returning the reaction chamber to atmospheric pressure. HMDSO gas was introduced into the chamber at approximately 1750 SCCM to achieve a pressure of 1.2 Pa. Subsequently, a 13.56 MHz RF power was coupled into the reactor at an applied power of 1000 W. The membrane was then transported through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds. At the end of this treatment time, the RF power and gas supply were stopped, and the reaction chamber was returned to atmospheric pressure.

[0068] Step 3 (Preparation of the surface layer): A peelable acrylate surface layer with a thickness of 400 nm is fabricated on the PET support layer using the method described in International Patent Application PCT / IB2022 / 061266 (“Planarized Inorganic Thin Film Transfer Article”).

[0069] Step 4 (Deposition of Inorganic Layer): A randomly nanostructured silicon resist (inorganic layer) was deposited onto the peelable acrylate layer prepared in Step 3 using a self-made parallel-plate capacitively coupled plasma reactor as described in U.S. Patent No. 6,696,157. The chamber had a central cylindrical energized electrode with a surface area of ​​1.7 square meters. After the membrane was placed on the energized electrode, the reaction chamber was pumped down to a base pressure of less than 1.3 Pa. O2 and HMDSO gases were introduced into the chamber at rates of 18 SCCM and 750 SCCM, respectively. Treatment was performed using plasma-enhanced CVD by coupling RF power into the reactor at a frequency of 13.56 MHz and an applied power of 7500 W. The treatment time was controlled by moving the membrane through the reaction zone at a rate of 6.7 m / min, resulting in an exposure time of approximately 13 seconds. After deposition was complete, the RF power was turned off and the gases were evacuated from the reactor.

[0070] Following the initial treatment, a second plasma treatment was performed in the same reactor without returning the reaction chamber to atmospheric pressure. Tetramethylsilane and O2 gas were introduced into the chamber at approximately 500 SCCM and 2000 SCCM, respectively. Subsequently, 13.56 MHz RF power was coupled into the reactor at an applied power of 2000 W. The membrane was then transported through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds.

[0071] Following 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 approximately 2000 SCCM. Subsequently, 13.56 MHz RF power was coupled into the reactor at an applied power of 2000 W. The membrane was then transported through the reaction zone at a rate of 9.1 m / min, resulting in an exposure time of approximately 10 seconds. At the end of this treatment time, the RF power and gas supply were stopped, and the reaction chamber was returned to atmospheric pressure.

[0072] Step 5 (Coating of the Anti-Biocontamination Layer): The fluoropolymer solution is coated onto the inorganic (SiOx) surface of the substrate from Step 4 using a slit die at a rate of 0.0508 m / s during a roll-to-roll process. The solution is coated over a width of 15.24 cm and pumped using a Harvard injection pump at a rate of 2.78 SCCM. The coating is then dried at 65°C for 4 minutes.

[0073] Step 6 (Adding Masking and Patterning): The release-treated template film created in Step 2 is slot-coated with paint solution 2 (PVA) at a rate of 0.0508 m / s. The web tension is set to approximately 0.0057 N / mm. A 15.24 cm wide strip of PVA solution is applied and pumped using a Harvard syringe pump at a rate of 5.8 SCCM. The coating is dried at 66°C for 3 minutes. After coating, the coated film is then passed through a roll gap of approximately 15 m. At the roll gap, the film prepared in Step 5 is laminated so that the anti-biocontamination layer contacts the PVA-coated surface of the release-treated template film. The roll gap consists of a rubber roller with a hardness of 90 and a steel roller set at 76.7°C. The roll gap is engaged by two Bimba cylinders pressurized at 0.55 MPa. The resulting structure is then peeled off, separating the PVA masking layer from the HMDSO release surface. The resulting multilayer film consists of a PET support layer, a peelable acrylate surface layer, an inorganic layer, an anti-biofouling layer, and a patterned masking layer, which includes pores in the opposite direction to the pillars of the template film.

[0074] Step 7 (Re-exposing the Inorganic Layer): The inorganic layer is re-exposed in the same homemade reaction chamber used for depositing the PECVD release layer. Figure 6 The membrane was subjected to reactive ion etching to create an etched membrane. After the coated membrane was placed on the energized electrode, the reaction chamber was pumped down to a base pressure less than 1.06 Pa. O2 gas was introduced into the chamber at a rate of 1000 SCCM. Subsequently, 13.56 MHz RF power was coupled into the reactor at an applied power of 4000 W. The membrane was then transported through the reaction zone at a rate of 4.6 m / min to achieve an exposure time of approximately 20 seconds. At the end of this processing time, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure. This step removed both the masking layer and the anti-biofouling layer to form pores and expose the inorganic layer at the base of the pores. In the area above the anti-biofouling layer in the shore platen region, the masking layer was not completely removed, thus shielding the area below from the reactive ion etching process.

[0075] The structure produced by steps 1 to 7 is similar to Figure 2 The structure shown.

[0076] Step 8 (Adding the Lamination Layer and Transfer Carrier): The transfer carrier is laminated onto the top side of the etched structured surface prepared in Step 7 by feeding acrylate resin A into the roll gap just before laminating the 1.5 mil PET carrier film. The acrylate adhesive resin is injected into the roll gap using a syringe to maintain a coating width of 10-12 cm. The roll gap consists of a rubber roller with a hardness of 90 and a steel roller set at 54°C. The roll gap is engaged by two Bimba cylinders pressurized at 0.27 MPa. The films are held in contact for approximately 1.5 μm, during which they are cured using molten D lamps. Subsequently, the support film is peeled off from the surface layer, exposing the surface layer.

[0077] Step 9 (Applying Adhesive): During the roll-to-roll process, apply a 6% by weight solution of block copolymer thermal adhesive (Kraton FG1901, A from Kraton) in toluene to the exposed surface of the surface layer through a slit die at a rate of 0.0254 m / s. Apply the solution to a 15.24 cm wide area and pump it using a Harvard injection pump at a rate of 0.8 SCCM. Dry the adhesive coating at 65°C for 4 minutes and introduce a polypropylene liner at the winding machine.

[0078] Step 10 (Lamination to Glass): The film is cut to the dimensions of an H-K9L glass wafer with a diameter of 100 mm and a thickness of 1 mm, sourced from University Wafer (Boston, Massachusetts, USA). The polypropylene liner is then peeled off from the adhesive and the final construction is placed on top of the wafer. The construction is then vacuum-laminated onto the wafer using NILT CNI tools.

[0079] Step 11 (Removal of Transfer Carrier and Lamination): After lamination onto the wafer, the transfer carrier and lamination layer are stripped from the construction, thereby removing the masking layer retained on the shore area after step 7, thus exposing the anti-biofouling layer deposited in step 5. If any masking layer remains, it is washed away with a suitable solvent (e.g., water) to expose the anti-biofouling layer.

[0080] The resulting structure is in Figure 8 As shown in the diagram, surface layer 520 is bonded to glass wafer 1500 via adhesive layer 1510. Structured substrate 500 includes inorganic layer 550 and anti-biocontamination layer 580. Inorganic layer 550 is bonded to surface layer 520. Anti-biocontamination layer 580 is bonded to inorganic layer 550 and includes a plurality of holes 570 extending from the surface of anti-biocontamination layer and terminating in exposed portions of inorganic layer.

[0081] Autofluorescence spectra were collected for (A) a 15 μm thick PET film from Example 1, (B) a 400 nm thick acrylate film from Example 2, and (C) a typical 30 μm thick PET layer from prior art methods. Samples were analyzed at three excitation wavelengths, and the resulting autofluorescence spectra were collected using a 5 nm bandpass covering the three emission wavelength ranges, as summarized in Table 3. The values ​​reported in Table 2 are the peak autofluorescence emission intensities for each wavelength range. The 400 nm thick acrylate film was adhesively mounted onto a borosilicate glass slide for processing. The autofluorescence of the combination of acrylate film, adhesive, and glass, as well as the autofluorescence of the glass alone, are reported in Table 3.

[0082] Table 2: Autofluorescence wavelength range .

[0083]

[0084] Table 3: Peak autofluorescence data 。

[0085]

Claims

1. An article comprising a skin having a first major skin surface and a second major skin surface; a structured substrate having a planar major surface adjacent the second major skin surface and a structured surface comprising a raised surface and a recessed surface; wherein the structured substrate comprises an anti-biofouling layer, an inorganic layer, and a masking layer; and a transfer carrier comprising a lamination layer having a first lamination surface bonded to the raised surface and the recessed surface.

2. The article of claim 1, wherein the inorganic layer has a first major inorganic surface bonded to the second major skin surface, the anti-biofouling layer has a first major anti-biofouling surface and a second major anti-biofouling surface bonded to a second major inorganic surface of the inorganic layer, wherein the anti-biofouling layer further comprises a plurality of pores extending through a thickness of the anti-biofouling layer from the second anti-biofouling surface, each pore terminating at an exposed portion of the second major inorganic surface of the inorganic layer, wherein the exposed portions collectively form the recessed surface, and the masking layer is bonded to the second major anti-biofouling surface forming the raised surface; wherein the second lamination surface is bonded to the masking layer and the exposed portions of the second major inorganic surface in the pores.

3. The article of claim 1, wherein the structured substrate further comprises a resin layer having a first major resin surface bonded to the second major skin surface and a plurality of projections, wherein each projection terminates at a distal end at a second major resin surface and is separated from adjacent projections by a land region of the second major resin surface, wherein the inorganic layer is bonded to the distal ends of the projections collectively forming the raised surface, the anti-biofouling layer is bonded to the second major resin surface in the land regions, the masking layer is bonded to the anti-biofouling layer in the land regions forming the recessed surface, and the second lamination surface is bonded to the inorganic layer at the distal ends of the projections and to the masking layer in the land regions.

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

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

6. The article of 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 of any one of claims 1 to 6, wherein the anti-biofouling layer comprises a methyl-terminated surface.

8. The article of any one of claims 1 to 6, wherein the anti-biofouling layer comprises a fluoropolymer.

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

10. The article of claim 9, wherein inorganic oxide comprises a silicon oxide. ​ 11. The article of any one of claims 1 to 10, wherein the skin layer has a thickness of 5 nm to 15 micrometers, inclusive.

12. The article of claim 11, wherein the skin layer has a thickness of 5 nm to 500 nm, inclusive.

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

14. The article of any one of claims 1 to 13, further comprising a support layer comprising a polymeric film releasably attached to the first major skin layer surface of the skin layer.

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

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

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

18. A method comprising: creating a structured substrate on a support structure comprising a support layer and a skin layer having a first major skin layer surface bonded to the support layer, the structured substrate having a planar major surface bonded to a second major skin layer surface of the skin layer and a structured surface comprising a protruding surface, a recessed surface, and a side surface connecting the protruding surface and the recessed surface, wherein the structured substrate comprises an anti-biofouling layer, an inorganic layer, and a masking layer; bonding a transfer carrier comprising 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; and separating the skin layer from the support layer, wherein the transfer carrier and structured substrate remain bonded to the skin layer, thereby forming a transferable structured substrate.

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

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

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

22. The method of claim 21, wherein at least a portion of the masking layer is removed upon separating the transfer carrier from the structured surface.

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