Laminate, transistor, method for manufacturing laminate, and method for manufacturing transistor

Abstract

A laminate includes a substrate, an amine generating layer, a copper wiring layer, and a copper wiring protective layer in this order.

Description

Technical Field

[0001] This invention relates to a laminate, a transistor, a method for manufacturing a laminate, and a method for manufacturing a transistor.

[0002] This application claims priority based on PCT / JP2023 / 034991, filed on September 26, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, in the manufacture of micro-devices such as semiconductor components, integrated circuits, and organic electroluminescence (EL) display devices, a method has been proposed to form patterns with different surface properties on a substrate and utilize the differences in these surface properties to fabricate micro-devices.

[0004] As a patterning method that utilizes differences in surface properties on a substrate, one method involves forming a region of chemically active substituents on a portion of the substrate. This method allows for close contact between a metallic, organic, or inorganic material and a portion of the substrate.

[0005] As a technique for forming a metal film by bonding metal materials on a substrate, there is an electroless plating process. For example, Patent Document 1 discloses a technique for forming fine wirings by an electroless plating process. Specifically, Patent Document 1 discloses using a catalyst activation layer and a photoresist to perform optical patterning from a state where the coating is on one side by etching or stripping.

[0006] [Existing technical documents]

[0007] [Patent Literature]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2006-2201 Summary of the Invention

[0009] The first embodiment of the present invention is a laminate, which sequentially includes a substrate, a base film layer, a copper wiring layer and a copper wiring protection layer, wherein the base film layer includes an amine generation layer. Attached Figure Description

[0010] Figure 1 This is a schematic cross-sectional view of an example of a laminated body in this embodiment.

[0011] Figure 2 This is a schematic cross-sectional view of an example of a transistor in this embodiment.

[0012] Figure 3 This is a schematic diagram illustrating an example of a manufacturing method for a laminated body according to this embodiment.

[0013] Figure 4 This is a schematic diagram illustrating an example of a manufacturing method for a laminated body according to this embodiment.

[0014] Figure 5 This is a schematic diagram illustrating an example of a manufacturing method for a laminated body according to this embodiment.

[0015] Figure 6 This is a diagram showing the source / drain electrode structure manufactured in Example 1.

[0016] Figure 7 This is a graph showing the results of the evaluation of the transfer characteristics of the transistor manufactured in Example 1.

[0017] Figure 8 This is a diagram showing the fine wiring manufactured in Example 2.

[0018] Figure 9 This is a diagram showing the source / drain electrode structure manufactured in Example 2.

[0019] Figure 10 This is a graph showing the results of the evaluation of the transfer characteristics of the transistor manufactured in Example 2.

[0020] Figure 11 This is a graph showing the relationship between exposure and photoreactivity based on UV irradiation for both single-cell NBC and single-cell iPrNBC.

[0021] Figure 12 This figure shows the precipitation results when NiP was deposited on various amine-generating layers with different exposure levels, specifically for polymer NBC and PiPrNBC-AEMA. Detailed Implementation

[0022] The laminate of this embodiment and its manufacturing method will be described below with reference to the accompanying drawings.

[0023] Furthermore, in all the following figures, the dimensions or ratios of the constituent parts are appropriately varied for ease of observation.

[0024] <Layered Body>

[0025] One embodiment of the present invention is a laminate, which sequentially includes a substrate, an amine generating layer, a copper wiring layer, and a copper wiring protection layer.

[0026] Figure 1 This is a schematic cross-sectional view of the laminate 1 of this embodiment. The laminate 1 includes a substrate 10, an amine generating layer 12, a copper wiring layer 14C, and a copper wiring protective layer 16.

[0027] Figure 1 In this process, the gate insulating layer 11 and the first catalyst layer 13 can have arbitrary structures.

[0028] An amine generating layer 12 and an arbitrary gate insulating layer 11 are formed on the entire surface of one main surface of the substrate 10. A copper wiring layer 14C is a fine copper wiring pattern formed on the amine generating layer 12. The copper wiring layer 14C is protected by a copper wiring protection layer 16. The copper wiring protection layer 16 is a conductive protective film.

[0029] The laminate 1 can be suitably used as a patterned electrode for a transistor. When the laminate 1 is used as a patterned electrode for a transistor, the copper wiring layer 14C constitutes either the source electrode or the drain electrode.

[0030] The substrate 10 can be either a light-transmitting substrate or a non-light-transmitting substrate. For example, it can be an inorganic material such as glass, quartz glass, silicon, or silicon nitride, or an organic polymer (resin) such as acrylic resin, polycarbonate resin, polyethylene terephthalate (PET), or polybutylene terephthalate (PBT).

[0031] The amines included in the amine generation layer 12 are, for example, primary amines (-NH2-) and secondary amines (-NH-).

[0032] When the stack 1 constitutes a bottom-gate type transistor, it is preferable to include a gate insulating layer 11 on the substrate 10. The gate insulating layer 11 may contain, for example, a methoxysilane coupling agent or polymethoxychalcone.

[0033] Furthermore, as an arbitrary structure, a metal wiring pattern including a gate electrode may be included on the entire surface or a portion of a main surface of the substrate 10 and under the gate insulating layer 11. The metal wiring pattern may, for example, include conductive materials containing molybdenum and aluminum, and is a fine metal wire of MAM (Mo-Al-Mo three-layer structure).

[0034] The copper wiring layer 14C is a metal wiring formed on the surface of the amine generation layer 12. The laminate 1 is manufactured by the manufacturing method of the laminate of this embodiment, which will be described later. In the manufacturing method of this embodiment, as a trace of the process of removing the first catalyst layer present in the opening of the photoresist layer, the first catalyst layer 13 may remain under the copper wiring layer 14C. The first catalyst layer 13 may be a layer containing palladium.

[0035] The upper surface and sides of the copper wiring layer 14C are protected by a copper wiring protection layer 16. The copper wiring protection layer 16 is a conductive protective film, specifically composed of nickel-phosphorus, nickel-boron, or palladium.

[0036] When the stack 1 constitutes a transistor, it is preferable to include a gold plating layer on the copper wiring protection layer.

[0037] Figure 2 This is a schematic cross-sectional view of a transistor including the stack and organic semiconductor layer of this embodiment.

[0038] Figure 2 In the transistor 2, there are a substrate 10, an amine generation layer 12, a source electrode 32, a drain electrode 31, and an organic semiconductor layer 33.

[0039] The source electrode 32 and the drain electrode 33 respectively include a copper wiring layer 14C, a copper wiring protection layer 16 and a gold plating layer 17.

[0040] and then, Figure 2 The transistor 2 shown includes a gate insulating layer 11 and a first catalyst layer 13.

[0041] The gold plating layer 17 and the copper wiring layer 14C are also metal wirings formed by electroless plating.

[0042] The copper wiring layer 14C becomes the first electrode constituting the source electrode 32 or the drain electrode 31, and the gold plating layer 17 becomes the second electrode constituting the source electrode 32 or the drain electrode 31.

[0043] The material constituting the second electrode is preferably a metallic material, namely gold (work function: 5.4 eV), which has a work function that facilitates electron (or hole) movement, due to the relationship between the highest occupied molecular orbital (HOMO) / lowest unoccupied molecular orbital (LUMO) energy levels of the organic semiconductor layer 33 forming material.

[0044] Based on the aforementioned reasons, a wiring method using nickel-phosphorus as the first electrode and gold as the second electrode was previously studied. However, when using nickel-phosphorus, the resistance increases as the transistor is enlarged, thus requiring a material with lower resistance.

[0045] The inventors, aiming to manufacture low-resistance transistors, have encountered a problem where, when copper is used as the first electrode and the copper wiring of the first electrode is coated with gold, migration occurs during transistor operation, leading to exposure and oxidation of the copper wiring.

[0046] Therefore, the idea of ​​using a copper wiring protection layer to protect the copper wiring layer was conceived, thus completing this invention.

[0047] Since the copper wiring layer of this embodiment is protected by the copper wiring protection layer, no migration occurs even when a gold plating layer is further formed to drive the transistor, thus providing a transistor with reduced resistance.

[0048] There are no particular limitations on the organic semiconductor materials used in transistors. They can include p-type semiconductors such as copper phthalocyanine (CuPc), pentaphenyl, rubrene, tetraphenyl, P3HT (poly(3-hexylthiophene-2,5-diyl)), fullerenes such as C60, n-type semiconductors such as perylene derivatives such as PTCDI-C8H (N,N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimide), and Ph-BTBT-10 (2-decyl-7-phenyl[1]benzothiophene[3,2-b][1]benzothiophene). Among them, soluble pentacene such as TIPS (6,13-bis(triisopropylsilylethynyl)pentacene), organic semiconductor polymers such as P3HT, or Ph-BTBT-10 which is soluble in organic solvents such as toluene, can form an organic semiconductor layer through a wet process, and are therefore preferred. The HOMO level of TIPS pentacene is 5.2 eV, and the HOMO level of Ph-BTBT-10 is -5.6 eV.

[0049] <Method for manufacturing laminates>

[0050] The manufacturing method of a laminate, which is one aspect of the present invention, will be described using the accompanying drawings.

[0051] Figure 3 The process indicated by symbol 3A is any process, but in the case of manufacturing a stack that constitutes a transistor, it is preferable to form a gate insulating layer 11 on the surface of the substrate 10.

[0052] The gate insulating layer 11 can be formed by coating the entire surface of one main surface of the substrate 10 with, for example, a methoxysilane coupling agent. Preferably, the gate insulating layer 11 is formed by further coating a photosensitive polymer material such as polyoxysilane after coating with the methoxysilane coupling agent, and then irradiating with ultraviolet light.

[0053] Furthermore, as an optional process, it may also include forming a metal wiring pattern on the entire surface or a portion of a main surface of the substrate 10, under the gate insulating layer 11. The metal wiring pattern may include conductive materials containing molybdenum and aluminum, or it may form fine metal wires of MAM (Mo-Al-Mo three-layer structure).

[0054] Next, as Figure 3 As indicated by symbol 3B, a photosensitive surface treatment agent is coated onto the substrate 10 or any arbitrarily formed gate insulating layer 11, and a photosensitive resin film 12A is formed. The photosensitive resin film 12A is exposed to form an amine generation layer 12 having an amine generation region in the exposed area. Figure 3 (The symbol 3C in the text).

[0055] The photosensitive resin film 12A can be exposed to its entire surface or to a pattern of a dielectric mask. From the viewpoint that a copper plating layer is formed on the entire surface of the substrate 10 in a subsequent process, it is preferable to expose the entire surface.

[0056] The photosensitive surface treatment agent used to form the photosensitive resin film 12A is not limited to any material that, upon light irradiation, causes the protective group to detach and generate an amine.

[0057] For example, a photosensitive surface treatment agent comprising photosensitive polymer 1 (polyisopropyl nitrobenzyl carbamate) as shown below is preferred.

[0058] [Chemistry 1]

[0059] If the photosensitive resin film 12A is exposed, an amine is generated in the exposed area, forming an amine generation layer 12 with an amine generation region 12X. Figure 3 The symbol 3C is used in this context. Amines are, for example, primary amines (-NH2-) and secondary amines (-NH-).

[0060] Next, as Figure 3 As shown by symbol 3D, a first catalyst layer 13 is formed on the amine generation layer 12, and electroless copper plating is performed to form a copper plating layer 14.

[0061] The first catalyst layer 13 contains a catalyst for electroless plating. The catalyst for electroless plating is a catalyst for reducing metal ions contained in the electroless plating solution, such as silver or palladium.

[0062] Amino groups are exposed on the surface of the amine generation layer 12. These amino groups can capture and reduce the electroless plating catalyst. Therefore, the electroless plating catalyst is captured on the amine generation layer 12, forming the first catalyst layer 13. Alternatively, the electroless plating catalyst can be a catalyst capable of supporting amino groups.

[0063] The catalyst used to form the first catalyst layer 13 is not limited to any catalyst suitable for electroless copper plating and capable of supporting amines; however, a metal catalyst with a pH of 3 to 12 at a measuring temperature of 20°C is preferred. Commercially available examples of such catalysts include Aktivator 7331, a palladium catalyst with a pH of 3.5 to 6.5 at a measuring temperature of 20°C, manufactured by Melplate.

[0064] Preferably, the activation process for the first catalyst layer 13 is performed after the formation of the first catalyst layer 13 and before the formation of the copper plating layer 14, as an optional step. The activation process for the first catalyst layer 13 is a process of reducing the metal chloride contained in the catalyst to a metal. For example, this could be a process of reducing palladium chloride contained in the catalyst to metallic palladium, or a process of reducing silver chloride to metallic silver.

[0065] The treatment to activate the first catalyst layer 13 can be performed using a known method, namely an acid or alkaline solution known as an accelerator. Specifically, a commercially available activator (such as Okuno Pharmaceutical Co., Ltd., OPC-150 Cryster RW) can be used.

[0066] By activating the first catalyst layer 13, metal chlorides can be metallized, thereby improving the deposition and adhesion of electroless copper plating.

[0067] After the first catalyst layer 13 is formed, an electroless plating process is performed to form a copper plating layer 14. In the electroless plating process, the substrate 10 is immersed in an electroless plating bath, and metal ions are reduced on the surface of the first catalyst layer 13, causing the copper plating layer 14 to precipitate. By forming an amine generation layer 12, which carries a sufficient amount of catalyst, a copper plating layer 14 with high adhesion to the substrate 10 can be formed.

[0068] Next, as Figure 4 As indicated by symbol 4A, photoresist material 15A is coated on the copper plating layer 14. A dielectric mask M exposes the photoresist material 15A in a pattern, forming an exposure area corresponding to the pattern of the copper wiring layer. Then, as... Figure 4 As indicated by symbol 4B, the photoresist in the unexposed area is removed to form a photoresist layer 15.

[0069] Photoresist material 15A can be any known material, such as a positive photoresist material.

[0070] Next, as Figure 4 As indicated by symbol 4C, a portion of the copper plating layer 14 is removed to form a copper wiring layer 14C. Through this process, a pre-pattern P including a photoresist layer 15 is formed on the copper wiring layer 14C.

[0071] Next, as Figure 4 As indicated by symbol 4D, the catalyst remover is brought into contact with the pre-pattern P to remove the first catalyst layer 13 present in the photoresist opening. One method for removing the first catalyst layer 13 is to immerse the substrate 10 in the catalyst remover. Preferably, the catalyst remover is an aqueous solution containing an organic amine.

[0072] If the substrate 10 is immersed in an aqueous solution containing organic amine, the metal catalyst constituting the first catalyst layer 13 forms a complex with the organic amine, increasing the solubility of the metal catalyst and allowing the first catalyst layer 13 to be removed. At this time, since the photoresist layer 15 does not dissolve in the aqueous solution containing organic amine, the first catalyst layer 13 can be removed while maintaining the photoresist layer 15.

[0073] As an aqueous solution containing organic amines, an aqueous solution containing ethylenediamine is preferred. For example, Postdip RP, manufactured by Okuno Pharmaceutical Co., Ltd., can be used as such a commercially available product.

[0074] When a copper plating layer 14 is formed on the entire surface of one main surface of the substrate 10, from the viewpoint of improving the adhesion between the substrate 10 and the copper plating layer 14, it is preferable to use a neutral metal catalyst that can deposit a large amount of copper and has a pH of 3.5 to 6.5 at a measurement temperature of 20°C. However, if a neutral metal catalyst remains, in the subsequent process of forming a copper wiring protection layer, the metal components constituting the copper wiring protection layer will be excessively deposited, resulting in an increase in resistance.

[0075] Therefore, although it is necessary to remove the first catalyst layer 13 present in the photoresist opening, the organic amine constituting the catalyst remover also forms a complex with copper. Therefore, if the substrate 10 is only immersed in an aqueous solution containing organic amine, the copper constituting the copper wiring layer 14C will dissolve and the copper wiring will be damaged.

[0076] In this embodiment, by bringing the catalyst remover into contact with the pre-pattern P, the photoresist layer 15 protects the copper wiring layer 14C from the influence of the catalyst remover, and the first catalyst layer 13 can be removed without damaging the copper wiring layer 14C.

[0077] Furthermore, although the upper surface of the copper wiring in the copper wiring layer 14C is protected by the photoresist layer 15, the sides are not protected. However, since the sides occupy a small proportion of the total area of ​​the copper wiring layer 14C, the damage to the sides caused by the catalyst remover is not easily apparent.

[0078] Furthermore, after removing the first catalyst layer 13 present at the photoresist opening, as... Figure 5As indicated by symbol 5A, remove the photoresist layer 15. The photoresist layer 15 can be removed using a known developer.

[0079] Furthermore, such as Figure 5 As indicated by symbol 5B, a second catalyst layer 20 is formed on the copper wiring layer 14C, followed by electroless plating to form a copper wiring protective layer 16. Figure 5 (5C in the diagram). The copper wiring protection layer 16 is formed on the upper surface and sides of the copper wiring covered by the copper wiring layer 14C. The copper wiring protection layer 16 is a conductive protective film, and the specific constituent materials are nickel-phosphorus, nickel-boron, or palladium.

[0080] To form the copper wiring protective layer 16, a second catalyst layer 20 is formed on the copper wiring layer 14C. The catalyst constituting the second catalyst layer is an electroless plating catalyst different from the electroless plating catalyst constituting the first catalyst layer 13. Preferably, the catalyst used is an acidic metal catalyst with a pH of 2 or less at a measuring temperature of 20°C. An example of such a catalyst is Aktivator 352, an acidic palladium catalyst with a pH of 1 or less at a measuring temperature of 20°C, manufactured by Melplate.

[0081] By forming a conductive protective layer 16, the gold constituting the electroless gold plating layer formed in any subsequent process and the copper constituting the copper wiring layer become less prone to migration, thus reducing the likelihood of short circuits caused by reduced migration.

[0082] Furthermore, as an arbitrary process, a gold plating layer 17 can also be formed. Figure 5 (The symbol 3D in the text). The gold plating layer 17, like the copper plating layer 14, can be formed simply by electroless plating.

[0083] <Methods for Manufacturing Transistors>

[0084] The transistor manufacturing method of this embodiment includes: after performing a process including a gold plating layer by the manufacturing method of the laminate of this embodiment, a process of forming an organic semiconductor layer in contact with the mutually facing surfaces of the source electrode and the drain electrode.

[0085] [Example]

[0086] The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments.

[0087] <Example 1>

[0088] [Process for forming the amine generation layer]

[0089] For silicon wafers with thermally oxidized films, a cyclopentanone solution of MCSC ((E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate) was spin-coated and then surface-treated. Subsequently, a 5 wt% cyclopentanone solution of PMC (poly(4-methoxychalcone)) was spin-coated (manufactured by Mikasa Corporation, MS-A150, at 1000 rpm) and then dried at 100°C for 20 minutes. The wafer was then irradiated with 1200 mJ / cm². 2 The gate insulating layer, which serves as the substrate, is fabricated by exposing ultraviolet (UV) light with a wavelength of 365 nm and heating it at 150°C for 60 minutes. Furthermore, in this embodiment 1, the silicon wafer functions as the gate electrode of the transistor.

[0090] The structures of MCSC and PMC are shown below.

[0091] [Chemistry 2]

[0092] Next, a 0.3 wt% cyclopentanone solution of PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) was applied at 1000 rpm by spin coating (Mikasa Inc., MS-A150), and then heated at 100°C for 20 minutes to form a photosensitive polymer layer.

[0093] The structure of PiPrNBC-AEMA is shown below.

[0094] [Chemistry 3]

[0095] Next, the substrate with the photosensitive polymer layer deposited on its entire surface was exposed to 1000 mJ / cm². 2 Light with a wavelength of 365 nm exposes the photosensitive polymer layer to light, forming an amine-producing layer.

[0096] [Process for forming the copper plating layer]

[0097] Next, the catalyst (Pd) was immersed in an electroless plating catalyst solution (Melplate Aktivator 7331, manufactured by Meltex Corporation) at room temperature for 10 minutes to attach the catalyst (Pd) to the amine-generating part. After rinsing the surface with water, it was immersed in a catalyst activation solution (OPC-150 Cryster RW, manufactured by Okuno Pharmaceutical Co., Ltd.) at room temperature for 1 minute to attach the catalyst (Pd) to the amine-generating part and activate it. Thus, the first catalyst layer was formed. Next, the catalyst was immersed in an electroless plating solution (OPC Copper HFS, manufactured by Okuno Pharmaceutical Co., Ltd.) at 40°C for 3 minutes to deposit electroless copper on the catalyst, forming a copper plating layer.

[0098] [Photoresist process]

[0099] Photoresist (PFI-34, manufactured by Sumitomo Chemical Co., Ltd.) was applied at 1500 rpm using a spin coater (Mikasa Co., Ltd., MS-A150), followed by heating at 105°C for 8 minutes, thereby forming a photoresist film. The film was then irradiated with a dielectric photomask at 100 mJ / cm². 2 After being exposed to UV light with a wavelength of 365 nm for 3 minutes at 105°C and then baked, the exposed parts were immersed in a developer (NMD-3, tetramethylammonium hydroxide 2.38%, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute to remove the photoresist from the exposed parts.

[0100] [Process for forming a pre-pattern]

[0101] The copper plating layer was partially removed by heating at 105°C for 5 minutes and then immersing in a copper etching solution (acetic acid / hydrogen peroxide / water = 1 / 1 / 20) at 30°C for 40 seconds. This resulted in the formation of a pre-pattern on the copper wiring layer, including a photoresist layer.

[0102] [Process for removing the first catalyst layer]

[0103] Next, the catalyst was immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 50°C for 15 minutes to remove the first catalyst layer, palladium, present at the opening of the photoresist.

[0104] [Process for removing the photoresist layer]

[0105] A copper micro-wire layer is fabricated by immersing the substrate in a photoresist stripper (N-342, manufactured by Nagase-Chemtex) for 4 minutes at room temperature to remove the photoresist.

[0106] [Process for forming the copper wiring protective layer]

[0107] The substrate was immersed in an electroless plating catalyst solution (Melplate Aktivator 352, manufactured by Meltex Corporation) at 30°C for 40 seconds, followed by immersion in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and then immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73°C for 3 minutes. Nickel phosphorus was deposited on the copper plating to form the micro-plated wiring included in the copper wiring protection layer, thus obtaining a laminate.

[0108] [Gold plating process]

[0109] Furthermore, the wires are immersed in an electroless plating solution (Flash Gold NC, manufactured by Okuno Pharmaceutical Co., Ltd.) at 55°C for 4 minutes to induce displacement gold deposition and create micro-plated wiring, which serves as the source / drain electrode.

[0110] The electrode surface was sequentially ultrasonically cleaned (45 kHz, 4 min) using cyclopentanone, xylene, and isopropanol (IPA), and then heated and dried at 120°C for 60 min. Next, it underwent UV cleaning for 8 min, followed by ultrasonic cleaning in IPA (45 kHz, 3 min), and then heated and dried at 120°C for 60 min. Then, the substrate was immersed in a 0.75 wt% ethanol solution of TFTFMBT (2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzenethiol, manufactured by Tokyo Chemical Industry Co., Ltd.) for 5 min at room temperature, removed, rinsed with ethanol, and dried by nitrogen blowing, thus forming a gold-thiol self-assembled monolayer (SAM) film on the electrode surface.

[0111] Next, a 0.1 wt% / 0.45 wt% xylene solution of polystyrene (manufactured by Merck) / organic semiconductor (Ph-BTBT-10,2-decyl-7-phenyl[1]benzothiophene[3,2-b][1]benzothiophene, manufactured by Tokyo Chemical Industry Co., Ltd.) was coated at 3000 rpm at 145°C using a heated spin coater. The solution was then dried at 120°C for 10 minutes and at 100°C for 60 minutes to fabricate an organic semiconductor layer, thereby obtaining the transistor of Example 1.

[0112] The fabricated source / drain electrode structure is shown in Figure 6 In all shapes with electrode spacing of 10 μm, 20 μm, 35 μm, 50 μm, and 80 μm, it was confirmed that fine details could be depicted.

[0113] Will Figure 7 The results of the transport characteristic evaluation of the organic thin film transistors (OTFTs) shown are presented in the figure. (Channel lengths L = 10 μm, 20 μm, 35 μm, 50 μm, 80 μm, channel width W = 500 μm) Figure 7 It can be confirmed that the system operates normally regardless of the channel length.

[0114] In Example 1, a thin copper plating of approximately 200 nm was used, which is susceptible to a decrease in conductivity caused by the chemical solution. Here, by removing palladium from the underside of the copper plating while the resist remains, excellent Au plating can be laminated without damaging the copper plating. The Au laminate maintains a resistivity of 0.22 Ω / □ compared to the sheet resistance of 0.19 Ω / □ after copper plating.

[0115] <Comparative Example 1>

[0116] Instead of performing the process of forming a photoresist layer, an additional process was added: immersing the transistor in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes before forming a copper wiring protection layer on the copper plating layer. Otherwise, the transistor of Comparative Example 1 was manufactured by the same method as in Example 1.

[0117] It was confirmed that the resistance of the sheet after copper plating was 0.38 Ω / □, while the conductivity decreased to 0.72 Ω / □ after Au lamination. It was also confirmed that immersion in the catalyst remover without resist protection increased the resistance value; ideally, exposure of the copper to the chemical solution should be avoided before applying the catalyst to the copper surface.

[0118] <Comparative Example 2>

[0119] The transistor of Comparative Example 2 was manufactured by immersing it in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute before forming a copper wiring protective layer on the copper plating layer. Otherwise, the transistor of Comparative Example 2 was manufactured by the same method as Comparative Example 1.

[0120] It was confirmed that the resistance of the sheet after copper plating was 0.34 Ω / □, while the conductivity of the Au laminate decreased to 1.02 Ω / □. It was also confirmed that immersion in the catalyst remover without resist protection increased the resistance value; ideally, exposure of the copper to the chemical solution should be avoided before applying the catalyst to the copper surface.

[0121] <Comparative Example 3>

[0122] The transistor of Comparative Example 3 was manufactured by immersing it in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 4 minutes before forming a copper wiring protective layer on the copper plating layer. Otherwise, the transistor of Comparative Example 3 was manufactured by the same method as Comparative Example 1.

[0123] It was confirmed that the resistance of the sheet after copper plating was 0.41 Ω / □, while the conductivity of the Au laminate decreased to 1.58 Ω / □. It was also confirmed that immersion in a catalyst remover without resist protection increased the resistance value; ideally, exposure of the copper to the chemical solution should be avoided before applying the catalyst to the copper surface.

[0124] The results of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 are summarized in Table 1.

[0125] [Table 1]

[0126] <Example 2>

[0127] [Process for forming the amine generation layer]

[0128] For polyethylene naphthalate (PEN) films (Teonex, manufactured by Teijin Corporation), a Mo / Al / Mo matrix (MAM) film was formed by dry deposition, followed by photolithography to create fine wiring within the MAM, thus forming the gate electrode. After a 3-minute UV / O3 cleaning, a 0.2 wt% cyclopentanone solution of MCSC ((E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate) was spin-coated and surface-treated. Subsequently, a 12 wt% / 1.2 wt% cyclopentanone solution of PVCI (polyvinyl cinnamate, manufactured by Merck) / MC (methoxychalcone, manufactured by Tokyo Chemical Co., Ltd.) was spin-coated at 2000 rpm using a Mikasa MS-A150 spin coater, followed by drying at 80°C for 20 minutes. A gate insulating layer was then fabricated by irradiation with 365 nm UV light at 624 mJ / cm², development using propylene glycol monomethyl ether acetate (PGMEA, manufactured by Tokyo Chemical Co., Ltd.), and heating at 150°C for 120 minutes.

[0129] Next, a 0.3 wt% cyclopentanone solution of PiPrNBC-AEMA was applied at 1000 rpm by spin coating (Mikasa Inc., MS-A150), and then heated at 100°C for 20 minutes to form a photosensitive polymer layer.

[0130] Next, the substrate with the photosensitive polymer layer deposited on its entire surface was exposed to 1000 mJ / cm². 2 Light with a wavelength of 365 nm exposes the photosensitive polymer layer to light, forming an amine-producing layer.

[0131] [Process for forming the copper plating layer]

[0132] Next, the catalyst (Pd) was immersed in an electroless plating catalyst solution (Melplate Aktivator 7331, manufactured by Meltex Corporation) for 10 minutes at room temperature to allow the catalyst to adhere to the amine-generating part. After rinsing the surface with water, it was immersed in a catalyst activation solution (OPC-150 Cryster RW, manufactured by Okuno Pharmaceutical Co., Ltd.) for 1 minute at room temperature to allow the catalyst (Pd) to adhere to the amine-generating part and activate it. Then, it was immersed in an electroless plating solution (OPC Copper HFS, manufactured by Okuno Pharmaceutical Co., Ltd.) at 40°C for 3 minutes to deposit electroless copper on the catalyst, forming a copper plating layer.

[0133] [Photoresist process]

[0134] Photoresist (OFPR5000, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied at 1500 rpm using a spin coater (Mikasa Co., Ltd., MS-A150), followed by heating at 105°C for 5 minutes, thereby forming a photoresist film. Irradiation with a dielectric photomask at 27 mJ / cm² was then performed. 2 After being exposed to UV light with a wavelength of 365 nm for 5 minutes at 105°C and then baked, the exposed parts were immersed in a developer (NMD-3, tetramethylammonium hydroxide 2.38%, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 25 seconds to remove the photoresist from the exposed parts.

[0135] [Process for forming a pre-pattern]

[0136] The copper plating layer was partially removed by heating at 105°C for 5 minutes and then immersing in a copper etching solution (acetic acid / hydrogen peroxide / water = 1 / 1 / 20) at 30°C for 40 seconds. This resulted in the formation of a pre-pattern on the copper wiring layer, including a photoresist layer.

[0137] [Process for removing the first catalyst layer]

[0138] Next, the catalyst was immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 50°C for 15 minutes to remove the first catalyst layer, palladium, present at the opening of the photoresist.

[0139] [Process for removing the photoresist layer]

[0140] A copper micro-wire layer is fabricated by immersing the substrate in a photoresist stripper (N-342, manufactured by Nagase-Chemtex) for 4 minutes at room temperature to remove the photoresist.

[0141] [Process for forming the copper wiring protective layer]

[0142] The substrate was immersed in an electroless plating catalyst solution (Melplate Aktivator 352, manufactured by Meltex Corporation) at 30°C for 40 seconds, followed by immersion in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and then immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73°C for 3 minutes. Nickel phosphorus was deposited on the copper plating to form the micro-plated wiring included in the copper wiring protection layer, thus obtaining a laminate.

[0143] [Gold plating process]

[0144] Furthermore, the wires are immersed in an electroless plating solution (Flash Gold NC, manufactured by Okuno Pharmaceutical Co., Ltd.) at 55°C for 4 minutes to induce displacement gold deposition and create micro-plated wiring, which serves as the source / drain electrode.

[0145] The electrode surface was subjected to UV cleaning for 8 minutes, ultrasonic cleaning in IPA (45 kHz, 3 minutes), and heat drying at 120°C for 60 minutes. Next, the substrate was immersed in a 0.75 wt% ethanol solution of TFTFMBT (2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzenethiol, manufactured by Tokyo Chemical Industry Co., Ltd.) for 5 minutes at room temperature, then removed, rinsed with ethanol, and dried by nitrogen blowing, thus forming a gold-thiol SAM film on the electrode surface.

[0146] Next, a 0.2 wt% / 0.45 wt% xylene solution of polystyrene (manufactured by Merck) / organic semiconductor (Ph-BTBT-10, 2-decyl-7-phenyl[1]benzothiophene[3,2-b][1]benzothiophene, manufactured by Tokyo Chemical Industry Co., Ltd.) was coated at 3000 rpm at 145°C using a heated spin coater, dried at 120°C for 10 minutes and then dried at 100°C for 60 minutes to produce an organic semiconductor layer.

[0147] The fine copper wiring processed on the film is shown. Figure 8 In the middle. Uniform and smooth copper plating can also be processed on the film, and there is no peeling after wiring, allowing for good drawing.

[0148] The fabricated source / drain electrode structure is shown in Figure 9 In the entire shape of the integrated thin film transistor (TFT), fine details can be depicted, indicating that only the Cu-plated areas can be selectively plated with Au layers.

[0149] Figure 10 The results of the evaluation of the transmission characteristics of the fabricated OTFT (channel length L = 20 μm, channel width W = 500 μm) are shown. This indicates that it also operates normally on the film substrate.

[0150] <Example 3>

[0151] In this embodiment, the photoreactivity of PiPrNBC-AEMA (polymer polyisopropyl nitrobenzylaminocarbamate-aminoethyl methacrylate) used in the formation of photosensitive resin film 12A in Examples 1 and 2 was evaluated.

[0152] The photoreactivity of monomers NBC (nitrobenzyl carbamate) and iPrNBC (isopropylnitrobenzyl carbamate) was evaluated. The structure of monomer NBC was designated as "NBC", and the structure of monomer iPrNBC was designated as "iPrNBC", as shown below.

[0153] [Chemistry 4]

[0154] Monomer NBC and monomer iPrNBC were each prepared into 0.1 mmol / L acetonitrile solutions and filled into quartz units with an optical path length of 10 mm. These were then irradiated with UV light at a wavelength of 365 nm. Photoreactivity was evaluated based on UV light exposure and the reduction rates of monomer NBC and monomer iPrNBC. The reduction rates of monomer NBC and monomer iPrNBC were determined using high-performance liquid chromatography-mass spectrometry (HPLC-MS).

[0155] Table 2 below shows the respective photoreactivity (reduction rate) for monomeric NBC and monomeric iPrNBC, corresponding to the exposure amount of UV irradiation.

[0156] The results in Table 2 are presented as a curve graph. Figure 11 middle. Figure 11 The relationship between the photoreactivity (reduction rate) of monomeric NBC and monomeric iPrNBC and UV-based exposure is shown. With increasing UV exposure, both monomeric NBC and monomeric iPrNBC induce deprotection of photosensitive desaturating groups. (See Table 2 and...) Figure 11 The results also confirm that NBC and iPrNBC decrease with increasing UV irradiance. Therefore, the rate of reduction of NBC and iPrNBC is considered as the photoreactivity. Table 3 shows the results using an illuminance of 21 mW / cm². 2 The reaction rate constant k ( / s) and half-life t of NBC and iPrNBC under UV irradiation device 1 / 2 The calculation result of (s).

[0157] [Table 2]

[0158] [Table 3]

[0159] according to Figure 11 As shown in Table 2, iPrNBC has a higher photoreactivity than NBC. Furthermore, according to the reaction rate constant k and half-life in Table 3, iPrNBC exhibits approximately 12 times the photosensitivity of NBC.

[0160] Next, the required photosensitivity as a substrate for plating was evaluated using polymer NBC and PiPrNBC-AEMA. The structure of polymer NBC is shown below.

[0161] [Chemistry 5]

[0162] Photosensitive resin films were formed on a film substrate using cyclopentanone solutions containing dissolved polymer NBC and cyclopentanone solutions containing dissolved PiPrNBC-AEMA, respectively. These photosensitive resin films were then exposed to varying amounts of light at a wavelength of 365 nm to form an amine-generating layer.

[0163] For photosensitive resin films using polymer NBC, at 2000 mJ / cm 2 1000 mJ / cm 2 500 mJ / cm 2 250 mJ / cm 2 100 mJ / cm 2 50 mJ / cm 2 10 mJ / cm 2 Exposure was performed at an exposure level of 2000 mJ / cm². For the photosensitive resin film using PiPrNBC-AEMA, exposure was performed at 2000 mJ / cm². 2 1500 mJ / cm 2 1000 mJ / cm 2 750 mJ / cm 2 500 mJ / cm 2 400mJ / cm 2 300 mJ / cm 2 200 mJ / cm 2 100 mJ / cm 2 50 mJ / cm 2 10 mJ / cm 2 0 mJ / cm 2 Exposure was performed at varying exposure levels to form an amine generation layer. Furthermore, the precipitation results when NiP plating was applied to each amine generation layer with different exposure levels are shown in the figure. Figure 12 middle.

[0164] The amine generation layer using polymer NBC requires 1000 mJ / cm² for NiP deposition. 2 The above exposure, in contrast, shows that the amine generation layer using PiPrNBC-AEMA at 200 mJ / cm 2 The above exposure results in precipitation. The reason for this is that PiPrNBC-AEMA has superior photosensitivity compared to polymeric NBC, thus reducing the exposure required for deposition as an amine-generating layer. Therefore, amine-generating layers using PiPrNBC can be deposited even with short exposure times, leading to high productivity.

[0165] Although NiP plating was used for evaluation, it is clear that the same trend is emerging in using copper plating for evaluation.

[0166] Based on the above, it can be seen that iPrNBC and PiPrNBC-AEMA not only have high photosensitivity in solution, but also exhibit high photoreactivity even when used as photosensitive resin films. Photosensitive resin films using iPrNBC and PiPrNBC-AEMA have high photosensitivity and can efficiently generate amines with low exposure, further promoting chemical reactions with the substrate or the catalysts and other chemical reactions.

[0167] The synthesis method of PiPrNBC-AEMA is described below.

[0168] <Synthesis of Isopropyl and 1-(3,4-Dimethoxyphenyl)-2-methylpropanone>

[0169] Under argon atmosphere, these were mixed in the following order: iodine (6.22 g (0.0490 mol, 0.0374 eq.), Tokyo Chemicals), o-dimethoxybenzene (180.4 g (1.31 mol, 1.00 eq.), Fujifilm and Koichi Chemicals), and isobutyric anhydride (414 g (2.62 mol, 2.00 eq.), Tokyo Chemicals). The mixture was heated and stirred at 170°C in an oil bath for 6 hours, followed by stirring at room temperature for 2 days. The mixture was then concentrated under reduced pressure to obtain 294 g of a black oily substance. Water (1.6 L) and IPE:isopropyl ether (1.6 L) were added, and the mixture was transferred to a separatory funnel. After separation of the organic layer, the aqueous layer was further extracted using IPE (800 mL). The mixture was washed sequentially with 5% sodium bicarbonate aqueous solution (1.6 L), saturated brine (1.6 L), and distilled water (1.6 L), and then dried with anhydrous magnesium sulfate. After removing the desiccant, the product was concentrated under reduced pressure to obtain 285 g of a brown oily substance. This was purified by silica gel column chromatography to obtain 222 g (81.6% yield) of isopropylidene (1-(3,4-dimethoxyphenyl)-2-methylpropanone). The structure was assigned using nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GCMS).

[0170] δ=1.22(6H)3.55(1H)3.94(3H)3.95(3H)6.90(1H)7.55(1H)7.60(1H)

[0171] [Chemistry 6]

[0172] <Synthesis of Nitro Compounds, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-one>

[0173] The isopropylidene (50.0 g (0.240 mol, 1.00 eq.)) was mixed with acetic acid (150 mL). A solution of acetic acid containing 69% nitric acid (100 mL) was added dropwise. The mixture was then heated and stirred at 50°C for 2 hours, and the disappearance of the starting material was confirmed by thin-layer chromatography (TLC). The reaction was then stopped. During the reaction treatment, ice water (800 g) was placed in the reactor, quenched, and then transferred to a separatory funnel. The reactor was thoroughly washed with ethyl acetate (1 L) and water (200 mL). The aqueous layer was separated and then washed separately with water (1 L). The mixture was then washed with a 5% sodium bicarbonate aqueous solution (1 L) and dried with a desiccant. After removing the desiccant, the mixture was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 38.7 g (64% yield) of the nitro compound (1-(4,5-dimethoxy-2-nitrophenyl)-2-methylprop-1-one). The structure was assigned using NMR and GC-MS.

[0174] δ=1.22(6H)2.91(1H)3.98(3H)3.99(3H)6.69(1H)7.66(1H)

[0175] [Chemistry 7]

[0176] <Synthesis of Isopropanol: 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-ol>

[0177] 13.8 g (54.5 mmol, 1.00 eq.) of the nitro compound, 180 mL of tetrahydrofuran (THF), and 120 mL of methanol were mixed. Then, 4.12 g (109 mmol, 2.00 eq.) of sodium borohydride was added at 0 °C. After 90 minutes from the start of addition, the mixture was stirred at room temperature for 30 minutes. The reaction mixture was then cooled with ice water, and 300 mL of 5% sodium bicarbonate aqueous solution was added, followed by stirring for 5 minutes. The reaction mixture was transferred to a separatory funnel and extracted with 600 mL of ethyl acetate. After washing the organic layer with 300 mL of saturated brine, it was dried with anhydrous magnesium sulfate. After removing the drying agent, the mixture was concentrated under reduced pressure to obtain an oily substance. The obtained crude material was purified by silica gel column chromatography to obtain 9.38 g (67% yield) of a yellow oily isopropanol (1-(4,5-dimethoxy-2-nitrophenyl)-2-methylprop-1-ol). The structure was assigned using NMR and GC-MS.

[0178] δ=0.96(6H)1.96-2.09(1H)2.23(1H)3.95(3H)3.99(3H)5.27(1H)7.21(1H)7.56(1H)

[0179] [Chemistry 8]

[0180] <Synthesis of monomer iPrNBC-AEMA>

[0181] Under argon atmosphere, 5.00 g (19.6 mmol, 1.00 eq.) of the isopropanol was dissolved in 100 ml of dry tetrahydrofuran. After adding 2.00 eq. of dibutyltin dilaurate, 3.65 g (23.5 mmol, 1.20 eq.) of ethyl 2-isocyanate methacrylate was added dropwise over 5 minutes. The mixture was then heated to a bath temperature of 75°C over 1 hour and refluxed at the same temperature for 3 hours. The reaction endpoint was confirmed by NMR and TLC. After cooling, the mixture was concentrated under reduced pressure to obtain 8.69 g of a yellow oil, iPrNBC-AEMA.

[0182] The obtained crude material was dissolved again in ethyl acetate (45 mL) and added dropwise to n-heptane (450 mL). The solid was filtered and dried under reduced pressure to obtain 6.47 g (80.5%) of the target iPrNBC-AEMA.

[0183] δ=0.98(6H)1.94(4H)2.16(1H)3.49(3H)3.95(6H)4.22(2H)4.64(1H)5.60(1H)6.12(1H)6.22(1H)6.89(1H)7.59(1H)

[0184] [Chemistry 9]

[0185] <Synthesis of PiPrNBC-AEMA>

[0186] In an argon atmosphere, 6.15 g (15.0 mmol, 1.00 eq.) of iPrNBC-AEMA was dissolved in 10 mL of superhydrated dimethylformamide (DMF) after 30 minutes of Ar bubbling. 0.123 g (0.75 mmol, 0.05 eq.) of AIBN was added, and the mixture was heated to a bath temperature of 65°C over 30 minutes and stirred at the same temperature for 21 hours. The reaction endpoint was confirmed by NMR. After cooling, the reaction mixture was added dropwise to 240 mL of methanol, and the precipitated solid was centrifuged. After removing the supernatant, another 240 mL of methanol was added, and the mixture was centrifuged again. After removing the supernatant, the crude solid was dissolved in 40 mL of chloroform and then added dropwise to 400 mL of methanol. After removing the supernatant, methanol (400 mL) was added, and solid-liquid separation was performed by centrifugation. The obtained solid was directly dried under reduced pressure in a centrifuge tube to obtain 4.01 g of PiPrNBC-AEMA.

[0187] [Chemistry 10]

[0188] <Example 4>

[0189] In this embodiment, for example Figure 3 The adhesion of the copper plating layer was evaluated when a base film formed under various conditions was used as the base film of the photosensitive resin film 12A between the substrate 10 and the photosensitive resin film 12A.

[0190] As described below, a base film is formed on an alkali-free glass substrate using epoxy resin or a silane coupling agent under various conditions. Subsequently, a 0.3 wt% solution of PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) is applied to the base film by spin coating (Mikasa, MS-A150, manufactured by Mikasa Corporation) at 1000 rpm, followed by heating at 100°C for 20 minutes, thereby forming a photosensitive resin film.

[0191] Next, the entire surface of the photosensitive resin film was exposed to 1000 mJ / cm. 2 UV light with a wavelength of 365 nm exposes the photosensitive resin film to light, thereby forming an amine-generating layer.

[0192] Next, the substrate was immersed in an electroless plating catalyst solution (manufactured by Okuno Pharmaceutical Co., Ltd.) at room temperature for 5 minutes to allow the catalyst (Pd) to adhere to the amine generation layer. After rinsing the surface with water, the substrate was immersed in a catalyst activation solution (OPC-150 Cryster R, manufactured by Okuno Pharmaceutical Co., Ltd.) at room temperature for 5 minutes to activate the catalyst (Pd) attached to the amine generation layer. Next, the substrate was immersed in an electroless plating solution (OPC Copper HFS, manufactured by Okuno Pharmaceutical Co., Ltd.) at 40°C for 3 minutes to deposit electroless copper on the catalyst, forming a copper plating layer.

[0193] [Closeness Assessment]

[0194] The formed copper plating layer was cut into a grid pattern with a 2 mm interval between the horizontal and vertical directions, and a strip peel test was performed. The adhesion between the glass substrate and the copper plating layer was evaluated through the strip peel test. Cases where the entire surface was peeled off were evaluated as "low adhesion" and recorded as "B" in Table 4, and cases where all other cases were peeled off were evaluated as "high adhesion" and recorded as "A" in Table 4.

[0195] Furthermore, in this embodiment, the epoxy resin or silane coupling agent separating the substrate 10 and the photosensitive resin film 12A may not be necessary. Figure 3 It functions as the gate insulating film 11 as shown.

[0196] <Condition A01>

[0197] An epoxy resin film (SU8-3005, manufactured by MicroChem) was used as the substrate for a photosensitive resin film on alkali-free glass. For the epoxy resin film, SU8-3005 was diluted with cyclopentanone at a solids concentration of 15 wt% to prepare a coating solution. For the alkali-free glass, the coating solution was applied by spin coating (Mikasa MS-A150) at 1000 rpm, followed by heating at 150°C for 5 minutes, thus forming an epoxy resin film on the entire surface of the alkali-free glass. The epoxy resin film was then exposed to 1000 mJ / cm². 2 Light with a wavelength of 365 nm was used to heat the epoxy resin film at 150°C for 20 minutes. The film thickness was 850 nm.

[0198] <Condition A02>

[0199] Before forming the photosensitive resin film on the epoxy resin film serving as the base film, the surface of the epoxy resin film was subjected to UV / O3 cleaning for 3 minutes. Otherwise, the epoxy resin film was formed using the same method as in condition A01. The thickness of the epoxy resin film was 850 nm.

[0200] <Condition A03>

[0201] After 5 minutes of UV / O3 cleaning of the alkali-free glass, an epoxy resin film was formed using the same method as in condition A02. Then, similarly to example A02, the surface of the epoxy resin film was cleaned with UV / O3 for 3 minutes before forming a photosensitive resin film. The epoxy resin film had a thickness of 850 nm.

[0202] <Condition A04>

[0203] After forming an epoxy resin film and a photosensitive resin film using the same method as in condition A03, a copper plating layer is formed. After forming the copper plating layer, it is heated at 100°C for 2 minutes, followed by heating at 150°C for 3 minutes.

[0204] <Condition A05>

[0205] After forming an epoxy resin film and a photosensitive resin film using the same method as in Example A03, a copper plating layer was formed. After forming the copper plating layer, it was heated at 100°C for 2 minutes, followed by heating at 250°C for 3 minutes.

[0206] <Condition A06>

[0207] An epoxy resin film (SU8-3005, manufactured by MicroChem) was used as the substrate for a photosensitive resin film on alkali-free glass. Regarding the epoxy resin film, SU8-3005 was diluted with cyclopentanone at a solids concentration of 10 wt% to prepare a coating solution. Using this coating solution, an epoxy resin film was formed over the entire surface of the alkali-free glass using the same method as in condition A04, followed by exposure at 1000 mJ / cm². 2 The film is heated at 150°C for 20 minutes with light of wavelength 365 nm. The epoxy resin film thickness is 400 nm. Other processes are the same as in condition A04.

[0208] <Condition A07>

[0209] Instead of exposing the epoxy resin film to 1000 mJ / cm under condition A06. 2 Light with a wavelength of 365 nm and a power of 200 mJ / cm 2 Expose, otherwise, it is the same as condition A06.

[0210] <Condition A08>

[0211] An epoxy resin film (SU8-3005, manufactured by MicroChem) was used as the substrate for a photosensitive resin film on alkali-free glass. Regarding the epoxy resin film, SU8-3005 was diluted with cyclopentanone at a solids concentration of 1 wt% to prepare a coating solution. Using this coating solution, an epoxy resin film was formed over the entire surface of the alkali-free glass. Subsequently, the photosensitive resin film was formed and copper was plated using the same method as in condition A07. The epoxy resin film thickness was 50 nm.

[0212] <Condition A09>

[0213] In condition A09, the epoxy resin film is applied by dip coating instead of spin coating. Alkali-free glass is dipped into a solution of SU8-3005 diluted with cyclopentanone at a solids concentration of 1 wt% at a speed of 10 mm / sec. The epoxy resin film is then formed by heating at 100°C for 5 minutes. The substrate with the epoxy resin film formed on its entire surface is exposed to 200 mJ / cm². 2 The epoxy resin film is 60 nm thick and is exposed to light with a wavelength of 365 nm.

[0214] In condition A09, the photosensitive resin film formed on the epoxy resin film is also coated by dip coating. A 0.3 wt% cyclopentanone solution of PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) is applied by dip coating (5 mm / sec), and heated at 100°C for 5 minutes, thereby forming the photosensitive resin film.

[0215] Next, the substrate with the photosensitive resin film deposited on its entire surface was exposed to 1000 mJ / cm². 2 Light with a wavelength of 365 nm is used to form an amine-generating layer. The subsequent processes until the copper plating layer is formed are the same as under condition A04.

[0216] <Condition A10>

[0217] Under these conditions, the epoxy resin film is formed by dip coating at a slower impregnation rate (5 mm / sec) than under condition A09. Otherwise, it is the same as under condition A09. The epoxy resin film thickness is 20 nm.

[0218] <Condition A11>

[0219] Under these conditions, an epoxy resin film mixed with GPSC as an epoxy silane was used as the substrate film. A coating solution was prepared by diluting cyclopentanone with 0.3 wt% 3-glycidoxypropyltrimethoxysilane (GPSC, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 wt% SU8-3005 (manufactured by MicroChem Co., Ltd.). The coating solution was spin-coated onto alkali-free glass at 1000 rpm, and the film was heated at 100°C for 5 minutes to form the epoxy resin film mixed with GPSC. Afterwards, the substrate with the epoxy resin film coated on its entire surface was exposed to 200 mJ / cm². 2 The wavelength is 365 nm. In addition, a copper plating layer is formed using the same method as in Example A08. The thickness of the substrate film is 100 nm.

[0220] <Condition A12>

[0221] In condition A11, an epoxy resin film containing GPSC as an epoxy silane was used as the base film. In condition A12, an epoxy resin film was laminated on GPSC as the base film. A coating solution was prepared by diluting 3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) with cyclopentanone at a ratio of 0.3 wt%. The GPSC coating solution was spin-coated onto alkali-free glass at 1000 rpm and heated at 150°C for 5 minutes. Afterwards, the solution was heated to 200 mJ / cm². 2 Light with a wavelength of 365 nm was exposed. After forming the GPSC layer, an epoxy resin film was formed in the same manner as in Example A08, forming a copper plating layer. The thickness of the substrate film was 100 nm.

[0222] <Condition B01>

[0223] A silane coupling agent was coated onto alkali-free glass as the base film for a photosensitive resin film. A coating solution was prepared by diluting iPrNBC-APTMOS (isopropylnitrobenzylaminocarbamate type silane coupling agent) at a solids concentration of 0.3 wt% using cyclopentanone. For alkali-free glass, the coating solution containing iPrNBC-APTMOS was applied by spin coating (Mikasa Corporation, MS-A150) at 1000 rpm, followed by heating at 150°C for 10 minutes, thereby forming a silane coupling layer. The remaining steps involved depositing a copper layer using the same method as in condition A01. The base film thickness was 2 nm.

[0224] The structure of iPrNBC-APTMOS is shown below.

[0225] [Chemistry 11]

[0226] <Condition B02>

[0227] After 5 minutes of UV / O3 cleaning of the alkali-free glass surface, a copper plating layer is formed using the same method as in condition B01.

[0228] <Condition B03>

[0229] After the copper plating layer is formed, it is heated at 100°C for 2 minutes, and then heated at 150°C for 3 minutes. Otherwise, the method is the same as that for condition B02.

[0230] <Condition C01>

[0231] As a comparative condition, an epoxy resin film is not formed on alkali-free glass; otherwise, a copper plating layer is formed using the same method as in condition A01.

[0232] <Condition C02>

[0233] As a comparison condition, only the GPSC layer was formed on alkali-free glass, and otherwise, a copper plating layer was formed using the same method as in condition B03. The GPSC layer was formed with a target thickness of less than 10 nm, and the average thickness after formation was 5.7 nm. Then, the copper plating layer was formed.

[0234] [evaluate]

[0235] The results of the adhesion evaluation for each condition are shown in Table 4. Adhesion evaluations were high for conditions A01–A12 and conditions B01–B03. In contrast, under condition C01, the entire surface of the copper plating layer peeled off, indicating low adhesion. Based on these results, it can be seen that by setting an epoxy resin film or a silane coupling layer as a base film between the glass substrate and the amine generation layer, the adhesion strength is improved. This is particularly effective when using substrates that are difficult to plate or adhere to, such as glass substrates.

[0236] [Table 4]

[0237] Specifically, a material capable of forming chemical bonds with the amino groups present in the amine-generating layer is used as the base film. Examples of chemical structures intermediate between the glass surface and the amino groups in the amine-generating layer include epoxy groups, alkoxysilanes, isocyanates, and acid anhydrides. In particular, epoxy groups or alkoxysilanes are ideal. These materials can also be used as the base layer in conditions A01 to A10 and conditions B01 to B03. The method of forming the base film is not particularly limited; it can be spin-coated or dip-coated as in conditions A01 to A10, or it can be sprayed or rolled.

[0238] It is believed that cross-linking of the epoxy-based base film with the hydroxyl groups of the glass substrate can achieve excellent adhesion to the substrate. Furthermore, cross-linking of the epoxy groups with the amino groups of the amine-generating layer also yields excellent adhesion to the amine-generating layer. Therefore, by using an epoxy-based material as the base film, the adhesion between the substrate and the amine-generating layer can be enhanced, thereby preventing the peeling of the copper plating layer.

[0239] The material contained in the base film is preferably a multifunctional epoxy group, and more preferably a photosensitive epoxy composition capable of photo-promoting crosslinking reactions. The hydroxyl groups on the glass substrate surface can form chemical bonds with the epoxy groups of the epoxy resin, and the amino groups in the amine-generating layer can form chemical bonds with the epoxy groups of the epoxy resin.

[0240] Furthermore, the iPrNBC-APTMOS, acting as a silane coupling agent, undergoes a transformation through exposure to form bonds with both amino and silane groups. The amino groups in the silane coupling agent exhibit high affinity for the amino groups in the amine generation layer, resulting in enhanced adhesion between the two. Consequently, since the silane groups form siloxane bonds with the glass substrate, high adhesion to the glass substrate is also achieved. Therefore, the silane coupling agent can also enhance the adhesion between the substrate and the amine generation layer, preventing the copper plating layer from peeling off.

[0241] Furthermore, under condition CO2, when a GPSC layer with an average film thickness of 5.7 nm was used as the base film, peeling was observed across the entire surface of the copper plating layer, indicating low adhesion. In contrast, when the epoxy resin film in condition A10 was 20 nm thick, no peeling of the copper plating layer was observed, indicating high adhesion. Therefore, it can be concluded that the film thickness of the epoxy-based base film is preferably 20 nm or more.

Claims

1. A laminate, comprising, in sequence, a substrate, an amine generating layer, a copper wiring layer, and a copper wiring protection layer.

2. The laminated body according to claim 1, wherein, A palladium-containing layer is included between the copper wiring layer and the amine generation layer.

3. The laminate according to claim 1 or 2, wherein, The copper wiring protective layer includes a gold plating layer.

4. A transistor comprising a stack according to claim 1 or 2, and an organic semiconductor layer.

5. A method for manufacturing a laminate, comprising the following steps: coating a photosensitive surface treatment agent onto a substrate to form a photosensitive resin film, exposing the photosensitive resin film to form an amine generation layer having an amine generation region in the exposed area; A first catalyst layer is formed on the amine generation layer, and then electroless copper plating is performed to form a copper plating layer. A photoresist layer is formed on the copper plating layer, and the photoresist layer is patterned and exposed to form an exposed area corresponding to the pattern of the copper wiring layer. The unexposed photoresist layer is then removed. A portion of the copper plating layer is removed to form a copper wiring layer, and a pre-pattern including a photoresist layer is formed on the copper wiring layer. The catalyst remover is brought into contact with the pre-pattern to remove the first catalyst layer present at the opening of the photoresist; Remove the photoresist layer on the copper wiring layer; and A second catalyst layer is formed on the copper wiring layer, and then electroless plating is performed to form a copper wiring protective layer.

6. A method for manufacturing a transistor, comprising the method for manufacturing a laminate according to claim 5.

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