Laminate containing an adhesion promoter layer and method for manufacturing the laminate

Abstract

In the IAP process, this invention provides a laminate in which the adhesive strength of a resist layer formed from a curable vinylbenzene monomer composition to a substrate is improved, and a method for forming the same. [Solution] The laminate may comprise a substrate 12, an adhesion promoter layer 13, and a coating layer 14, wherein the adhesion promoter layer contains a silane compound of formula (1), TIFF2026071177000022.tif1553 X is a C1-C3-alkyl group, n is 1 to 5, and R1 and R2 are independently alkyl, aryl, alkoxy, or aryloxy groups. The adhesion promoter layer can provide strong adhesion of the coating layer to the substrate by forming covalent bonds with the substrate and with the coating layer.

Description

[Technical Field]

[0001] This disclosure relates to a laminate comprising a substrate, an adhesion promoter layer, and a coating layer, and to a method for manufacturing the laminate, wherein the adhesion promoter layer comprises a silane compound. [Background technology]

[0002] UV-curable materials in the field of inkjet adaptive planarization (IAP) can include vinylbenzene-based polymerizable materials for forming a cured resist layer with high etching resistance and high thermal stability. However, one drawback of such a cured resist layer is its weak adhesion to the underlying substrate.

[0003] In particular, in the IAP process, it is necessary to improve the adhesion strength of the resist layer formed from a curable vinylbenzene monomer composition to the underlying substrate. [Overview of the Initiative] [Means for solving the problem]

[0004] In one embodiment, the laminate may comprise a substrate, an adhesion promoter layer directly overlapping the substrate, and a coating layer directly overlapping the adhesion promoter layer, wherein the adhesion promoter layer comprises a silane compound of formula (1). TIFF2026071177000002.tif1553X is a C1-C3 alkyl group, n is 1 to 5, and R1 and R2 are independently alkyl, aryl, alkoxy, or aryloxy.

[0005] On one side of the laminate, R1 and R2 of the silane compound of formula (1) are independently C1-C3-alkyl, C1-C3-alkyloxy, or a combination thereof.

[0006] In certain aspects, the silane compound of formula (1) is TIFF2026071177000003.tif1653 or Includes TIFF2026071177000004.tif1853 or combinations thereof.

[0007] In another aspect of the laminate, the substrate material comprises silicon, aluminum, zirconium, tin, titanium, nickel, or any oxide thereof.

[0008] In a further aspect of the laminate, the thickness of the adhesion promoter layer is at least 0.4 nm and 100 nm or less.

[0009] In yet another aspect of the laminate, the amount of the silane compound of formula (1) in the adhesion promoter layer is at least 90% by weight, based on the total weight of the adhesion promoter layer.

[0010] In a further aspect, the coating layer of the laminate is a cured resist of a polyfunctional vinylbenzene-based IAP material. In a specific aspect, the vinylbenzene-based IAP material is a curable composition comprising at least 80% by weight of a polyfunctional vinylbenzene monomer.

[0011] In yet another specific aspect, the polyfunctional vinylbenzene-based IAP material is essentially acrylate monomer-free.

[0012] In a further aspect of the laminate, the vapor pressure of the silane compound of formula (1) is at least 0.1 Torre at 25°C.

[0013] In another aspect of the laminate, the coating layer has an adhesive strength to the substrate of at least 2.5 MPa.

[0014] In one embodiment, a method for forming a laminate is to directly apply an adhesion promoter layer to the outer surface of a substrate, wherein the adhesion promoter layer comprises a silane compound of formula (1), TIFF2026071177000005.tif1553X is a C1-C3 alkyl, n is 1 to 5, and R1 and R2 are independently alkyl, or aryl, or alkoxy, or aryloxy, and a coating layer is applied that directly overlaps the adhesion promoter layer.

[0015] In one aspect of the above method, applying the adhesion promoter layer comprises depositing the silane compound of formula (1) onto the outer surface of the substrate.

[0016] In another aspect, the method comprises forming a covalent bond between the adhesion promoter layer and the substrate, and forming a covalent bond between the adhesion promoter layer and the coating layer.

[0017] In a further aspect of the above method, applying the coating layer includes applying a liquid photocurable composition to the adhesion promoter layer and curing the photocurable composition to form the coating layer.

[0018] In yet another aspect of the method described above, the liquid photocurable composition comprises a polymerizable material comprising at least 80% by weight of at least one polyfunctional vinylbenzene monomer, based on the total weight of the polymerizable material.

[0019] In one aspect of the above method, after applying the adhesion promoter layer and before applying the coating layer, the water contact angle with respect to the adhesion promoter layer is at least 10 degrees and no more than 45 degrees.

[0020] In another aspect of the above method, the water vapor pressure of the silane compound is at least 0.1 Torre at 25°C.

[0021] In a further aspect of the above method, after applying the adhesion promoter layer and before applying the coating layer, the surface free energy of the adhesion promoter layer is at least 55 mJ / cm². 2 That is the case.

[0022] In one embodiment, a kit for forming a laminate comprises a first composition, the first composition being adapted to form an adhesion promoter layer and comprising at least one silane compound of formula (1), TIFF2026071177000006.tif1554X where TIFF2026071177000006.tif1554X is C1-C3-alkyl, n is from 1 to 5, and R1 and R2 are independently alkyl, or aryl, or alkoxy, or aryloxy, and a second composition, the second composition being a liquid photocurable composition adapted to form a coating layer that directly overlaps the adhesion promoter layer.

[0023] On one side of the kit, the liquid photocurable composition comprises a polymeric material comprising at least 80% by weight of at least one polyfunctional vinylbenzene monomer based on the total weight of the polymeric material.

[0024] In another embodiment, a method of manufacturing an article comprises applying a layer of a photocurable composition to a substrate, the substrate comprising on an outer surface an adhesion promoter layer comprising a silane compound of formula (1), TIFF2026071177000007.tif1453X where TIFF2026071177000007.tif1453X is C1-C3-alkyl, n is from 1 to 5, and R1 and R2 are independently alkyl, or aryl, or alkoxy, or aryloxy, the photocurable composition directly overlapping the adhesion promoter layer, bringing the photocurable composition into intimate contact, irradiating the photocurable composition with light to form a cured layer, removing the substrate from the cured layer to obtain a laminate, and manufacturing an article from the laminate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Embodiments are shown by way of example and are not limited to the accompanying drawings. [Figure 1A] FIG. 1A includes a view of a laminate in one embodiment. [Figure 1B]Figure 1B includes a diagram of an assembly for testing the adhesion strength of a coating layer to a substrate of the laminate shown in Figure 1A in one embodiment. Those skilled in the art will understand that elements in the drawings are shown for simplification and clarity and are not necessarily drawn to scale. For example, some dimensions of elements in the drawings may be exaggerated relative to others to facilitate understanding of embodiments of the invention. [Modes for carrying out the invention]

[0026] The following description, combined with the drawings, is provided to aid in understanding the teachings disclosed herein. The following discussion focuses on specific implementations and embodiments of the teachings. This focus is provided to aid in illustrating the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Materials, methods, and examples are illustrative and not intended to limit the scope of the invention. Many details relating to specific materials and processing procedures, beyond what is described herein, are conventional and can be found in textbooks and other sources within the field of imprint and lithography.

[0028] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof shall cover non-exclusive inclusion. For example, a process, method, article, or apparatus comprising a list of features is not necessarily limited to those features alone and may include other features not expressly listed or specific to such process, method, article, or apparatus.

[0029] As used herein, “or” means inclusive or exclusive unless expressly stated otherwise. For example, condition A or B satisfies one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0030] Furthermore, the use of “one (a)” or “one (an)” is used to describe the elements and components described in the specification. This is used simply for convenience to give a general meaning to the scope of the invention. This description should be read as including one or at least one, and the singular form includes the plural form unless it is explicitly intended not to be plural.

[0031] As used herein, the terms "alkyl" or "aryl" are used to include unsubstituted groups (e.g., unsubstituted alkyl groups), but may also include substituted groups (e.g., substituted alkyl groups or substituted aromatic rings).

[0032] In one embodiment, as shown in Figure 1A, the present disclosure relates to a laminate (11) comprising a substrate (12), an adhesion promoter layer (13) directly overlapping the substrate (12), and a coating layer (14) directly overlapping the adhesion promoter layer (13). The adhesion promoter layer (13) may contain a silane compound of formula (1), TIFF2026071177000008.tif1553X is a C1-C3 alkyl group, n is 1 to 5, and R1 and R2 are independently a substituted or unsubstituted alkyl group, or an aryl group, or an alkoxy group, or an aryloxy group.

[0033] As shown in the embodiments of this specification, the adhesion promoter layer of the laminate can help ensure good adhesion of the coating layer to the substrate.

[0034] In one respect, R1 and R2 of the silane compound of formula (1) are independently C1-C3-alkyl, C1-C3-alkoxy, or a combination thereof.

[0035] In certain embodiments, the silane compound of formula (1) may comprise one alkyl group, two alkoxy groups, and one alkyl-thiol group. A non-limiting example for such embodiments may be structure (2).

[0036] TIFF2026071177000009.tif1753

[0037] In another specific embodiment, the silane compound of formula (1) may comprise three alkoxy groups and one alkylthiol group. A typical non-limiting example of such a silane compound may be structure (3).

[0038] TIFF2026071177000010.tif1853

[0039] In certain respects, the silane compounds of formula (1) are small molecules having molecular weights of 500 g / mol or less, 300 g / mol or less, 400 g / mol or less, 300 g / mol or less, or 200 g / mol or less.

[0040] In one aspect, the silane compound of formula (1) in the adhesion promoter layer (13) can form covalent bonds with the substrate (12) and with the coating layer (14). In a particular aspect, the alkoxy group of the silane compound of formula (1) can form covalent bonds with functional groups of the substrate, for example, hydroxyl groups present on the surface of the substrate. In another particular aspect, the thiol group of the silane compound may form covalent bonds with vinyl groups of vinyl monomers contained in the coating composition.

[0041] As used herein, the phrase "silane compound of formula (1)" is interchangeable with the term "adhesion promoter" unless otherwise specified.

[0042] As used herein, the term “laminated structure” shall be referred to as “coated substrate” or “multilayer structure” unless otherwise specified.

[0043] In one embodiment, a method for forming the laminate (11) of the present disclosure may include i) directly applying an adhesion promoter layer (13) to a substrate (12), and (ii) directly applying a coating layer (14) to the adhesion promoter layer (13).

[0044] The substrate (12) of the laminate (11) is a material selected from metals, metal alloys, metal oxides, ceramics, glass, or polymers. In aspect, the substrate may comprise silicon, aluminum, zirconium, tin, titanium, or nickel. In particular, the substrate is a silicon wafer. Although not bound by theory, functional groups contained in the outer surface region of the substrate can react by forming covalent bonds with the functional groups of the adhesion promoter of formula (1).

[0045] In one particular aspect, the adhesion promoter layer can be applied to the substrate by vapor deposition. The vapor deposition can be adapted so that only a single layer of adhesion promoter molecules is deposited on the substrate. In another aspect, the adhesion promoter layer can contain multiple adhesion promoter molecules along the thickness direction of the adhesion promoter layer.

[0046] Deposition can be carried out using a bubbler or vaporizer, or manually. The bubbler and vaporizer may use an inert gas, typically nitrogen, to vaporize the adhesion promoter, and the vapor can be blown into a closed chamber containing the substrate (e.g., a Si wafer) on which the adhesion promoter is deposited. After a certain time, the wafer may have a sufficient amount of adhesion promoter deposited on its surface and may be used for an IAP or NIL process.

[0047] Compared to spin coating, evaporation can be easily integrated into automated IAP processes, which can improve throughput.

[0048] In terms of manual evaporation, as used herein, a specified amount of adhesion promoter is added to an open container, such as a Petri dish, and placed together with the substrate (e.g., a silicon wafer) in a sealed container such as a desiccator or wafer hoop. Depending on the vapor pressure of the adhesion promoter, the adhesion promoter evaporates in the sealed container and deposits onto the substrate over a specified period of time. The required time for a particular deposition can be evaluated by preliminary experiments with varying deposition times. The deposition time is considered suitable for this disclosure when the adhesion strength of the IAP test resist applied to the adhesion promoter layer is at least 2.5 MPa.

[0049] To achieve the desired deposition rate, the vapor pressure of the silane compound of formula (1) at 25°C is at least 0.1 toll, at least 0.2 toll, at least 0.3 toll, at least 0.4 toll, at least 0.5 toll, at least 1.0 toll, at least 5 toll, at least 15 toll, or at least 20 toll. In another aspect, the vapor pressure of the silane compound of formula (1) may be 100 toll or less, 80 toll or less, 50 toll or less, or 30 toll or less.

[0050] In another specific aspect, the adhesion promoter layer can be applied by immersing the substrate in a liquid adhesion promoter or a solution containing an adhesion promoter dissolved in a solvent and then drying it, thereby allowing the adhesion promoter to be adsorbed onto the substrate surface.

[0051] In other respects, the adhesion promoter layer can be applied to the substrate by spin coating, spraying, or brushing.

[0052] In certain aspects, the silane compound of formula (1) can be partially self-crosslinked during or after deposition, before the application of the coating layer.

[0053] In a further aspect, the thickness of the adhesion promoter layer is at least 0.4 nm, for example, at least 0.6 nm, at least 1 nm, at least 2 nm, at least 3 nm, at least 5 nm, or at least 10 nm. In another aspect, the thickness of the adhesion promoter layer is 100 nm or less, for example, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, or 5 nm or less. The thickness of the adhesion promoter layer is a value between any of the minimum and maximum values ​​described above, and in a specific aspect, it is 0.4 nm to 10 nm or 0.5 nm to 5 nm.

[0054] In one aspect, the amount of adhesion promoter in the adhesion promoter layer is at least 90% by weight, at least 92% by weight, at least 94% by weight, at least 96% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight, or at least 99.9% by weight, based on the total weight of the adhesion promoter layer. In a particular aspect, the adhesion promoter layer is essentially composed of adhesion promoter, excluding unavoidable impurities.

[0055] In one embodiment, the coating layer (14) is a cured resist formed by curing a curable composition. As used herein, unless otherwise specified, the term “curable composition” refers to a curable composition for forming the coating layer (14) of a laminate (11). In certain aspects, the curable composition is referred to herein as “IAP resist” or “curable resist”.

[0056] In one respect, a curable composition may comprise a polymerizable material that forms a polymer network when polymerization is initiated by light and / or heat.

[0057] The polymerizable material of a curable composition may contain at least one polyfunctional vinylbenzene monomer. As used herein, the term polyfunctional vinylbenzene monomer of a polymerizable material refers to a polymerizable monomer comprising one or more benzene rings and at least two vinyl groups directly bonded to one or more benzene rings. In certain aspects, a polyfunctional vinylbenzene monomer may comprise at least three vinyl groups or at least four vinyl groups. In certain aspects, a polyfunctional vinylbenzene monomer may comprise two benzene rings and three vinyl groups bonded to the benzene rings. A non-limiting example of such a monomer is 3,4',5-trivinyl-1,1'biphenyl (3VPH).

[0058] In a particular aspect, the amount of at least one polyfunctional vinylbenzene monomer is at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, or at least 98% by weight, based on the total weight of the polymerizable material. In another aspect, 100% of the polymerizable material is at least one polyfunctional vinylbenzene monomer, or 97% by weight or less, 95% by weight or less, or 90% by weight or less.

[0059] In certain aspects, polymerizable materials may comprise up to 20% by weight of polymerizable monomers distinct from polyfunctional vinylbenzene monomers.

[0060] In one aspect, the polymerizable material of a curable composition may comprise an acrylate monomer in an amount of at least 1% to 20% by weight, at least 2% to 15% by weight, 10% by weight or less, or 5% by weight or less. In a particular aspect, the polymerizable material of a curable composition may not essentially contain an acrylate monomer. As used herein, essentially not containing an acrylate monomer means that the amount of acrylate monomer is 1% by weight or less based on the total weight of the polymerizable material. As further used herein, the term acrylate monomer refers to any polymerizable monomer containing one or more acrylate groups, where the acrylate groups may or may not be substituted. For example, substituted acrylates are C1-C5 alkyl acrylates, e.g., methacrylates.

[0061] The amount of polymerizable material contained in the curable composition is at least 40% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight, based on the total weight of the curable composition. In other words, the amount of polymerizable material may be 99% by weight or less, 96% by weight or less, or 92% by weight or less, based on the total weight of the curable composition.

[0062] In a further aspect, the curable composition may contain a solvent that is not polymerizable and can be removed by drying before and / or during polymerization. In another specific aspect, the photocurable composition may be essentially solvent-free. As used herein, essentially solvent-free means that the amount of solvent in the curable composition is less than 5% by weight, based on the total weight of the curable composition.

[0063] In another respect, the curable composition does not need to contain the particles required for the IAP process.

[0064] In one embodiment, the viscosity of the curable composition at 23°C is at least 1.0 mPa·s, at least 5 mPa·s, at least 10 mPa·s, at least 15 mPa·s, at least 20 mPa·s, or at least 30 mPa·s. In another embodiment, the viscosity may be 100 mPa·s or less, for example, 70 mPa·s or less, 50 mPa·s or less, 40 mPa·s or less, or 30 mPa·s or less. The viscosity of the photocurable composition is a value between any of the minimum and maximum values ​​described above. All viscosities listed herein are measured by the Brookfield method using a Brookfield Viscometer LVDV-II+Pro at 200 rpm, spindle size #18, and spin speed of 135 rpm.

[0065] In a further aspect, the curable composition for forming the coating layer (14) may contain at least one additive. Non-limiting examples of additives include surfactants, dispersants, stabilizers, cosolvents, initiators, inhibitors, or any combination thereof.

[0066] In certain embodiments, the coating layer (14) of the laminate is an imprint resist layer bonded to the wafer substrate (12) by an adhesion promoter layer (13) and adapted for a nanolithography process.

[0067] The contact angle of a curable composition (e.g., IAP resist) with respect to the substrate application surface is a critical parameter in nanoimprint lithography because it affects droplet spreading of the resist and further performance during the process. Measuring the water contact angle is an indicator of the droplet diffusion behavior of the IAP resist. As a general principle, the smaller the water contact angle, the faster the droplet spreads. On one hand, the water contact angle with respect to the adhesion promoter layer (before applying the coating layer) is 45 degrees or less, e.g., 40 degrees or less, 35 degrees or less, 30 degrees or less, 25 degrees or less, or 20 degrees or less. On the other hand, the water contact angle may be at least 5 degrees, at least 10 degrees, or at least 15 degrees.

[0068] In another embodiment, the thickness of the coating layer after curing is at least 10 nm, at least 50 nm, or at least 100 nm. In another aspect, the thickness of the coating layer may be 1000 nm or less, 500 nm or less, 100 nm or less, or 50 nm or less.

[0069] In one aspect, the adhesive strength of the coating layer (14) of the laminate (11) to the substrate (12) at 23°C, also known herein as pull-off strength, is at least 2.5 MPa, for example, at least 3.0 MPa, at least 3.5 MPa, at least 4.0 MPa, at least 4.5 MPa, at least 5.0 MPa, at least 5.5 MPa, at least 6.0 MPa, at least 6.5 MPa, for example, at least 7.0 MPa, at least 7.5 MPa, at least 8.0 MPa, or at least 8.5 MPa. In another aspect, the adhesive strength may be 20 MPa or less, for example, 15 MPa or less, or 10 MPa or less.

[0070] In a further embodiment, the disclosure relates to a kit for forming the laminate described above. The kit may comprise a first composition and a second composition. The first composition is adapted for forming an adhesion promoter layer and comprises at least one silane compound of formula (1), TIFF2026071177000011.tif1553X is C1-C3-alkyl, n is 1 to 5, and R1 and R2 are independently alkyl, or aryl, or alkoxy, or aryloxy. The second composition may be a liquid photocurable composition adapted to form a coating layer that directly overlaps the adhesion promoter layer.

[0071] In one aspect of the kit, the first composition is essentially composed of an adhesion promoter of formula (1). As used herein, essentially composed of an adhesion promoter of formula (1) means that the first composition comprises the adhesion promoter of formula (1) in an amount of at least 99% by weight, based on the total weight of the first composition.

[0072] In a further respect, the photocurable composition of the second composition of the kit is the aforementioned photocurable composition for forming the coating layer (14) of the laminate (11).

[0073] In a further embodiment, the disclosure relates to a method for bonding a coating layer (e.g., an IAP resist layer) to a substrate. The method comprises the following steps: applying the adhesion promoter layer described above to the outer surface of the substrate; directly applying the layer of the curable composition described above to the adhesion promoter layer; and curing the curable composition.

[0074] In certain embodiments, the curable composition can be applied to a substrate containing an adhesion promoter layer by an inkjet method. Depending on the material of the curable composition, curing can be carried out by UV radiation, heat treatment, or a combination thereof.

[0075] In another embodiment, the disclosure relates to a method for forming an article comprising the laminate described above. The method may comprise forming the adhesion promoter layer described above on a substrate. A curable composition (e.g., liquid imprint resist) is then applied over the adhesion promoter layer, and SuperStraight is brought into contact with the curable composition so that the curable composition forms a planar layer. The curable composition can then be irradiated with light, e.g., UV light, and / or treated with heat to form a cured planar layer. After curing of the curable composition, SuperStraight is removed from the cured layer to obtain the laminate. As used herein, the terms “cured layer” or “planar layer” are interchangeable with the term “coating layer” unless otherwise specified.

[0076] Laminates comprising a cured flat layer may be used to form articles. For example, the flat layer may be used as an interlayer insulating film in semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, and D-RDRAMs, or as a resist film used in semiconductor manufacturing processes.

[0077] In embodiments where the cured coating layer is used as a resist film, the coating layer can function as an etching mask.

[0078] Similarly, the cured layer may be used as a resist film for etching and / or ion implantation in processes for manufacturing optical components or device components such as microfluidic channel structures and patterned media structures.

[0079] In a process for manufacturing a circuit board or electronic component, the cured layer may be ultimately removed from the substrate or left as a component of the device.

[0080] As further demonstrated in the examples, surprisingly, the adhesion promoter having the structure of formula (1) can provide good adhesion of the coating layer to the substrate, and it was found that the coating layer is formed by a curable composition containing a large amount of polyfunctional vinylbenzene monomer. Therefore, the laminates of this disclosure are very suitable for IAP processes.

[0081] Examples

[0082] The following non-limiting embodiments illustrate the concepts described herein.

[0083] Example 1

[0084] Formation of a laminate having the structure of silicon wafer / adhesion promoter layer / coating layer (IAP resist)

[0085] material:

[0086] Adhesion promoter:

[0087] Typical examples of suitable adhesion promoters for fabricating the laminates of this disclosure include the following: 3-Mercaptopropyl(dimethoxy)methylsilane(S1), (3-mercaptopropyl)trimethoxysilane(S2), 1-(dimethoxymethylsilyl)methanethiol (S3), 1-(trimethoxysilyl)-methanethiol, 2-(dimethoxymethylsilyl)ethanethiol (S4), 2-(dimethoxymethylsilyl)ethanethiol (S5), and 2-(trimethoxysilyl)ethanethiol (S6).

[0088] As a comparative example, acryloxymethyltrimethoxysilane (Comparative Example C1) was used as the adhesion promoter. Please refer to Table 1 for the exact structure with the calculated vapor pressure. The vapor pressure was calculated using ACD software.

[0089] [Table 1]

[0090] Coating layer (IAP test resist):

[0091] The coating layer was formed from a UV-curable composition, also referred to herein as "IAP test resist." The IAP test resist contained 100 parts of 3,5,3'-vinyldiphenyl-methane, 1.5 parts of the photoinitiator Irgacure 1316, 4 parts of the photoinitiator Irgacure 651, and 3 parts of the surfactant SA3070, manufactured by Aoki Oil & Fat Co., Ltd.

[0092] Formation of a laminate:

[0093] A silicon wafer with a diameter of 12 inches and a thickness of 750 microns was cut into four quarters.

[0094] Subsequently, the wafer was placed in a small vacuum desiccator (Kimlet) with a diameter of 150 mm, and a Petri dish containing 0.5 g of adhesion promoter was placed at the bottom of the vacuum desiccator. The vacuum desiccator was closed with its lid, and the silicon wafer was maintained in the desiccator for various periods (1 hour, 1.5 hours, and 24 hours) at standard air pressure and room temperature (without vacuum).

[0095] After depositing the adhesion promoter layer, the wafer was cut to a size of 2 inches x 1 inch, and the aforementioned IAP test resist composition was applied onto the adhesion promoter layer by dispensing three drops of IAP test resist with a pipette, each drop having a volume of 3 microliters. A slide glass coated with Cytop (manufactured by ACG Chemicals Americas, Inc.) was placed on top of the dispensed IAP test resist, with the Cytop-coated side of the slide glass facing the IAP test resist.

[0096] The IAP test resist contained in the stack is 30 mJ / cm². 2 Using the total radiant energy, a solid IAP resist layer, also referred to herein as the coating layer (14), was formed by curing with UV radiation having a wavelength of 365 nm. After curing, the slide glass was removed, and a laminate with a layer structure of silicon wafer / adhesion promoter layer / coating layer (IAP resist layer) was obtained, with a cured IAP resist layer thickness of approximately 200 microns.

[0097] Measurement of adhesive strength

[0098] For testing the adhesive strength of the cured IAP resist layer (coating layer) to the silicon substrate, also referred to herein as the replaceable “pull-off strength,” the force required to pull off the IAP layer (14) from the substrate (12) was measured via an adhesively bonded glass rod (17).

[0099] Specifically, as shown in Figure 1B, the following assembly was prepared for the adhesion test.

[0100] A glass rod (17) (Technical Glass Products, WE 214 fused quartz rod) having a diameter of 5 mm and a length of 12 mm was adhesively bonded to the IAP layer (14) of the laminate (11). To bond the glass rod to the IAP layer, one end of the glass rod was coated with an adhesive primer (hereinafter also simply called primer) using a cotton swab, and baked at a temperature of 180°C to obtain strong adhesion between the primer and the rod. The adhesive primer contained 81 g of IsoRad 501 (aromatic polyacrylate, manufactured by Schenectady International, Inc. in Schenectady, New York), 18 g of Cymel 303ULF (comprising hexamethoxymethyl-melamine (HMMM) as the main component), and 1 g of catalyst (Cycat 4040). Subsequently, the primer-coated end of the glass rod (16) was coated with NIL resist, and the rod with the NIL resist-coated end (15) was bonded to the laminate by centering it in the cured outer IAP layer (14) of the laminate (11). The NIL resist was exposed to 365 nm UV radiation and 290 mW / cm². 2 The glass rods were bonded to the IAP layer of the laminate by curing at a light intensity of 10 minutes. The NIL resist was selected to ensure that the adhesive strength of the glass rods (17) to the IAP layer (14) via the cured NIL (15) was greater than the adhesive strength of the IAP layer (14) to the silicon wafer (12) via the adhesion promoter layer (13). The exact composition of the NIL resist was 10 wt% isobornyl acrylate, 35 wt% benzyl acrylate, 50 wt% neopentyl glycol diacrylate, 3 wt% Darocur 4265 (BASF), and 2 wt% TPO (BASF).

[0101] Subsequently, the laminate containing the bonded glass rods was bonded to an aluminum plate (18) measuring 1 inch × 25 inch × 1 / 8 inch on its reverse side (silicon wafer side) using an epoxy adhesive (Gorilla Epoxy Adhesive Clear, manufactured by Gorilla Glue Company). The epoxy adhesive was selected under the condition that the adhesive strength of the aluminum plate to the silicon wafer was greater than the adhesive strength of the photocurable resist layer (14) to the silicon wafer (12).

[0102] The actual adhesion test (measuring pull-off strength) was performed using an Instron Model 5542 Tensile Tester, by measuring the force required to pull off the IAP layer (14) from the substrate via the bonded glass rod (17).

[0103] For testing, the aforementioned laminate containing a glass rod (17) bonded to an aluminum plate (18) via a silicon wafer (12) and fixed at one end to the IAP layer (14) of the laminate via a photocurable NIL resist (15) was placed in a fixed position in a Tensile Tester. The moving head from the Instron tensile tester was adjusted so that it moved toward the glass rod at a speed of 0.5 mm per minute and struck the glass rod sideways at a position 5.3–5.4 mm away from the end of the glass rod bonded to the resist. The force required to separate the glass rod with the bonded IAP resist layer (14) from the silicon substrate (12) was recorded. The adhesive strength (i.e., the pull-off strength of the IAP resist relative to the silicon wafer) was measured in pounds per force (lbf) at 19.62 mm from the end of the glass rod. 2 By dividing by the surface area, lbf / mm 2 Normalized to . Normalized lbf / mm 2 The values ​​were further converted to MPa units by multiplying by a coefficient of 4.4482. A diagram of the layered assembly containing the laminate in Figure 1A is shown in Figure 1B.

[0104] For each sample, the test was repeated eight times, and the average pull-off intensity was calculated.

[0105] The results of measuring the adhesive strength of laminates S1 and S2 at different deposition times (1 hour, 1.5 hours, and 24 hours) are summarized in Table 2. It can be seen that the adhesive strength increases with increasing deposition time. However, the adhesive strength obtained after only 1 hour of deposition was 5.4 MPa for sample S1 and 4.6 MPa for sample S2, which is considered to satisfy the desired adhesive strength for the IAP coating layer. The objective is to form a laminate in which the IAP coating layer has an adhesive strength of at least 2.5 MPa.

[0106] [Table 2]

[0107] Although the deposition time was the same at 1 hour, the adhesive strength of the IAP coating layer of laminate S2 was approximately 0.7 MPa lower than that of the IAP layer of laminate S1. This difference in adhesive strength can be explained by the lower vapor pressure of the adhesion promoter used to fabricate laminate S2.

[0108] Without the use of an adhesion promoter, the IAP resist layer exhibited an adhesion strength that was below measurable (close to zero), which was unsatisfactory.

[0109] Example 2

[0110] Following the adhesive strength of the IAP layer, other important properties for manufacturing high-quality IAP laminates are the water contact angle with respect to the adhesion promoter layer and the surface free energy of the adhesion promoter layer.

[0111] Water contact angle with adhesion promoter layer

[0112] The water contact angle can be considered a suitable parameter for evaluating the droplet spreading of IAP, and low water levels are desirable for good droplet spreading.

[0113] Table 3 below summarizes the water contact angles for the adhesion promoter layers formed after 1 hour and 24 hours of deposition for samples S1 and S2. For comparison, a known adhesion promoter that does not contain SH groups as a functional group, comparative sample C1 (see Table 1 above), was also used.

[0114] Samples S1 and S2 have low water contact angles of 35 degrees or less, while the water contact angle of comparative sample C1 is 49.5 degrees, which is significantly larger than that of samples S1 and S2. It is interesting to observe that the water contact angle increases with increasing deposition time, and that a 1-hour deposition time yielded the best combination of good adhesion strength and a low water contact angle.

[0115] [Table 3]

[0116] Measurement of water contact angle:

[0117] The water contact angle was measured using a Drop Master DM-701 contact angle meter manufactured by Kyowa Interface Science Co., Ltd. (Japan).

[0118] For the test, 2 ml of deionized water was added to a syringe, and 2 μl of this sample was applied by machine to the surface of a silicon wafer coated with an adhesion promoter layer for each test. Droplet images were continuously captured by a CCD camera from the moment the water droplet touched the layer surface. The contact angle was automatically calculated by software based on the image analysis. The water contact angles shown in Table 3 are the contact angles 3 seconds after the water droplet touches the surface of the adhesion promoter layer.

[0119] Surface free energy (SFE) of the adhesion promoter layer

[0120] The surface free energy (SFE) was measured for the adhesion promoter layers of samples S1 and S2, comparative sample C1, the primer-coated glass rod, and the bare silicon wafer.

[0121] The SFE measurement was performed using the Drop master DM-701 described above. In the first measurement, the contact angle of water was measured, and in the second measurement, the contact angle of iodomethane with respect to the target surface (the photocurable polymer layer corresponding to the material of the soft mold) was measured. The surface free energy was calculated using the Owens-Wendt method with the analysis software FAMAS installed in the Drop master DM-701 device based on the values of both contact angles.

[0122] The results of the measurements are summarized in Table 4. The SFE of the adhesion promoter layers S1 and S2 (63.2 and 70.5 mJ / cm 2 ) is found to be much larger than that of the comparative sample C1 (53.1 mJ / cm 2 ). Increasing the evaporation time from 1 hour to 24 hours did not further increase the SFE but caused a decrease. The primer coating with 48.2 mJ / cm 2 is similar to that of the comparative sample C1, while the bare silicon wafer without the adhesion promoter layer had a maximum SFE of 73.6 mJ / cm 2 .

[0123] The SFE measurement demonstrates that the adhesion promoter layer of the present disclosure can substantially maintain the high SFE of the bare silicon wafer. The data further shows that a high SFE corresponds to a low water contact angle.

[0124] Without being bound by theory, it is considered that the SH groups of the adhesion promoter layer are oriented upward and can easily react with the vinyl groups of the monomers of the IAP resist material during UV exposure, thereby forming a strong adhesion between the cured IAP resist and the silicon wafer.

[0125]

Table 4

[0126] The description and drawings of the embodiments described herein are intended to provide a general understanding of the structures of various embodiments. The description and drawings are not intended to exhaustively and comprehensively describe all elements and features of apparatuses and systems that use the structures or methods described herein. Different embodiments may be provided in combination in a single embodiment, and conversely, for simplicity, various features described in the context of a single embodiment may be provided separately or in any subcombination. Furthermore, references to values ​​in a range include each and all values ​​within that range. Many other embodiments will become apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure so as to be structurally, logically, or otherwise modified without departing from the scope of this disclosure. Accordingly, this disclosure should be considered illustrative, not restrictive.

Claims

1. It is a laminate, circuit board and A bonding promoter layer directly overlapping the aforementioned substrate, A coating layer that directly overlaps the aforementioned adhesion promoter layer, Equipped with, The adhesion promoter layer comprises a silane compound of formula (1), X is C １ -C ３ -It is an alkyl group, n is 1 to 5, R １ and R ２ These are independently alkyl, or aryl, or alkoxy, A laminate characterized by the following features.

2. R of the silane compound of formula (1) １ and R ２ are independently C １ -C ３ -alkyl, or C １ -C ３ -alkyloxy, or a combination thereof, and the laminate according to claim 1, characterized in that

3. The silane compound of formula (1) is or or combinations thereof The laminate according to feature 2.

4. The laminate according to claim 1, characterized in that the substrate material comprises silicon, aluminum, zirconium, tin, titanium, nickel, or any oxide thereof.

5. The laminate according to claim 1, characterized in that the thickness of the adhesion promoter layer is at least 0.5 nm and 100 nm or less.

6. The laminate according to claim 1, characterized in that the amount of the silane compound of formula (1) in the adhesion promoter layer is at least 90% by weight, based on the total weight of the adhesion promoter layer.

7. The laminate according to claim 1, characterized in that the coating layer is a cured resist of a polyfunctional vinylbenzene-based IAP material.

8. The laminate according to claim 7, characterized in that the polyfunctional vinylbenzene-based IAP material is a photocurable composition comprising at least 80% by weight of a polyfunctional vinylbenzene monomer.

9. The laminate according to claim 8, characterized in that the polyfunctional vinylbenzene-based IAP material is essentially free of acrylate monomers.

10. The laminate according to claim 1, characterized in that the vapor pressure of the silane compound is at least 0.1 toll at 25°C.

11. The laminate according to claim 1, characterized in that the coating layer has an adhesive strength to the substrate of at least 2.5 MPa.

12. A method for forming a laminate, This involves directly applying an adhesion promoter layer to the outer surface of the substrate, The adhesion promoter layer comprises a silane compound of formula (1), X is C １ -C ３ -It is an alkyl group, n is 1 to 5, R １ and R ２ The fact that each is independently alkyl, aryl, alkoxy, or aryloxy, Applying a coating layer that directly overlaps the aforementioned adhesion promoter layer, A method characterized by comprising:

13. The method according to 12, characterized in that applying the adhesion promoter layer comprises depositing the silane compound onto the outer surface of the substrate.

14. The method according to 12, characterized in that it includes forming a covalent bond between the adhesion promoter layer and the substrate, and forming a covalent bond between the adhesion promoter layer and the coating layer.

15. The method according to 12, characterized in that applying the coating layer includes applying a liquid photocurable composition to the adhesion promoter layer and curing the liquid photocurable composition to form the coating layer.

16. The method according to 15, characterized in that the liquid photocurable composition comprises a polymerizable material containing at least 80% by weight of at least one polyfunctional vinylbenzene monomer, based on the total weight of the polymerizable material.

17. The method according to 12, characterized in that, after applying the adhesion promoter layer and before applying the coating layer, the water contact angle with respect to the adhesion promoter layer is at least 10 degrees and 45 degrees or less.

18. The method according to 12, characterized in that the water vapor pressure of the silane compound is at least 0.1 Torr at 25°C.

19. After applying the adhesion promoter layer and before applying the coating layer, the surface free energy of the adhesion promoter layer is at least 55 mJ / cm². ２ The method according to 12, characterized in that...

20. A kit for forming a laminate, A first composition, wherein the first composition is adapted to form an adhesion promoter layer and comprises at least one silane compound of formula (1), X is C １ -C ３ -It is an alkyl group, n is 1 to 5, R １ and R ２ These are independently alkyl, aryl, alkoxy, or aryloxy, A second composition, wherein the second composition is a liquid photocurable composition adapted to form a coating layer that directly overlaps the adhesion promoter layer, A kit characterized by comprising the following features.

21. The kit according to claim 20, characterized in that the liquid photocurable composition comprises a polymerizable material containing at least 80% by weight of at least one polyfunctional vinylbenzene monomer, based on the total weight of the polymerizable material.

22. A method for manufacturing articles, The method involves applying a layer of a photocurable composition to a substrate, wherein the substrate has an adhesion promoter layer on its outer surface containing a silane compound of formula (1), X is C １ -C ３ -It is an alkyl group, n is 1 to 5, R １ and R ２ These are independently alkyl, or aryl, or alkoxy, and the photocurable composition overlaps directly with the adhesion promoter layer. The photocurable composition is brought into contact with the superstraight, The photocurable composition is irradiated with light to form a cured layer, The superstraight is removed from the hardened layer to obtain a laminate, Manufacturing an article from the aforementioned laminate, A method characterized by comprising:

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