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

Abstract

A laminate comprising a substrate, an amine generation layer, a copper wiring layer, and a copper wiring protection layer in this order.

Description

Stacked body, transistor, manufacturing method of stacked body, and manufacturing method of transistor

[0001] This application claims priority to PCT / JP2023 / 034991 filed on September 26, 2023, the contents of which are incorporated herein by reference.

[0002] In recent years, in the manufacture of microdevices such as semiconductor elements, integrated circuits, and devices for organic EL displays, a method has been proposed in which patterns with different surface properties are formed on a substrate and the differences in surface properties are utilized to create microdevices.

[0003] One example of a pattern formation method that utilizes differences in surface properties on a substrate is to form a region in which chemically active substituents are generated on a part of the substrate, which allows a metal material, organic material, or inorganic material to adhere to that part of the substrate.

[0004] Electroless plating is a technique for adhering a metal material to a substrate to form a metal film. For example, Patent Document 1 discloses a technique for forming fine wiring by electroless plating. Specifically, Patent Document 1 discloses a technique for using a catalyst activation layer and a photoresist to perform photopatterning by etching or lift-off after plating the entire surface.

[0005] Japanese Patent Application Laid-Open No. 2006-2201

[0006] A first aspect of the present invention is a laminate comprising a substrate, an undercoat layer, a copper wiring layer, and a copper wiring protection layer in this order, the undercoat layer comprising an amine generating layer.

[0007] FIG. 1 is a schematic cross-sectional view of an example of a laminate according to the present embodiment. FIG. 2 is a schematic cross-sectional view of an example of a transistor according to the present embodiment. FIG. 3 is a schematic view for explaining the steps of an example of a manufacturing method for the laminate according to the present embodiment. FIG. 4 is a schematic view for explaining the steps of an example of a manufacturing method for the laminate according to the present embodiment. FIG. 5 is a schematic view for explaining the steps of an example of a manufacturing method for the laminate according to the present embodiment. FIG. 6 is a view showing a source / drain electrode structure manufactured in Example 1. FIG. 7 is a view showing the results of a transfer characteristic evaluation of the transistor manufactured in Example 1. FIG. 8 is a view showing fine wiring manufactured in Example 2. FIG. 9 is a view showing a source / drain electrode structure manufactured in Example 2. FIG. 10 is a view showing the results of a transfer characteristic evaluation of the transistor manufactured in Example 2. FIG. 11 is a view showing the relationship between the exposure dose by UV irradiation and the photoreaction rate for monomer NBC and monomer iPrNBC. FIG. 12 is a view showing the deposition results when NiP plating treatment was performed on each amine generating layer with different exposure doses for polymer NBC and PiPrNBC-AEMA.

[0008] The laminate and the method for manufacturing the laminate of the present embodiment will be described below with reference to the drawings. Note that in all the drawings below, the dimensions and proportions of the components are appropriately changed to make the drawings easier to understand.

[0009] <Laminate> One aspect of the present invention is a laminate comprising, in this order, a substrate, an amine generating layer, a copper wiring layer, and a copper wiring protection layer. Figure 1 is a schematic cross-sectional view of laminate 1 of this embodiment. Laminate 1 comprises substrate 10, amine generating layer 12, copper wiring layer 14C, and copper wiring protection layer 16. In Figure 1, gate insulating layer 11 and first catalyst layer 13 are optional.

[0010] Amine generating layer 12 and optional gate insulating layer 11 are formed over the entire surface of one main surface of substrate 10. Copper wiring layer 14C is a fine copper wiring pattern formed on amine generating layer 12. Copper wiring layer 14C is protected by copper wiring protection layer 16. Copper wiring protection layer 16 is a conductive protective film.

[0011] The laminate 1 can be suitably used as a patterned electrode of a transistor. When the laminate 1 is used as a patterned electrode of a transistor, the copper wiring layer 14C forms a source electrode or a drain electrode, respectively.

[0012] The substrate 10 may be either optically transparent or non-optically transparent, and may be made of, for example, inorganic materials such as glass, quartz glass, silicon, or silicon nitride, or organic polymers (resins) such as acrylic resin, polycarbonate resin, or polyester resins such as PET (polyethylene terephthalate) or PBT (polybutylene terephthalate).

[0013] The amine contained in the amine generating layer 12 is, for example, a primary amine (—NH ２ -), and secondary amine (-NH-).

[0014] When the stack 1 constitutes a bottom-gate transistor, it is preferable to provide a gate insulating layer 11 on the substrate 10. The gate insulating layer 11 contains, for example, a methoxysilane coupling agent or polymethoxychalcone. As an optional configuration, a metal wiring pattern including a gate electrode may be provided on the entire or part of one main surface of the substrate 10, below the gate insulating layer 11. This metal wiring pattern may be made of, for example, a conductive material containing molybdenum and aluminum, and is a fine metal wire of MAM (a three-layer structure of Mo (molybdenum), Al (aluminum), and Mo (molybdenum)).

[0015] Copper wiring layer 14C is a metal wiring formed on the surface of amine generating layer 12. Laminate 1 is manufactured by the laminate manufacturing method of this embodiment, which will be described later. In the manufacturing method of this embodiment, first catalyst layer 13 may remain under copper wiring layer 14C as a trace of the step of removing the first catalyst layer present in the openings of the photoresist layer. First catalyst layer 13 may be a layer containing palladium.

[0016] The top and side surfaces of the copper wiring layer 14C are protected by a copper wiring protection layer 16. The copper wiring protection layer 16 is a protective film having electrical conductivity, and specific constituent materials thereof are nickel phosphorus, nickel boron, or palladium.

[0017] When the laminate 1 constitutes a transistor, it is preferable to provide a gold plating layer on the copper wiring protection layer. Fig. 2 shows a schematic cross-sectional view of a transistor including the laminate of this embodiment and an organic semiconductor layer.

[0018] 2 , the transistor 2 includes a substrate 10, an amine generating layer 12, a source electrode 32, a drain electrode 31, and an organic semiconductor layer 33. The source electrode 32 and the drain electrode 33 each include a copper wiring layer 14C, a copper wiring protection layer 16, and a gold plating layer 17. The transistor 2 shown in FIG. 2 further includes a gate insulating layer 11 and a first catalyst layer 13.

[0019] The gold plating layer 17 is a metal wiring formed by electroless plating, similar to the copper wiring layer 14C.

[0020] The copper wiring layer 14C serves as a first electrode constituting the source electrode 32 or the drain electrode 31, and the gold plating layer 17 serves as a second electrode constituting the source electrode 32 or the drain electrode 31. In relation to the HOMO / LUMO levels of the material forming the organic semiconductor layer 33, the material constituting the second electrode is preferably gold (work function: 5.4 eV), which is a metal material having a work function that facilitates electron (or hole) movement.

[0021] For the above reasons, conventional wiring using nickel phosphorus as the first electrode and gold as the second electrode has been considered. However, when nickel phosphorus is used, the resistance increases when the transistor is enlarged, so a material with lower resistance has been sought.

[0022] The inventors aimed to manufacture a low-resistance transistor and used copper for the first electrode. However, when the copper wiring of the first electrode was coated with gold, migration occurred when the transistor was driven, and the copper wiring was exposed and oxidized. This was a problem.

[0023] Therefore, the inventors came up with the idea of ​​protecting the copper wiring layer with a copper wiring protection layer, and completed the present invention.

[0024] In the laminate of this embodiment, the copper wiring layer is protected by the copper wiring protection layer, so even if a gold plating layer is further formed to drive the transistor, migration does not occur and a transistor with reduced resistance can be provided.

[0025] The organic semiconductor material used in the transistor is not particularly limited, and examples thereof include p-type semiconductors such as copper phthalocyanine (CuPc), pentacene, rubrene, tetracene, and P3HT (poly(3-hexylthiophene-2,5-diyl)), n-type semiconductors such as fullerenes such as C60 and perylene derivatives such as PTCDI-CH (N,N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimide), and Ph-BTBT-10 (2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene). Among these, soluble pentacenes such as TIPS pentacene (6,13-Bis(triisopropylsilylethylenyl)pentacene), organic semiconductor polymers such as P3HT, and Ph-BTBT-10 are preferred because they are soluble in organic solvents such as toluene and allow the formation of organic semiconductor layers by wet processes. The HOMO level of TIPS pentacene is 5.2 eV, and the HOMO level of Ph-BTBT-10 is −5.6 eV.

[0026] <Method for manufacturing laminate> A method for manufacturing a laminate according to one embodiment of the present invention will be described with reference to the drawings. The step shown in FIG. 3A is an optional step, but when manufacturing a laminate constituting a transistor, it is preferable to form a gate insulating layer 11 on the surface of a substrate 10.

[0027] The gate insulating layer 11 can be formed by applying, for example, a methoxysilane coupling agent to the entire surface of one main surface of the substrate 10. The gate insulating layer 11 is preferably formed by applying the methoxysilane coupling agent, then further applying a photosensitive polymer material such as polymethoxychalcone, and irradiating it with ultraviolet light.

[0028] Furthermore, as an optional step, a step of forming a metal wiring pattern on the entire or part of one main surface of the substrate 10, below the gate insulating layer 11, may be included. This metal wiring pattern may be made of, for example, a conductive material containing molybdenum and aluminum, and may be formed as fine metal wires of MAM (a three-layer structure of Mo (molybdenum), Al (aluminum), and Mo (molybdenum)).

[0029] Next, as shown in Fig. 3, symbol 3B, a photosensitive surface treatment agent is applied to substrate 10 or optionally formed gate insulating layer 11 to form photosensitive resin film 12A. Photosensitive resin film 12A is exposed to light to form amine generating layer 12 having an amine generating region in the exposed portion (Fig. 3, symbol 3C).

[0030] The photosensitive resin film 12A may be exposed to light over the entire surface or may be exposed to light in a pattern through a mask. However, from the viewpoint of forming a copper plating layer over the entire surface of the substrate 10 in a later step, it is preferable to expose the entire surface.

[0031] The photosensitive surface treatment agent for forming the photosensitive resin film 12A is not limited as long as it is a material that can eliminate a protecting group and generate an amine upon irradiation with light. For example, a photosensitive surface treatment agent containing the following photosensitive polymer 1 (polyisopropylnitrobenzyl carbamate) is preferred.

[0032]

[0033] When the photosensitive resin film 12A is exposed to light, amines are generated in the exposed areas, forming the amine generating layer 12 having amine generating regions 12X (FIG. 3, reference numeral 3C). The amines are, for example, primary amines (—NH ２ -), and secondary amine (-NH-).

[0034] 3, reference numeral 3D, a first catalyst layer 13 is formed on the amine generating layer 12, and electroless copper plating is performed to form a copper plating layer 14. The first catalyst layer 13 is composed of an electroless plating catalyst. The electroless plating catalyst is a catalyst that reduces metal ions contained in the plating solution for electroless plating, and examples of such catalysts include silver and palladium.

[0035] Amino groups are exposed on the surface of amine generating layer 12. The amino groups are capable of capturing and reducing the electroless plating catalyst described above. Therefore, the electroless plating catalyst is captured on amine generating layer 12, forming first catalyst layer 13. In addition, the electroless plating catalyst can be one that can support amino groups.

[0036] The catalyst used to form the first catalyst layer 13 is not limited as long as it is a catalyst for electroless copper plating and can support an amine, but is preferably a metal catalyst having a pH of 3 to 12 at a measurement temperature of 20° C. An example of a commercially available catalyst of this kind is Activator 7331 manufactured by Melplate, which is a palladium catalyst having a pH of 3.5 to 6.5 at a measurement temperature of 20° C.

[0037] After forming the first catalytic layer 13, it is preferable to perform an optional process of activating the first catalytic layer 13 before forming the copper plating layer 14. The activation process of the first catalytic layer 13 is a process of reducing metal chlorides contained in the applied catalyst to metals. For example, this is a process of reducing palladium chloride contained in the applied catalyst to metallic palladium, or a process of reducing silver chloride to metallic silver.

[0038] The treatment for activating the first catalyst layer 13 is a known method, and an acid or alkaline solution called an accelerator can be used, specifically, a commercially available activator (for example, OPC-150 Crystal RW manufactured by Okuno Chemical Industries Co., Ltd.) can be used. Activating the first catalyst layer 13 metallizes the metal chloride, thereby improving the deposition and adhesion of electroless copper plating.

[0039] After forming first catalyst layer 13, electroless plating is performed to form copper plating layer 14. In the electroless plating, substrate 10 is immersed in an electroless plating bath to reduce metal ions on the surface of first catalyst layer 13, thereby depositing copper plating layer 14. Formation of amine generating layer 12 supports a sufficient amount of catalyst, allowing the formation of copper plating layer 14 with high adhesion to substrate 10.

[0040] Next, as shown in Fig. 4, reference numeral 4A, a photoresist material 15A is applied onto the copper plating layer 14, and the photoresist material 15A is pattern-exposed through a mask M to form exposed portions corresponding to the pattern of the copper wiring layer. Thereafter, as shown in Fig. 4, reference numeral 4B, the photoresist in the unexposed portions is removed to form a photoresist layer 15.

[0041] The photoresist material 15A may be any known material, such as a positive photoresist material.

[0042] 4, a copper wiring layer 14C is formed by removing a portion of the copper plating layer 14. Through this process, a preliminary pattern P including a photoresist layer 15 is formed on the copper wiring layer 14C.

[0043] Next, as shown in Figure 4, reference numeral 4D, a catalyst remover is brought into contact with the preliminary pattern P to remove the first catalyst layer 13 present in the photoresist openings. One method for removing the first catalyst layer 13 is to immerse the substrate 10 in the catalyst remover. The catalyst remover is preferably an aqueous solution containing an organic amine.

[0044] When substrate 10 is immersed in an aqueous solution containing an organic amine, the metal catalyst constituting first catalyst layer 13 and the organic amine form a complex, which improves the solubility of the metal catalyst and enables removal of first catalyst layer 13. At this time, photoresist layer 15 does not dissolve in the aqueous solution containing an organic amine, so first catalyst layer 13 can be removed while leaving photoresist layer 15 intact.

[0045] The aqueous solution containing an organic amine is preferably an aqueous solution containing ethylenediamine. An example of such a commercially available product is ICP Postdip RP manufactured by Okuno Chemical Industries Co., Ltd.

[0046] When forming the copper plating layer 14 over the entire surface of one main surface of the substrate 10, it is preferable to use a neutral metal catalyst having a pH of 3.5 to 6.5 at a measurement temperature of 20° C., which can precipitate a large amount of copper in order to enhance adhesion between the substrate 10 and the copper plating layer 14. However, if the neutral metal catalyst remains, the metal components that constitute the copper wiring protection layer will be excessively precipitated in the subsequent step of forming the copper wiring protection layer, resulting in an increase in resistance value.

[0047] For this reason, it is necessary to remove the first catalyst layer 13 present in the photoresist openings. However, since the organic amine that constitutes the catalyst remover also forms a complex with copper, simply immersing the substrate 10 in an aqueous solution containing the organic amine will dissolve the copper that constitutes the copper wiring layer 14C, damaging the copper wiring.

[0048] In this embodiment, by contacting the preliminary pattern P with a catalyst remover, the photoresist layer 15 protects the copper wiring layer 14C from the catalyst remover, and the first catalyst layer 13 can be removed without damaging the copper wiring layer 14C.

[0049] Although the top surface of the copper wiring in copper wiring layer 14C is protected by photoresist layer 15, the side surfaces are not protected. However, since the area ratio of the side surfaces to the entire copper wiring layer 14C is small, damage to the side surfaces caused by the catalyst remover is unlikely to become apparent.

[0050] Furthermore, after removing the first catalyst layer 13 present in the photoresist openings, the photoresist layer 15 is removed as shown in Fig. 5, reference numeral 5A. The photoresist layer 15 may be removed using a known developer.

[0051] Furthermore, as shown in Fig. 5B, a second catalyst layer 20 is formed on the copper wiring layer 14C, and electroless plating is then performed to form a copper wiring protection layer 16 (Fig. 5C). The copper wiring protection layer 16 is formed so as to cover the top and side surfaces of the copper wiring in the copper wiring layer 14C. The copper wiring protection layer 16 is a protective film having electrical conductivity, and specific constituent materials are nickel phosphorus, nickel boron, or palladium.

[0052] To form copper wiring protection layer 16, second catalyst layer 20 is formed on copper wiring layer 14C. The catalyst constituting the second catalyst layer is an electroless plating catalyst different from the electroless plating catalyst constituting first catalyst layer 13, and the catalyst used here is preferably an acidic metal catalyst having a pH of 2 or less at a measurement temperature of 20°C. An example of such a catalyst is Activator 352 manufactured by Melplate, which is an acidic palladium catalyst having a pH of 1 or less at a measurement temperature of 20°C.

[0053] By forming the conductive protective layer 16, the gold that constitutes the electroless gold plating layer and the copper that constitutes the copper wiring layer, which will be formed in a later optional process, are less likely to migrate, making it less likely that short circuits will occur due to reduced migration.

[0054] Furthermore, as an optional step, a gold plating layer 17 may be formed (FIG. 5, reference numeral 3D). The gold plating layer 17 may be formed by electroless plating, similar to the copper plating layer 14.

[0055] <Method for manufacturing transistor> The method for manufacturing a transistor of the present embodiment includes a step of forming an organic semiconductor layer in contact with opposing surfaces of a source electrode and a drain electrode, after performing the steps up to the step of providing a gold plating layer by the method for manufacturing a laminate of the present embodiment described above.

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0057] Example 1 [Step of Forming an Amine Generating Layer] A silicon wafer with a thermally oxidized film was subjected to surface treatment by forming a film of a cyclopentanone solution of MCSC ((E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate) by spin coating. A 5 wt % cyclopentanone solution of PMC (Poly(4-Methoxychalcone)) was then applied by spin coating (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm), and then dried at 100°C for 20 minutes. UV light with a wavelength of 365 nm was applied at 1200 mJ / cm. ２A gate insulating layer serving as a base was formed by irradiating the silicon wafer with light and heating it for 60 minutes at 150° C. In this Example 1, the silicon wafer functions as a gate electrode of a transistor.

[0058] The structures of MCSC and PMC are shown below.

[0059]

[0060] Next, a 0.3 wt % solution of PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) in cyclopentanone was applied by spin coating (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm, and heated at 100° C. for 20 minutes to form a photosensitive polymer layer.

[0061] The structure of PiPrNBC-AEMA is shown below.

[0062]

[0063] Next, the substrate on which the photosensitive polymer layer was formed on the entire surface was irradiated with light of 365 nm wavelength at 1000 mJ / cm ２ The photopolymer layer was exposed to light to form an amine-generating layer.

[0064] [Step of forming a copper plating layer] Next, the substrate was immersed in a catalyst solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) at room temperature for 10 minutes, thereby attaching a catalyst (Pd) to the amine-generating portion. After rinsing the surface with water, the substrate was immersed in a catalyst activation solution (OPC-150 Crystal RW, manufactured by Okuno Pharmaceutical Industries) at room temperature for 1 minute, thereby attaching and activating the catalyst (Pd) to the amine-generating portion. This formed a first catalyst layer. Subsequently, the substrate was immersed in an electroless plating solution (OPC Copper HFS, manufactured by Okuno Pharmaceutical Industries) at 40°C for 3 minutes, thereby depositing electroless copper on the catalyst to form a copper plating layer.

[0065] [Photoresist Process] A photoresist (PFI-34, manufactured by Sumitomo Chemical Co., Ltd.) was applied by spin coating (MS-A150, manufactured by Mikasa Co., Ltd.) at 1500 rpm and heated at 105°C for 8 minutes to form a photoresist layer. UV light with a wavelength of 365 nm was irradiated through a photomask at 100 mJ / cm. ２After irradiation and post-baking at 105° C. for 3 minutes, the exposed photoresist was removed by immersion in a developer (NMD-3, 2.38% tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute.

[0066] [Step of forming a preliminary pattern] The copper plating layer was partially removed by heating at 105° C. for 5 minutes and immersing in a copper etching solution (acetic acid / hydrogen peroxide / water=1 / 1 / 20) at 30° C. for 40 seconds, thereby forming a preliminary pattern comprising a photoresist layer on the copper wiring layer.

[0067] [Step of Removing the First Catalyst Layer] Subsequently, the substrate was immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 50° C. for 15 minutes to remove the palladium, which was the first catalyst layer, present in the openings of the photoresist.

[0068] [Step of Removing Photoresist Layer] The substrate was immersed in a resist remover (N-342, manufactured by Nagase ChemteX Corporation) at room temperature for 4 minutes to remove the photoresist, thereby forming a copper fine wiring layer.

[0069] [Step of forming copper wiring protective layer] The substrate was immersed in a catalyst solution for electroless plating (Melplate Activator 352, manufactured by Meltex) at 30°C for 40 seconds, then immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 25°C for 1 minute, and then immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex) at 73°C for 3 minutes, whereby nickel phosphorus was deposited on the copper plating to produce fine plated wiring with a copper wiring protective layer, and a laminate was obtained.

[0070] [Gold Plating Step] The substrate was then immersed in an electroless plating solution (Flash Gold NC, manufactured by Okuno Chemical Industries Co., Ltd.) at 55° C. for 4 minutes to deposit displacement gold plating, thereby producing fine plated wiring as source / drain electrodes.

[0071] The electrode surface was ultrasonically cleaned (45 kHz, 4 minutes) in cyclopentanone, xylene, and IPA, followed by heating and drying at 120°C for 60 minutes. This was followed by UV cleaning for 8 minutes and ultrasonic cleaning in IPA (45 kHz, 3 minutes), and then heating and drying at 120°C for 60 minutes. The substrate was then 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.) at room temperature for 5 minutes, removed, rinsed with ethanol, and dried with a nitrogen spray, forming a gold-thiol SAM film on the electrode surface.

[0072] Next, a 0.1 / 0.45 wt % xylene solution of polystyrene (manufactured by Merck) / organic semiconductor (Ph-BTBT-10, 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene, manufactured by Tokyo Chemical Industry Co., Ltd.) was applied using a heated spin coater at 145°C and 3000 rpm, and dried at 120°C for 10 minutes and then at 100°C for 60 minutes to prepare an organic semiconductor layer, and the transistor of Example 1 was obtained.

[0073] The fabricated source / drain electrode structure is shown in Figure 6. It was confirmed that detailed writing was possible for all shapes with inter-electrode distances of 10, 20, 35, 50, and 80 μm.

[0074] The results of the transfer characteristic evaluation of the OTFTs (channel lengths L=10, 20, 35, 50, and 80 μm, channel width W=500 μm) shown in Fig. 7 are shown in Fig. 7. It was confirmed that all of them operated normally, regardless of the channel length.

[0075] In Example 1, a thin copper plating of approximately 200 nm was used, which is susceptible to the effects of chemicals that reduce conductivity. By removing the palladium underneath the copper plating while leaving the resist in place, it was possible to deposit an excellent Au plating without damaging the copper plating. While the sheet resistance after copper plating was 0.19 Ω / □, it was possible to maintain a 0.22 Ω / □ after Au deposition.

[0076] Comparative Example 1 A transistor of Comparative Example 1 was manufactured in the same manner as in Example 1, except that the step of forming a photoresist layer was not performed and a step of immersing the substrate in a catalyst remover (ICP Post-Dip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 25°C for 2 minutes was added before forming a copper wiring protection layer on the copper plating layer.

[0077] The sheet resistance after copper plating was 0.38 Ω / □, while after Au lamination it was 0.72 Ω / □, confirming a decrease in conductivity. It has been confirmed that immersion in a catalyst remover without resist protection leads to an increase in resistance, so it is advisable to avoid exposing the copper to chemicals before applying a catalyst to the copper surface.

[0078] Comparative Example 2 A transistor of Comparative Example 2 was manufactured in the same manner as in Comparative Example 1, except that the copper plating layer was immersed in a catalyst remover (ICP Post-Dip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 25°C for 1 minute before forming a copper wiring protection layer on the copper plating layer.

[0079] The sheet resistance after copper plating was 0.34 Ω / □, while after Au lamination, the conductivity was confirmed to be 1.02 Ω / □. It has been confirmed that immersion in a catalyst remover without resist protection leads to an increase in resistance, so it is desirable to avoid exposing the copper to chemicals before applying a catalyst to the copper surface.

[0080] Comparative Example 3 A transistor of Comparative Example 3 was manufactured in the same manner as in Comparative Example 1, except that the copper plating layer was immersed in a catalyst remover (ICP Post-Dip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 25°C for 4 minutes before forming a copper wiring protection layer on the copper plating layer.

[0081] The sheet resistance after copper plating was 0.41 Ω / □, while after Au lamination it was 1.58 Ω / □, confirming a decrease in conductivity. It has been confirmed that immersion in a catalyst remover without resist protection leads to an increase in resistance, so it is advisable to avoid exposing the copper to chemicals before applying a catalyst to the copper surface.

[0082] The results of Example 1 and Comparative Examples 1, 2, and 3 are summarized in Table 1.

[0083]

[0084] Example 2 [Process for Forming an Amine Generating Layer] A MAM (Mo / Al / Mo) film was dry-formed on a PEN (Teonex, polyethylene terephthalate, manufactured by Teijin) film, and fine wiring of the MAM was formed by photolithography to form a gate electrode. After UV / O3 cleaning for 3 minutes, a 0.2 wt % cyclopentanone solution of MCSC ((E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate) was spin-coated to form a film for surface treatment. A 12 / 1.2 wt % cyclopentanone solution of PVCI (polyvinyl cinnamate, manufactured by Merck) / MC (methoxychalcone, manufactured by Tokyo Chemical Industry Co., Ltd.) was then spin-coated (MS-A150, manufactured by Mikasa Co., Ltd.) at 2000 rpm, followed by drying at 80°C for 20 minutes. The film was irradiated with 624 mJ / cm 2 of UV light having a wavelength of 365 nm, developed with PGMEA (propylene glycol monomethyl ether acetate, manufactured by Tokyo Chemical Industry Co., Ltd.), and heated at 150° C. for 120 minutes to form a gate insulating layer.

[0085] Next, a 0.3 wt % solution of PiPrNBC-AEMA in cyclopentanone was applied at 1000 rpm using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) and heated at 100° C. for 20 minutes to form a photosensitive polymer layer.

[0086] Next, the substrate on which the photosensitive polymer layer was formed on the entire surface was irradiated with light of 365 nm wavelength at 1000 mJ / cm ２ The photopolymer layer was exposed to light to form an amine-generating layer.

[0087] [Step of forming a copper plating layer] Next, the substrate was immersed in a catalyst solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) at room temperature for 10 minutes to attach a catalyst (Pd) to the amine-generating portion. After rinsing the surface with water, the substrate was immersed in a catalyst activation solution (OPC-150 Crystal RW, manufactured by Okuno Pharmaceutical Industries) at room temperature for 1 minute to attach and activate the catalyst (Pd) to the amine-generating portion. Subsequently, the substrate was immersed in an electroless plating solution (OPC Copper HFS, manufactured by Okuno Pharmaceutical Industries) at 40°C for 3 minutes to deposit electroless copper on the catalyst, producing a copper plating layer.

[0088] [Photoresist Process] A photoresist (OFPR5000, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied by spin coating (MS-A150, manufactured by Mikasa Co., Ltd.) at 1500 rpm and heated at 105°C for 5 minutes to form a photoresist layer. UV light having a wavelength of 365 nm was irradiated through a photomask at 27 mJ / cm. ２ After irradiation and post-baking at 105° C. for 5 minutes, the exposed photoresist was removed by immersion in a developer (NMD-3, 2.38% tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 25 seconds.

[0089] [Step of forming a preliminary pattern] The copper plating layer was partially removed by heating at 105° C. for 5 minutes and immersing in a copper etching solution (acetic acid / hydrogen peroxide / water=1 / 1 / 20) at 30° C. for 40 seconds, thereby forming a preliminary pattern comprising a photoresist layer on the copper wiring layer.

[0090] [Step of Removing the First Catalyst Layer] Subsequently, the substrate was immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 50° C. for 15 minutes to remove the palladium of the first catalyst layer present in the openings of the photoresist.

[0091] [Step of Removing Photoresist Layer] The substrate was immersed in a resist remover (N-342, manufactured by Nagase ChemteX Corporation) at room temperature for 4 minutes to remove the photoresist, thereby forming a copper fine wiring layer.

[0092] [Step of forming copper wiring protective layer] The substrate was immersed in a catalyst solution for electroless plating (Melplate Activator 352, manufactured by Meltex) at 30°C for 40 seconds, then immersed in a catalyst remover (ICP Postdip RP-C, manufactured by Okuno Chemical Industries Co., Ltd.) at 25°C for 1 minute, and then immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex) at 73°C for 3 minutes, whereby nickel phosphorus was deposited on the copper plating to produce fine plated wiring with a copper wiring protective layer, and a laminate was obtained.

[0093] [Gold Plating Step] The substrate was then immersed in an electroless plating solution (Flash Gold NC, manufactured by Okuno Chemical Industries Co., Ltd.) at 55° C. for 4 minutes to deposit displacement gold plating, thereby producing fine plated wiring as source / drain electrodes.

[0094] The electrode surface was subjected to UV cleaning for 8 minutes, ultrasonic cleaning in IPA (45 kHz, 3 minutes), and then heated and dried for 60 minutes at 120° C. 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.) at room temperature for 5 minutes, removed, rinsed with ethanol, and dried with a nitrogen spray to form a gold-thiol SAM film on the electrode surface.

[0095] Next, a 0.2 / 0.45 wt % xylene solution of polystyrene (manufactured by Merck) / organic semiconductor (Ph-BTBT-10, 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene, manufactured by Tokyo Chemical Industry Co., Ltd.) was applied using a heated spin coater at 145°C and 3000 rpm, and dried at 120°C for 10 minutes and then at 100°C for 60 minutes to prepare an organic semiconductor layer.

[0096] The copper fine wiring processed on the film is shown in Figure 8. Even on the film, uniform and smooth copper plating was achieved, and good patterning was possible without peeling even after wiring processing.

[0097] The fabricated source / drain electrode structure is shown in Figure 9. It shows that the entire TFT integrated shape was patterned in detail, and that Au layer plating was selectively formed only in the Cu plated areas.

[0098] Figure 10 shows the results of evaluation of the transfer characteristics of the fabricated OTFT (channel length L = 20 μm, channel width W = 500 μm). It shows that the OTFT operates normally even on a film substrate.

[0099] Example 3 In this example, the photoreaction characteristics of PiPrNBC-AEMA (polymer polyisopropylnitrobenzylcarbamate-aminoethylmethylacrylate) used in forming the photosensitive resin film 12A in Examples 1 and 2 were evaluated.

[0100] Photoreactivity evaluation was performed on the monomer NBC (nitrobenzyl carbamate) and the monomer iPrNBC (isopropyl nitrobenzyl carbamate). The structure of the monomer NBC is designated as "NBC" and the structure of the monomer iPrNBC is designated as "iPrNBC", and the structures are shown below.

[0101]

[0102] Monomer NBC and monomer iPrNBC were each prepared as acetonitrile solutions at a concentration of 0.1 mMol / L and filled into a quartz cell 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 the amount of UV light exposure and the respective reduction rates of monomer NBC and monomer iPrNBC. The respective reduction rates of monomer NBC and monomer iPrNBC were measured using high-performance liquid chromatography mass spectrometry (HPLC-MS).

[0103] Table 2 below shows the photoreaction rates (reduction rates) of monomer NBC and monomer iPrNBC depending on the amount of UV irradiation. The results of Table 2 are shown as a graph in FIG. 11. FIG. 11 shows the relationship between the photoreaction rates (reduction rates) of monomer NBC and monomer iPrNBC and the amount of UV irradiation exposure. In monomer NBC and monomer iPrNBC, deprotection of the photosensitive leaving group is induced as the amount of UV irradiation increases. The results shown in Table 2 and FIG. 11 also confirmed that NBC and iPrNBC decrease as the amount of UV irradiation increases. Therefore, the reduction rates of NBC and iPrNBC were considered to be the photoreaction rates. Table 3 shows the results for monomer NBC and monomer iPrNBC at an illuminance of 21 mW / cm. ２ The reaction rate constant k ( / s) and half-life t of NBC and iPrNBC when using a UV irradiation device １／２ The calculation results of (s) are shown below.

[0104]

[0105]

[0106] 11 and Table 2, it can be seen that iPrNBC has a higher photoreaction rate than NBC. Furthermore, the reaction rate constant k and half-life in Table 3 show that iPrNBC exhibits photosensitivity characteristics approximately 12 times that of NBC.

[0107] Next, the photosensitivity required for the underlayer for plating was evaluated using polymer NBC and PiPrNBC-AEMA. The structure of polymer NBC is shown below.

[0108]

[0109] A photosensitive resin film was formed on a film substrate using a cyclopentanone solution containing polymer NBC and a cyclopentanone solution containing PiPrNBC-AEMA. These photosensitive resin films were then exposed to 365 nm light at varying exposure doses to form an amine generating layer.

[0110] For the photosensitive resin film using polymer NBC, 2000, 1000, 500, 250, 100, 50, and 10 mJ / cm ２ The photosensitive resin film using PiPrNBC-AEMA was exposed at an exposure dose of 2000, 1500, 1000, 750, 500, 400, 300, 200, 100, 50, 10, and 0 mJ / cm. ２ The amine generating layers were formed by exposure at an exposure dose of 1000 ppm. The deposition results when NiP plating was performed on the amine generating layers with different exposure doses are shown in FIG.

[0111] The amine generating layer using polymer NBC requires 1000 mJ / cm for NiP plating deposition. ２ The amine generating layer using PiPrNBC-AEMA requires an exposure of 200 mJ / cm ２ Deposition occurred with exposure to light exceeding this limit. This is thought to be because PiPrNBC-AEMA has better photosensitivity than polymer NBC, so the amount of exposure required for plating deposition as an amine generating layer is smaller. Therefore, an amine generating layer using PiPrNBC can be plated even with short exposure times, and high productivity can be expected.

[0112] Although NiP plating was used for the evaluation, it is clear that the same tendency would be observed when copper plating was used for the evaluation.

[0113] From the above, it was found that iPrNBC and PiPrNBC-AEMA not only have high photosensitivity in solution, but also exhibit high photoreactivity when used as a photosensitive resin film. Photosensitive resin films using iPrNBC and PiPrNBC-AEMA have high photosensitivity, enabling efficient generation of amines with a small amount of exposure, further promoting chemical reactions with the underlayer and catalytic reactions in plating.

[0114] A method for synthesizing PiPrNBC-AEMA will be described below.

[0115] <Synthesis of isopropyl derivative, 1-(3,4-dimethoxyphenyl)-2-methylpropanone> Under an argon atmosphere, iodine (6.22 g (0.0490 mol, 0.0374 eq.), Tokyo Chemical Industry Co., Ltd.), o-dimethoxybenzene (180.4 g (1.31 mol, 1.00 eq.), Fujifilm Wako Pure Chemical Industries, Ltd.), and isobutyric anhydride (414 g (2.62 mol, 2.00 eq.), Tokyo Chemical Industry Co., Ltd.) were mixed in this order. The mixture was heated and stirred at an oil bath temperature of 170°C for 6 hours, and then stirred 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 to the mixture, and the mixture was transferred to a separatory funnel. After separating the organic layer, the aqueous layer was further extracted with IPE (800 mL). The residue was washed successively with a 5% aqueous solution of sodium bicarbonate (1.6 L), saturated saline (1.6 L), and distilled water (1.6 L), and then dried over anhydrous magnesium sulfate. After removing the desiccant, the residue was concentrated under reduced pressure to obtain 285 g of a brown oil. This was purified using a silica gel column to obtain 222 g (yield 81.6%) of the isopropyl form (1-(3,4-Dimethoxyphenyl)-2-methylpropanone). The structure was assigned by NMR and GCMS.

[0116] δ=1.22 (6H) 3.55 (1H) 3.94 (3H) 3.95 (3H) 6.90 (1H) 7.55 (1H) 7.60 (1H)

[0117]

[0118] <Synthesis of nitro compound, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-one> The above isopropyl derivative (50.0 g (0.240 mol, 1.00 eq.)) and acetic acid (150 mL) were mixed. A solution of 69% nitric acid in acetic acid (100 mL) was added dropwise thereto. The mixture was then heated and stirred at 50°C for 2 hours, after which the disappearance of the raw materials was confirmed by thin layer chromatography (TLC). The reaction was then terminated. The reaction was quenched by adding ice water (800 g) to a reactor, and then transferred to a separatory funnel and washed with ethyl acetate (1 L) and water (200 mL). The aqueous layer was separated and further washed with water (1 L) for liquid separation. The mixture was then washed with a 5% aqueous sodium bicarbonate solution (1 L) and dried using a desiccant. After removing the drying agent, the mixture was concentrated under reduced pressure and purified with a silica gel column to obtain 38.7 g (yield 64%) of a nitro compound (1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-one). The structure was identified by NMR and GCMS.

[0119] δ=1.22 (6H) 2.91 (1H) 3.98 (3H) 3.99 (3H) 6.69 (1H) 7.66 (1H)

[0120]

[0121] <Synthesis of isopropyl alcohol: 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-ol> 13.8 g (54.5 mmol, 1.00 eq.) of the above 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. Ninety minutes after the start of the addition, the mixture was stirred at room temperature for 30 minutes, and then the reaction solution was cooled with ice water. A 5% aqueous solution of sodium bicarbonate (300 mL) was added, followed by stirring for 5 minutes. The reaction solution was transferred to a separatory funnel and extracted with ethyl acetate (600 mL). The organic layer was washed with saturated brine (300 mL) and then dried over anhydrous magnesium sulfate. After removing the desiccant, the mixture was concentrated under reduced pressure to obtain an oily product. The resulting crude product was purified using a silica gel column to obtain 9.38 g (yield 67%) of an isopropyl alcohol derivative (1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropan-1-ol) as a yellow oil. The structure was identified by NMR and GCMS.

[0122] 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)

[0123]

[0124] <Synthesis of Monomer iPrNBC-AEMA> Under an argon atmosphere, dry tetrahydrofuran (100 ml) was added to 5.00 g (19.6 mmol, 1.00 eq.) of the above isopropyl alcohol compound and dissolved. Dibutyltin dilaurate (2.00 eq.) was then added thereto, followed by dropwise addition of 3.65 g (23.5 mmol, 1.20 eq.) of 2-isocyanatoethyl methacrylate over 5 minutes. The bath temperature was then raised to 75°C over 1 hour and heated under reflux at the same temperature for 3 hours. The reaction endpoint was confirmed by NMR and TLC, and the mixture was allowed to cool and then concentrated under reduced pressure to obtain 8.69 g of a yellow oily substance, iPrNBC-AEMA. The resulting crude product was again dissolved in ethyl acetate (45 mL) and added dropwise to n-heptane (450 mL). The solid was collected by filtration and dried under reduced pressure to obtain 6.47 g (80.5%) of the target iPrNBC-AEMA.

[0125] 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)

[0126]

[0127] <Synthesis of PiPrNBC-AEMA> Under an argon atmosphere, 6.15 g (15.0 mmol, 1.00 eq.) of iPrNBC-AEMA was dissolved in 10 ml of ultra-dehydrated DMF that had been bubbled with Ar for 30 minutes. After adding 0.123 g (0.75 mmol, 0.05 eq.) of AIBN, the bath temperature was raised to 65°C over 30 minutes and the mixture was heated and stirred at the same temperature for 21 hours. The reaction end point was confirmed by NMR, and after cooling, the reaction solution was added dropwise to methanol (240 mL) and the precipitated solid was centrifuged. After removing the supernatant, methanol (240 mL) was added again and centrifuged. After removing the supernatant, the crude product was redissolved in chloroform (40 mL) and added dropwise to methanol (400 mL). After removing the supernatant, methanol (400 mL) was added and the mixture was centrifuged for solid-liquid separation. The resulting solid was dried under reduced pressure while still in the centrifuge tube to obtain 4.01 g of PiPrNBC-AEMA.

[0128]

[0129] Example 4 In this example, the adhesion of a copper plating layer was evaluated when underlayers formed under various conditions were used as underlayers for the photosensitive resin film 12A between the substrate 10 and the photosensitive resin film 12A, as shown in Figure 3. Underlayers were formed on alkali-free glass substrates using epoxy resin or silane coupling agents under various conditions, as described below. A cyclopentanone solution containing 0.3 wt% PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) was then applied to the underlayer using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm, followed by heating at 100°C for 20 minutes to form a photosensitive resin film.

[0130] Next, UV light with a wavelength of 365 nm was applied to the entire surface of the photosensitive resin film at 1000 mJ / cm. ２The photosensitive resin film was exposed to light to form an amine generating layer.

[0131] The substrate was then immersed in an electroless plating catalyst solution (Okuno Pharmaceutical Industries, Ltd.) at room temperature for 5 minutes to deposit a catalyst (Pd) on the amine generating layer. After rinsing the surface with water, the substrate was immersed in a catalyst activation solution (OPC-150 Crystal R, Okuno Pharmaceutical Industries, Ltd.) at room temperature for 5 minutes to activate the catalyst (Pd) deposited on the amine generating layer. The substrate was then immersed in an electroless plating solution (OPC Copper HFS, Okuno Pharmaceutical Industries, Ltd.) at 40°C for 3 minutes to deposit electroless copper on the catalyst, forming a copper plating layer.

[0132] [Adhesion Evaluation] The formed copper plating layer was cut into a grid pattern at intervals of 2 mm vertically and horizontally, and a tape peeling test was performed using tape. The adhesion between the glass substrate and the copper plating layer was evaluated by the tape peeling test. Cases where the entire surface peeled off were evaluated as having "low adhesion" and recorded as "B" in Table 4, and cases other than this were evaluated as having "high adhesion" and recorded as "A" in Table 4.

[0133] In this embodiment, the epoxy resin or silane coupling agent interposed between the substrate 10 and the photosensitive resin film 12A does not necessarily have to function as the gate insulating film 11 as shown in FIG.

[0134] <Condition A01> An epoxy resin film (SU8-3005, manufactured by MicroChem) was formed on alkali-free glass as a base film for a photosensitive resin film. The epoxy resin film was prepared by diluting SU8-3005 with cyclopentanone to a solids concentration of 15 wt % to prepare a coating solution. The coating solution was applied to the alkali-free glass using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm and heated at 150°C for 5 minutes to form an epoxy resin film over the entire surface of the alkali-free glass. The epoxy resin film was then irradiated with light of 365 nm wavelength at 1000 mJ / cm. ２ After exposure, the film was heated for 20 minutes at 150° C. The thickness of the epoxy resin film was 850 nm.

[0135] <Condition A02> Before forming a photosensitive resin film on the epoxy resin film as the base film, UV / O is applied to the surface of the epoxy resin film. ３An epoxy resin film was formed in the same manner as in Condition A01, except that the cleaning was carried out for 3 minutes. The thickness of the epoxy resin film was 850 nm.

[0136] <Condition A03> UV / O on alkali-free glass ３ After the cleaning was carried out for 5 minutes, an epoxy resin film was formed in the same manner as in Condition A02. Then, in the same manner as in Example A02, UV / O was applied to the surface of the epoxy resin film. ３ After washing for 3 minutes, a photosensitive resin film was formed on the substrate, with a thickness of 850 nm.

[0137] <Condition A04> After forming an epoxy resin film and a photosensitive resin film in the same manner as in Condition A03, a copper plating layer was formed. After forming the copper plating layer, heating was performed at 100°C for 2 minutes, and then at 150°C for 3 minutes.

[0138] <Condition A05> After forming an epoxy resin film and a photosensitive resin film in the same manner as in Example A03, a copper plating layer was formed. After the copper plating layer was formed, heating was performed at 100°C for 2 minutes, and then at 250°C for 3 minutes.

[0139] <Condition A06> An epoxy resin film (SU8-3005, manufactured by MicroChem) was formed on alkali-free glass as a base film for a photosensitive resin film. The epoxy resin film was prepared by diluting SU8-3005 with cyclopentanone to a solids concentration of 10 wt % to prepare a coating solution. Using this coating solution, an epoxy resin film was formed on the entire surface of the alkali-free glass in the same manner as in Condition A04, and then irradiated with light of 365 nm at 1000 mJ / cm. ２ The film was exposed to light and heated at 150° C. for 20 minutes. The thickness of the epoxy resin film was 400 nm. The other steps were the same as those under condition A04.

[0140] <Condition A07> Under condition A06, light with a wavelength of 365 nm was applied to the epoxy resin film at 1000 mJ / cm ２ Instead of exposing to light, 200 mJ / cm ２ The conditions were the same as A06 except that the exposure was performed under the following conditions.

[0141] <Condition A08> An epoxy resin film (SU8-3005, manufactured by MicroChem) was formed on alkali-free glass as a base film for the photosensitive resin film. The epoxy resin film was prepared by diluting SU8-3005 with cyclopentanone to a solids concentration of 1 wt % to prepare a coating solution. The photosensitive resin film was formed and copper plating was carried out in the same manner as in Condition A07, except that the epoxy resin film was formed over the entire surface of the alkali-free glass using this coating solution. The thickness of the epoxy resin film was 50 nm.

[0142] <Condition A09> In condition A09, the epoxy resin film was applied by dip coating instead of spin coating. The alkali-free glass was immersed at a speed of 10 mm / sec into a solution in which SU8-3005 was diluted with cyclopentanone to a solids concentration of 1 wt %. The glass was then heated at 100°C for 5 minutes to form an epoxy resin film. The substrate, on which the epoxy resin film had been formed entirely, was irradiated with light of 365 nm wavelength at 200 mJ / cm. ２ The epoxy resin film was exposed to light and had a thickness of 60 nm.

[0143] Under condition A09, the photosensitive resin film formed on the epoxy resin film was also applied by dip coating. A cyclopentanone solution containing 0.3 wt% of PiPrNBC-AEMA (polyisopropyl nitrobenzyl carbamate) was applied by dip coating (5 mm / sec) and heated at 100°C for 5 minutes to form a photosensitive resin film. Next, light with a wavelength of 365 nm was applied at 1000 mJ / cm to the substrate on which the photosensitive resin film had been formed over the entire surface. ２ The amine generating layer was formed by exposure to light. The subsequent steps up to the formation of the copper plating layer were the same as those under condition A04.

[0144] <Condition A10> Under this condition, an epoxy resin film was formed by dip coating at a slower immersion speed (5 mm / sec) than under condition A09. The other conditions were the same as under condition A09. The thickness of the epoxy resin film was 20 nm.

[0145] <Condition A11> Under these conditions, an epoxy resin film mixed with GPSC, an epoxy silane, was used as the base film. A coating solution was prepared by diluting 0.3 wt% of 3-glycidyloxypropyltrimethoxysilane (GPSC, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 wt% of SU8-3005 (manufactured by MicroChem) with cyclopentanone. The coating solution was applied to alkali-free glass by spin coating at 1000 rpm and heated at 100°C for 5 minutes to form an epoxy resin film mixed with GPSC. Thereafter, 200 mJ / cm of light with a wavelength of 365 nm was applied to the substrate on which the epoxy resin film had been formed over the entire surface. ２ The copper plating layer was formed in the same manner as in Example A08 except for the above. The thickness of the undercoat film was 100 nm.

[0146] <Condition A12> In condition A11, an epoxy resin film mixed with GPSC, an epoxy silane, was used as the base film, but in this condition A12, an epoxy resin film was laminated on GPSC as the base film. 3-glycidyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) was diluted with cyclopentanone to a ratio of 0.3 wt % to prepare a coating solution. The GPSC coating solution was applied to alkali-free glass by spin coating at 1000 rpm and heated at 150°C for 5 minutes. After that, light with a wavelength of 365 nm was applied at 200 mJ / cm. ２ After forming the GPSC layer, an epoxy resin film was formed in the same manner as in Example A08, and a copper plating layer was then formed. The thickness of the undercoat film was 100 nm.

[0147] <Condition B01> A silane coupling agent was applied to alkali-free glass as a base film for a photosensitive resin film. iPrNBC-APTMOS (isopropyl nitrobenzyl carbamate-type silane coupling agent) was diluted with cyclopentanone to a solids concentration of 0.3 wt% to prepare a coating solution. The coating solution containing iPrNBC-APTMOS was applied to the alkali-free glass using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm, and then heated at 150°C for 10 minutes to form a silane coupling layer. A copper plating layer was formed using the same method as in Condition A01, except for the other steps. The thickness of the base film was 2 nm. The structure of iPrNBC-APTMOS is shown below.

[0148]

[0149] <Condition B02> UV / O is applied to the surface of non-alkali glass ３ After washing for 5 minutes, a copper plating layer was formed in the same manner as in condition B01.

[0150] <Condition B03> This was the same as condition B02, except that after the copper plating layer was formed, heating was performed at 100° C. for 2 minutes, and then heating was performed at 150° C. for 3 minutes.

[0151] <Condition C01> As a comparative condition, a copper plating layer was formed in the same manner as in condition A01, except that no epoxy resin film was formed on the alkali-free glass.

[0152] <Condition C02> As a comparative condition, a copper plating layer was formed in the same manner as in Condition B03, except that only a GPSC layer was formed on alkali-free glass. The GPSC layer was formed to a thin film thickness of 10 nm or less, and the average film thickness after film formation was 5.7 nm. Then, a copper plating layer was formed.

[0153] [Evaluation] Table 4 shows a table of each condition and the results of the adhesion evaluation. Under conditions A01 to A12 and B01 to B03, the adhesion evaluation was high. In contrast, under condition C01, complete peeling of the copper plating layer was observed, indicating poor adhesion. These results demonstrate that the adhesion strength can be increased by providing an epoxy resin film or silane coupling layer as an undercoat between the glass substrate and the amine generating layer. This is particularly effective when using substrates that are difficult to plate or adhere to, such as glass substrates.

[0154]

[0155] Specifically, a material capable of forming a chemical bond with the amino group in the amine generating layer is used as the base film. Examples of chemical structures that mediate the connection between the glass surface and the amino group in the amine generating layer include epoxy, alkoxysilane, isocyanate, and acid anhydride. Epoxy and alkoxysilane are particularly desirable. These materials may be used to form the base layer as in conditions A01 to A10 and B01 to B03. The method for forming the base film is not particularly limited; spin coating or dip coating may be used as in conditions A01 to A10, but spray coating, roll coating, and other methods may also be used.

[0156] It is believed that an undercoat film containing epoxy groups crosslinks with the hydroxyl groups of the glass substrate, providing excellent adhesion to the substrate. Furthermore, the epoxy groups also crosslink with the amino groups of the amine generating layer, providing excellent adhesion to the amine generating layer. Therefore, using a material containing epoxy groups as the undercoat film can strengthen the adhesion between the substrate and the amine generating layer, preventing peeling of the copper plating layer.

[0157] The material contained in the undercoat film is preferably a polyfunctional epoxy group, and is preferably a photosensitive epoxy composition capable of accelerating the crosslinking reaction with light. Hydroxyl groups on the glass substrate surface and epoxy groups in the epoxy resin, and amino groups in the amine generating layer and epoxy groups in the epoxy resin can form chemical bonds.

[0158] Furthermore, the silane coupling agent iPrNBC-APTMOS changes into a bond containing an amino group and a silyl group upon exposure to light. The amino group of the silane coupling agent has a high affinity with the amino group in the amine generating layer, increasing the adhesion between the two. Furthermore, the silyl group forms a siloxane bond with the glass substrate, resulting in high adhesion to the glass substrate. Therefore, the silane coupling agent can also strengthen the adhesion between the substrate and the amine generating layer, preventing peeling of the copper plating layer.

[0159] Furthermore, under condition C02, in which a GPSC layer with an average thickness of 5.7 nm was used as the undercoat film, peeling of the copper plating layer was observed across the entire surface, indicating poor adhesion. In contrast, under condition A10, in which the epoxy resin film was 20 nm thick, no peeling of the copper plating layer was observed and adhesion was high, indicating that the thickness of the undercoat film having epoxy groups is preferably 20 nm or more.

Claims

1. A laminate comprising a substrate, an amine generating layer, a copper wiring layer, and a copper wiring protective layer in that order.

2. The laminate according to claim 1, further comprising a palladium-containing layer between the copper wiring layer and the amine generating layer.

3. The laminate according to claim 1 or 2, further comprising a gold plating layer on the copper wiring protective layer.

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

5. A step of applying a photosensitive surface treatment agent onto a substrate to form a photosensitive resin film, exposing the photosensitive resin film to light to form an amine generating layer having an amine generating region in the exposed area, The process involves forming a first catalyst layer on the amine generating layer, and then performing electroless copper plating to form a copper plating layer. A method for manufacturing a laminate, comprising the steps of forming a photoresist layer on the copper plating layer, pattern-exposing the photoresist layer to form exposed areas corresponding to the pattern of the copper wiring layer, and removing the unexposed areas of the photoresist layer.

6. A portion of the copper plating layer is removed to form a copper wiring layer, and a preliminary pattern comprising a photoresist layer is formed on the copper wiring layer, The steps include bringing the catalyst removal agent into contact with the preliminary pattern to remove the first catalyst layer present in the photoresist openings, A step of removing the photoresist layer on the copper wiring layer, The method for manufacturing a laminate according to claim 5, further comprising the steps of forming a second catalyst layer on the copper wiring layer, and then performing electroless plating to form a copper wiring protective layer.

7. The method for manufacturing a laminate according to claim 5, wherein the photosensitive resin film comprises a photosensitive polymer 1 represented by the following formula. 【Chemistry 1】

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

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