Membrane-free chemically differentiated nanostructured substrates on rigid substrates

Abstract

A chemically differentiated nanostructured substrate (330) is described. These substrates are bonded (160) directly to a rigid adhesive (180) without the use of an intermediate film. Methods of making chemically differentiated nanostructured substrates and bonding them to rigid substrates are also described.

Description

Technical Field

[0001] This disclosure relates to membrane-free, chemically differentiated structured substrates. The substrates are designed to allow them to be bonded to rigid substrates such as glass. Methods for manufacturing such membrane-free structured substrates are also described. Summary of the Invention

[0002] In summary, in one aspect, this disclosure provides a structured article comprising a rigid substrate, an adhesive bonded to the rigid substrate, and the structured substrate itself. The structured substrate comprises: an inorganic layer having a first primary surface and a second primary surface, the first primary surface being directly bonded to the adhesive; and an anti-biofouling layer having a first primary surface and a second primary surface, the first primary surface of the anti-biofouling layer being bonded to a first portion of the second primary surface of the inorganic layer. The structured substrate includes a protruding surface and a recessed surface, the protruding surface including the second primary surface of the anti-biofouling layer, and the recessed surface including a second exposed portion of the second primary surface of the inorganic layer.

[0003] In another aspect, this disclosure provides a method for manufacturing a structured article. The method includes providing a release layer bonded to a support layer; manufacturing a structured intermediate substrate comprising: (i) a masking layer having a first main surface bonded to the release layer and a second main surface including structures forming recessed and protruding surfaces; (ii) an anti-biofouling layer bonded to the recessed surface; and (iii) an inorganic layer having a protruding surface bonded to the masking layer and bonded to the second main surface of the anti-biofouling layer; and applying an adhesive layer to the first main surface of the inorganic layer such that the first main surface of the inorganic layer is directly bonded to the first main surface of the adhesive layer.

[0004] In some cases, manufacturing a structured intermediate substrate includes: (a) pressing a second primary surface of a masking layer against a structured mold surface to form a structure of the second primary surface of the masking layer, wherein the structure corresponds to the inversion of a pattern in the structured mold surface; (b) applying an anti-biocontamination layer over the second primary surface of the masking layer; and (c) etching the anti-biocontamination layer to remove the anti-biocontamination layer from the protruding surface while retaining the anti-biocontamination layer covering at least a portion of the recessed surface. Attached Figure Description

[0005] Figure 1 Intermediate structures formed in some methods of the present invention are illustrated.

[0006] Figure 2A A transferable structured substrate according to an embodiment of the present invention is illustrated.

[0007] Figure 2B Another transferable structured substrate according to an embodiment of the invention is illustrated.

[0008] Figure 3A An example is a membrane-free, chemically differentiated nanostructured substrate on a rigid substrate according to an embodiment of the present invention.

[0009] Figure 3B An example is illustrated of another membrane-free, chemically differentiated nanostructured substrate on a rigid substrate according to an embodiment of the present invention. Detailed Implementation

[0010] 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 nanometers to 2000 nanometers (nm). The pores are then filled with a hydrogel containing chemical components selected for binding the target DNA sample.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] Co-owned U.S. Provisional Patent Application No. 63 / 502277 (Transferable Film-Based Structured Substrates, Kayla et al., PCT / IB2024 / 053858) describes the use of thin surface layers to facilitate the transfer of structured substrates to rigid supports such as glass or silicon. Using thin surface layers reduces the influence of autofluorescence compared to thicker supports; however, some of the surface layers can still fluoresce. Furthermore, the adhesion between layers must be controlled to avoid damaging the functional layers of the structured substrate when removing temporary layers and transferring structures with thin surface layers.

[0015] Robust processes for producing film-based nanopatterned substrates remain needed, particularly cost-effective roll-to-roll processes. Furthermore, 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 necessary.

[0016] The inventors have developed a method for producing chemically differentiated nanostructured substrates that are bonded to rigid substrates without the need for thick carrier films or thin surface layers constructed using existing techniques. By eliminating such films from the final structure, the articles of the present invention eliminate concerns about autofluorescence and thickness uniformity or flatness associated with such films. Furthermore, the method remains applicable to cost-effective roll-to-roll processing even without such films in the final structure.

[0017] The method disclosed herein begins with a support comprising a flexible support layer and a release layer. A structured layer is then fabricated on the release layer, which can be performed using a roll-to-roll process. This structured layer can then be transferred to a rigid substrate and the support layer and release layer are removed. In prior art methods, a transparent, non-autofluorescent substrate (carrier layer or surface layer) is required because these layers remain in the final structure. In this disclosure, both the support layer and the release layer are removed prior to use, and these limitations are not required.

[0018] A wide range of substrates can be used for the support layer. 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 (e.g., polypropylene and polyethylene), cyclic olefin polymers (COP), cyclic olefin copolymers (COC), poly(meth)acrylates, polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide, polyurethane, polyethersulfone, cellulose acetate-based materials, polymethyl methacrylate, polyvinyl chloride, polylactic acid, 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.

[0019] In some cases, the release layer is releasably bonded to the support layer. In such cases, the structured substrate built on the release layer can first be separated from the support substrate at the release layer / support substrate interface. Subsequently, the release layer is removed from the structured substrate. In other cases, the release layer is more firmly bonded to the support layer. In such cases, the structured substrate built on the release layer can be peeled off from the release layer without separating the release layer from the support layer.

[0020] Since the release layer does not remain part of the article during use, a thin, low-autofluorescence material is not required. The composition of the release layer is not particularly limited and can be, for example, thermoplastic or thermosetting. Examples of suitable materials for the release layer include acrylates, methacrylates, silicones, fluoropolymers, olefin or hydrocarbon polymers (e.g., polyethylene and polypropylene), styrene derivatives, polyurethanes, cyclic olefin polymers and copolymers, polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).

[0021] The adhesion between the release layer and the support layer can be adjusted to provide a peelable or non-peelable release layer. This can be achieved by selecting a support layer composition, a release layer composition, or both. The surface of the support layer can also be treated with known materials and processes to obtain the desired peel force. The peel force required to separate the release layer from the support layer can be determined using standard test methods, including 90-degree or 180-degree peel tests.

[0022] If the release layer is to be separated from the support substrate (i.e., the peelable release layer), the peel force should be low enough to allow the release layer to be cleanly peeled from the support layer without damaging or distorting the structure built on the release layer. In some cases, the peel force between the release 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, or even at least 2 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 the end values.

[0023] If the release layer is to remain attached to the support substrate (i.e., a non-releasable release layer), the peel force must be high enough to allow removal of the structure built on the release layer without removing it from the support substrate. Generally, the lower limit of the peel force between the release layer and the support layer is greater than the peel force between the structured layer and the release layer. The release force required to separate the release layer from the support layer can be determined using standard test methods (including 90-degree or 180-degree peel tests) and is also referred to as the peel force. In some cases, the peel force between the release layer and the support layer is at least 1.5 times that between the structured layer and the release layer, for example, at least 2 times or even at least 3 times that between the structured layer and the release layer. Generally, there is no upper limit to the peel force for such non-releasable release layers.

[0024] Chemically differentiated structures (e.g., microstructures, nanostructures, or both) are constructed on the release layer of the support. Such structures may also be referred to as functionalized structures. Known methods for manufacturing such chemically differentiated structures can be used, including roll-to-roll methods. 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.

[0025] These structures include protruding surfaces and recessed surfaces. As used herein, the terms "protruding surface" and "recessed surface" refer to the relative positions of the exposed surfaces of the structured layers. Thus, in the case of a protrusion (e.g., a column) surrounded by a shore region, the exposed distal end of the column is the protruding surface relative to the recessed exposed shore region between the columns. Similarly, in the case of a hole, the exposed base of the hole is the recessed surface relative to the protruding surface of the shore region surrounding the hole.

[0026] In some cases, the structure is a nanostructure, meaning that one or more dimensions of the structure are between 5 nanometers and 5000 nanometers, for example, 5 nm to 1500 nm, 10 nm to 1500 nm, 50 nm to 1000 nm, or even 50 nm to 500 nm. For example, in some cases, one or more of the diameter, height, and spacing between protrusions or pillars are between 5 nanometers and 5000 nanometers, for example, 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 grooves or holes are between 5 nanometers and 5000 nanometers, for example, 5 nm to 1500 nm, 10 nm to 1500 nm, 50 nm to 1000 nm, or even 50 nm to 500 nm.

[0027] Generally, chemically differentiated structured substrates include a masking layer, a biofouling-resistant layer, and an inorganic layer. The structured substrate is bonded to a rigid substrate with an adhesive, eliminating the need for prior art intermediary membranes, such as carrier membranes or surface layers. As used herein, when referring to the bonding of a first layer to a second layer, the term "bonding" includes both direct 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 can be indirectly bonded to the second layer via an intermediate layer, such as an adhesive layer.

[0028] Masking layer. A masking layer is a removable layer (e.g., a washable or 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 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.

[0029] Anti-biocontamination layer. An anti-biocontamination layer is a hydrophobic, non-reactive layer that resists or prevents 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.

[0030] Biofouling resistant materials may include components made of thermoplastics, such as fluoropolymers, polyolefins (having straight or cyclic groups in the main chain), polyesters, silicones, polyethers, poly(meth)acrylates (i.e., polyacrylates and polymethacrylates) (e.g., C18) having straight-chain alkyl chains with high density of -CH3 ends that can crystallize or due to branching, and silicone (meth)acrylates. In some cases, fluoropolymers are preferred.

[0031] Inorganic layers. Inorganic layers comprise metals, quasi-metals, metal oxides, or quasi-metal oxides. Vapor-depositable materials suitable for functionalization with adhesion 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 oxides of TiO, aluminum oxides (such as AlOx), other metals (such as Au, Sn, Ge, Ga, Zn, and In), and mixtures and combinations 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.

[0032] The support is typically a rigid substrate. Exemplary substrates include glass and silicon substrates, such as glass and silicon wafers.

[0033] Exemplary adhesives include hot melt adhesives or pressure-sensitive adhesives. The adhesive layer is typically optically transparent and exhibits 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 even 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.

[0034] Example

[0035] Step 1: (Fabrication of the Structured Template Film) A nano-characterized template film is prepared by molding acrylate resin A onto a polycarbonate film. The coated film is pressed onto a nanostructured 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 nanostructured nickel tool consists of a 10 cm × 10 cm patterned area with 250 nm pores spaced at a pitch of 600 nm. Features are arranged on a hexagonal grid. The features are approximately 200 nm deep and have sidewall angles of approximately 4 degrees. The coating thickness of acrylate resin A on the film is sufficient to completely wet the nickel surface and forms rolling beads of resin when the coated film is pressed onto the nanostructured nickel surface. When in contact with the nanostructured nickel surface, the resin-coated 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. After the film was peeled off from the nanostructured nickel surface, the nanostructured side of the acrylate resin template film was again exposed to radiation from the Fusion UV lamp systems.

[0036] Step 2: (Release Treatment of the Nanocharacterized Template Film) A silicon-containing release film layer, 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 nanocharacterized template film prepared in Step 1 in a parallel-plate capacitively coupled plasma reactor to generate a nanocharacterized template film. The chamber has a central cylindrical energized electrode with a surface area of ​​1.7 square meters. After the nanocharacterized template film is placed on 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. Treatment is performed using a plasma-enhanced CVD method 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 nanocharacterized template film 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 (9 mTorr). Subsequently, 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 to form the released, nanocharacterized molded membrane. At the end of this treatment time, the RF power and gas supply were stopped, and the reaction chamber was returned to atmospheric pressure.

[0037] Step 3: (Manufacturing the release layer on the support film) A 400 nm thick acrylate peelable release layer is manufactured on the PET support layer using the method described in International Patent Application PCT / IB2022 / 061266 (“Planarized Inorganic Thin Film Transfer Article”).

[0038] Step 4: (Making the Masking Layer) The release-treated nano-characterized mold film produced in Step 2 was slot-coated with coating solution 1 (PVA) at a speed of 0.05 m / s. The solution was applied to a width of 10.16 cm and pumped at a rate of 6.8 sccm using a Harvard injection pump. The film was dried at 65.5°C for 3 minutes and then introduced into the roll gap. At the roll gap, the film produced in Step 3 and the coated film were laminated together so that the release layer contacted the PVA film. The roll gap consisted of a rubber roller with a hardness of 90 and a steel roller set at 76.7°C. The roll gap was joined by two Bimba cylinders pressurized at 0.55 MPa. The web tension was set to approximately 0.0057 N / mm. The dried PVA masking layer was then separated from the release-treated mold film. This produced a nano-structured masking layer bonded to the PET support layer. The nanostructures on the PVA masking layer are the inverse of the patterns on the nanocharacterized mold film; that is, the masking layer has a column pattern corresponding to the pores in the nanocharacterized mold film, wherein the columns are surrounded by shore regions.

[0039] Step 5: (Manufacturing the Anti-Biocontamination Layer) Using a slit die, the fluoropolymer solution was applied to the nano-characterized masking layer in a roll-to-roll process at a rate of 0.0381 m / s. The solution was coated to a width of 15.24 cm and pumped using a Harvard syringe pump at a rate of 5.63 sccm. The coating was dried at 65.5°C for 3 minutes. The resulting intermediate structure... Figure 1 As shown in the image.

[0040] refer to Figure 1 The intermediate structure 100 includes a nano-characterized masking layer 110, which is bonded to a release layer 120 on the main surface of the support layer 130. The structured surface of the masking layer 110 includes a recessed shore region 112 surrounding the protruding pillar 114. An anti-biofouling layer 140 covers the structured surface of the nano-characterized masking layer 110, thereby providing a flat exposed surface 142.

[0041] The following steps are predictable and will not be performed.

[0042] Step 6: (Exposing the Masking Layer) Remove the anti-biocontamination material deposited in Step 5 from the top of the masking layer pillar using plasma etching. Using known methods, such as those described in U.S. Provisional Patent Application No. 63 / 502277 (Transferable Film-Based Structured Substrates, Kayla et al., PCT / IB2024 / 053858), the linear velocity and etching conditions are selected such that the duration of exposure to the etching conditions is sufficient to remove the anti-biocontamination material from the top of the pillar, but limited to such that at least some of the anti-biocontamination material remains on the shore plate region.

[0043] In some cases, the etching duration and conditions can be controlled such that the anti-biofouling layer is removed from the top of the post and a portion extending along the side of the post from the shore region. However, at least some of the anti-biofouling material remains on the shore region. This results in a structured intermediate substrate with surfaces including recessed portions and protruding portions. The protruding portions of the surfaces include the exposed surface of the masking material forming the top of the post, and the recessed portions include the surface of the anti-biofouling layer in the shore region.

[0044] In some cases, the etching duration and conditions can be controlled such that the anti-biocontamination layer is removed only from the top of the column. This will produce a flat surface that includes the surface of the anti-biocontamination material in the shore platform area and the exposed surface of the masking material forming the top of the column.

[0045] Step 7: (Deposit Inorganic Layer) An inorganic layer is then deposited on the patterned anti-biocontamination / masking surface from Step 6. This inorganic layer can be deposited using a parallel-plate capacitively coupled plasma reactor as described in U.S. Patent No. 6,696,157 (“Diamond-Like Glass Thin Films”, David et al.). This inorganic layer covers the anti-biocontamination layer in the shore plateau region between the masking materials on the tops of the columns.

[0046] If the etching duration and conditions are controlled such that the anti-biocontamination layer is removed only from the top of the column, the inorganic layer will have a flat surface adjacent to the surface of the anti-biocontamination material in the shore plateau region and the exposed surface of the masking material forming the top of the column. If the etching duration and conditions are controlled such that the anti-biocontamination layer is removed from the top of the column and from a portion extending along the side of the column from the shore plateau region, the inorganic layer will have a structured surface comprising a recessed surface and a protruding surface, wherein the inorganic layer is adjacent to the masking layer at the top of the column at the recessed surface and to the anti-biocontamination layer in the shore plateau region at the protruding surface.

[0047] Step 8: (Depositing Adhesive) Apply the adhesive to the inorganic layer from Step 7 (e.g., coat it onto the inorganic layer or laminate it to the inorganic layer) to form a continuous layer. The adhesive can be dissolved in a solvent or solvent mixture to aid coating and achieve the desired adhesive thickness. The liner can be laminated to the adhesive. The resulting structures from two alternative solutions are shown in... Figure 2A and Figure 2B As shown in the image.

[0048] refer to Figure 2AThe transferable structured membrane 200 includes a structured membrane 250 bonded to a release layer 120 bonded to a support layer 130. Starting with the release layer, the structured membrane 250 includes a masking layer 110 having pillars 114 surrounded by a shore region 112. The shore region 112 is covered by an anti-biofouling layer 140. An inorganic layer 150 covers the exposed portions of the pillars and the anti-biofouling layer in the shore region, as well as those portions of the sides of the pillars that remain uncovered by the anti-biofouling layer. An adhesive 160 is bonded to the inorganic layer 150 of the structured membrane 200 and is covered by a liner 170. The transferable structured membrane 200 is produced by a method in which the etching duration and conditions are controlled such that the anti-biofouling layer is removed from the top of the pillars and from a portion extending along the sides of the pillars in the shore region. Therefore, the surface of the inorganic layer 150 includes a recessed portion 154 adjacent to the top of the pillars 114 and a protrusion 156 adjacent to the anti-biofouling layer 140 in the shore region 112.

[0049] refer to Figure 2B The transferable structured membrane 201 includes a structured membrane 251 bonded to a release layer 120 on a support layer 130. Starting with the release layer, the structured membrane 251 includes a masking layer 110 having a pillar 114 surrounded by a shore region 112. The shore region 112 is covered by an anti-biofouling layer 141. An inorganic layer 151 covers the exposed portion of the pillar and the anti-biofouling layer in the shore region. An adhesive 160 is bonded to the inorganic layer 151 of the structured membrane 201 and is covered by a gasket 170. The transferable structured membrane 201 will be produced by a method in which the etching duration and conditions are controlled such that the anti-biofouling layer is removed from the top of the pillar. Therefore, the surface 158 of the inorganic layer 151 is flat and adjacent to both the top of the pillar and the anti-biofouling layer in the shore region.

[0050] Step 9: (Lamination to Glass) The adhesive-coated film from Step 8 can be cut to the size of the target rigid substrate (e.g., a glass wafer). Remove the liner to expose the adhesive layer. Place the resulting construct on top of the glass wafer (or other rigid substrate), with the adhesive in contact with the glass, and then vacuum laminate it to the rigid substrate using a NILT CNI tool.

[0051] If the release layer is a peelable release layer, the support layer can be removed before or after lamination to the rigid substrate. If the release layer is a non-peelable release layer, the support layer is removed after lamination to the rigid substrate.

[0052] Step 10: (Removal of Release and Mask Layers) After lamination, the release and mask layers (and support layer, if present) can be removed from the fabric using any suitable method. In some cases, etching can be used to remove the release layer, followed by washing to remove the mask layer. In some cases, the release and mask layers can be stripped. In some cases, the release and support layers can be stripped, and then the mask layer can be washed away. In some cases, the support layer, release layer, and mask layer can be stripped.

[0053] Regardless of the removal process, this step will expose the structure of the boreholes, including an inorganic layer at the bottom and a biofouling-resistant layer in the shore platform region between the boreholes. Figure 3A and Figure 3B The alternative options are shown below.

[0054] refer to Figure 3A The structured article 300 includes a nanostructured substrate 330 bonded to a rigid substrate 180 by an adhesive 160. The nanostructured substrate 330 includes an inorganic layer 150 and an anti-biofouling layer 140. A plurality of pores 310 are formed in the inorganic layer 150, thereby forming exposed surfaces at the base of the pores and optionally at least a portion of the sidewalls of the pores. The anti-biofouling layer 140 covers a shore region 320 surrounding the pores 310, thereby creating a chemically differentiated nanostructured surface. This structure will be used by... Figure 2A A transferable structured membrane 200 is produced.

[0055] refer to Figure 3B The structured article 301 includes a nanostructured substrate 331 bonded to a rigid substrate 180 by an adhesive 160. The nanostructured substrate 331 includes an inorganic layer 151 having a flat surface 158 and an anti-biofouling layer 140. The anti-biofouling layer 140 surrounds a plurality of pores 410, wherein the exposed surface at the base of the pores includes a portion of the flat surface 158 of the inorganic layer 151. Surfaces 142 of the anti-biofouling layer 140 form shore regions 420 surrounding the pores 410, thereby creating a chemically differentiated nanostructured surface. This structure will be used by... Figure 2B The transferable structured membrane 201 is generated.

[0056] Compared to existing technologies, this method eliminates the need for an additional membrane between the adhesive and the nanostructured substrate; the adhesive is directly bonded to the inorganic layer of the nanostructured substrate. Therefore, the resulting product is a membrane-free, chemically differentiated nanostructured substrate on a rigid substrate.

Claims

1. A structured article comprising a structured substrate bonded to a rigid substrate by an adhesive; The structured substrate includes: An inorganic layer having a first main surface and a second main surface, the first main surface being directly bonded to the adhesive; The structured substrate includes an anti-biofouling layer having a first primary surface and a second primary surface, the first primary surface of the anti-biofouling layer being bonded to a first portion of the second primary surface of the inorganic layer, and wherein the structured substrate includes a protruding surface and a recessed surface, the protruding surface including the second primary surface of the anti-biofouling layer, and the recessed surface including an exposed second portion of the second primary surface of the inorganic layer.

2. The structured article according to claim 1, wherein the second primary surface of the inorganic layer is flat.

3. The structured article according to claim 1, wherein a second portion of the second main surface of the inorganic layer is recessed relative to a first portion of the second main surface of the inorganic layer.

4. The structured article according to any one of the preceding claims, wherein the structured substrate includes a plurality of holes surrounded by a shore region, wherein each hole has a base, and wherein the recessed surface includes the base of the hole, and the protruding surface includes the shore region.

5. The structured article according to any one of the preceding claims, wherein the anti-biofouling layer comprises a fluoropolymer, an olefin polymer, a silicone resin, a polyether, or a poly(meth)acrylate.

6. The structured article according to any one of the preceding claims, wherein the inorganic layer comprises at least one of an oxide of silicon, an oxide of titanium, and an oxide of aluminum.

7. The structured article according to claim 6, wherein the inorganic oxide includes silicon oxide.

8. The structured article according to any one of the preceding claims, wherein the rigid substrate comprises at least one of glass and silicon.

9. The structured article according to any one of the preceding claims, wherein the thickness of the anti-biofouling layer is from 5 nanometers to 5000 nanometers.

10. The structured article according to claim 9, wherein the thickness of the anti-biofouling layer is 50 nanometers to 500 nanometers.

11. The structured article according to any one of claims 4 to 10, wherein at least one dimension of the pore is from 5 nanometers to 5000 nanometers.

12. The structured article of claim 11, wherein at least one dimension of the pore is 50 nanometers to 500 nanometers.

13. A method for manufacturing a structured article, the method comprising: Provides a release layer that is bonded to the support layer; A structured intermediate substrate is manufactured, the structured intermediate substrate comprising: (i) a masking layer having a first main surface bonded to the release layer and a second main surface including structures forming recessed and protruding surfaces; (ii) an anti-biofouling layer bonded to the recessed surface; and (iii) an inorganic layer having a protruding surface bonded to the masking layer and bonded to the second main surface of the anti-biofouling layer; and An adhesive layer is applied to the first main surface of the inorganic layer, such that the first main surface of the inorganic layer is directly bonded to the first main surface of the adhesive layer.

14. The method of claim 13, wherein manufacturing the structured intermediate substrate comprises: (a) pressing the second main surface of the masking layer against the surface of the structured mold to form a structure of the second main surface of the masking layer, wherein the structure corresponds to the inversion of a pattern in the surface of the structured mold; (b) applying the anti-biocontamination layer over the second main surface of the masking layer; and (c) etching the anti-biocontamination layer to remove the anti-biocontamination layer from the protruding surface while retaining the anti-biocontamination layer covering at least a portion of the recessed surface.

15. The method of claim 13 or 14, further comprising bonding a second primary surface of the adhesive layer to a rigid substrate and removing the release layer and the masking layer.

16. The method of claim 15, wherein removing the release layer comprises etching the release layer.

17. The method of claim 15, wherein removing the release layer comprises peeling the release layer off the masking layer.

18. The method according to any one of claims 15 to 17, wherein removing the masking layer comprises dissolving the masking layer.

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