Metal pattern forming method, substrate including metal pattern, and electronic device including metal pattern

Abstract

Provided is a metal pattern forming method (embossing patterning) according to an embodiment. The metal pattern forming method comprises the steps of: preparing a substrate; forming a metal adhesion inhibiting layer on the substrate; forming a metal adhesion pattern on the metal adhesion inhibiting layer; and forming a metal pattern on the metal adhesion pattern by applying and / or depositing metal onto the substrate, wherein the metal adhesion inhibiting layer includes a water-soluble polymer and a cellulose material.

Description

Method for forming a metal pattern, a substrate including a metal pattern, and an electronic device including the metal pattern

[0001] The present invention relates to a method for forming a metal pattern.

[0002] Flexible wiring and / or flexible electrodes can be formed to form a flexible device.

[0003] Liquid metal can be used as a material for flexible wiring or flexible electrodes. Representative methods for patterning liquid metal include nozzle printing on a stencil mask, screen printing, spray coating, and mold injection, but these methods are unsuitable for high-resolution patterning processes. Therefore, a method for patterning liquid metal at high resolution is desirable or required.

[0004] It is to provide a method for forming metal patterns at high resolution.

[0005] A method for forming a metal pattern according to embodiments of the present disclosure is provided.

[0006] The above metal pattern forming method

[0007] Step of preparing the substrate;

[0008] A step of forming a metal adhesion inhibition layer on the above substrate;

[0009] A step of forming a metal adhesion pattern on the metal adhesion inhibiting layer; and

[0010] The step of forming a metal pattern on the metal adhesive pattern by applying and / or depositing a metal over the substrate;

[0011] The metal adhesion inhibition layer described above includes a water-soluble polymer and a cellulose material.

[0012] The above water-soluble polymer may include polyvinyl alcohol, polyacrylic acid, or a combination thereof.

[0013] The above cellulose material may include nanofibers, nanocrystals, microfibers, microcrystals, or combinations thereof, including cellulose, methylcellulose, ethyl cellulose, or combinations thereof.

[0014] In one embodiment, the step of removing the metal adhesion inhibitor layer exposed by the metal pattern may be further included.

[0015] The step of removing the metal adhesion inhibitor layer may include the step of washing the substrate with water.

[0016] In one embodiment, the step of forming the metal adhesion inhibiting layer may further include the step of treating the surface of the metal adhesion inhibiting layer with a hydrophobic material.

[0017] The above hydrophobic material may include fluorotetrahydrooctyltrimethylchlorosilane (FOTS), fluorodecyltrichlorosilane (FDTS), methacryloxypropyltrimethoxysilane (MPTMS), undecenyltrichlorosilane (UTS), vinyl-trichlorosilane (VTS), decyltrichlorosilane (DTS), octadecyltrichlorosilane (OTS), dimethyldichlorosilane (DDMS), dodecenyltrichlorosilane (DDTS), perfluorooctyldimethylchlorosilane, aminopropylmethoxysilane (APTMS), or a combination thereof.

[0018] The above substrate may include a flexible substrate.

[0019] The above metal may include a liquid metal (low melting point metal).

[0020] The above metal may include silver (Ag), gold (Au), aluminum (Al), copper (Cu), magnesium (Mg), or a combination thereof.

[0021] The above liquid metal may include a gallium-indium eutectic alloy (EGaIn), a gallium-indium-tin eutectic alloy (Galinstan), or a combination thereof.

[0022] The above metal adhesive pattern may include a flexible polymer.

[0023] The application of the metal may include roller application, stamp application, or a combination thereof.

[0024] The method may further include the step of forming a sealing layer over the metal pattern.

[0025] The weight ratio of the cellulose material and the water-soluble polymer may be in the range of 0.1:1 to 4:1.

[0026] A method for forming a metal pattern according to another embodiment is provided.

[0027] The above metal pattern forming method

[0028] Step of preparing the substrate;

[0029] A step of forming a metal adhesion inhibition pattern on the substrate;

[0030] A step of applying and / or depositing a metal over the substrate to form a metal pattern between the metal adhesion inhibition patterns; and

[0031] The step of selectively removing the metal adhesion inhibition pattern; comprising

[0032] The above metal adhesion inhibition pattern includes a water-soluble polymer and a cellulose material.

[0033] Detailed information regarding the substrate, the water-soluble polymer, the cellulose material, the metal, and the coating of the metal is provided in this specification.

[0034] The step of selectively removing the metal adhesion inhibition pattern may include the step of washing the substrate with water.

[0035] In one embodiment, the step of forming the metal adhesion inhibition pattern may further include the step of treating the surface of the metal adhesion inhibition petan with a hydrophobic material.

[0036] For detailed information regarding the above hydrophobic material, refer to the foregoing.

[0037] In one embodiment, the step of forming a sealing layer over the metal pattern may be further included.

[0038] The weight ratio of the cellulose material to the water-soluble polymer may be in the range of 0.1:1 to 4:1.

[0039] A substrate including a metal pattern according to one embodiment is provided.

[0040] The substrate including the above metal pattern is

[0041] Substrate;

[0042] A metal adhesion inhibitor layer on the above substrate; and

[0043] Metal pattern structure on the metal adhesion inhibition layer; comprising

[0044] The metal adhesion inhibitor layer comprises a composition of a cellulose material and a water-soluble polymer, and

[0045] The metal pattern structure includes a metal adhesive pattern; and a metal pattern on the metal adhesive pattern.

[0046] The above metal pattern may include liquid metal.

[0047] The above metal adhesive pattern may include a flexible polymer.

[0048] An electronic device according to one embodiment may include a substrate including the metal pattern.

[0049] Metal patterns can be formed at high resolution by using a metal adhesion inhibition pattern containing a water-soluble polymer and a cellulose material.

[0050] FIG. 1 is a flowchart schematically illustrating the sequence of a metal pattern formation method according to one embodiment.

[0051] FIGS. 2a to 2e are schematic cross-sectional views illustrating, in sequence, a method for forming a metal pattern according to one embodiment.

[0052] FIG. 3 is a flowchart schematically illustrating the sequence of a metal pattern formation method according to one embodiment.

[0053] FIGS. 4a to 4d are schematic cross-sectional views illustrating, in sequence, a method for forming a metal pattern according to one embodiment.

[0054] Figure 5a shows optical microscope images of the upper surfaces of the PVA substrate of Comparative Test Example 1 and the PVACF substrate of Test Example 1.

[0055] Figure 5b is a graph showing the roughness measured by scanning the upper surface of the PVA substrate and PVACF substrate of Figure 5a in the direction of the arrow using a scratch test device.

[0056] Figure 6 shows photographs of the PVA substrate of Comparative Test Example 2 and the PVACF substrate of Test Example 2.

[0057] FIG. 7 shows photographs of EGaIn patterns formed by rolling a roller coated with EGaIn on the substrates of Comparative Test Example 3 and Test Examples 3 to 9, respectively.

[0058] Figure 8 shows photographs of EGaIn patterns formed by roller application on the substrates of Test Examples 10 and 11, respectively.

[0059] Figure 9 shows photographs of EGaIn patterns formed by roller coating on the substrates of Test Example 12 and Comparative Test Example 4, respectively.

[0060] FIGS. 10a to 10c are optical microscope images of the upper surface of the PDMS-PVACF substrate during the EGaIn pattern formation process of Test Example 13.

[0061] Figure 11 is a photograph of the upper surface of a substrate in which EGaIn is embossed with an LM pattern in Test Example 14.

[0062] FIG. 12 shows top-surface optical microscope images of embossed patterned EGaIn lines in Test Examples 15 to 17.

[0063] FIGS. 13a to 13c are optical microscope images of the upper surface of the PDMS-PVACF substrate during the EGaIn pattern formation process of Test Example 18.

[0064] Figure 14 is a photograph of the upper surface of a substrate in which EGaIn is engraved with an LM pattern in Test Example 19.

[0065] FIG. 15 shows top-surface optical microscope images of embossed patterned EGaIn lines in Test Examples 20 to 23.

[0066] Figure 16 is a graph measuring the change in resistance over the stretching cycle of the PDMS / EGaIn strap of Test Example 24.

[0067] Figure 17 is a graph measuring the change in resistance over the stretching cycle of the PDMS / EGaIn strap of Test Example 25.

[0068] Figure 18 shows optical microscope images of the upper surface of the glass-PVACF substrate during the EGaIn pattern formation process of Test Example 26.

[0069] The present invention is capable of various modifications and may have various embodiments; specific embodiments are illustrated in the drawings and described in more detail in the detailed description. The effects and features of the present invention, and the methods for achieving them, will become clear by referring to the embodiments described below in detail together with the drawings. However, the present invention is not limited to the embodiments disclosed below but can be implemented in various forms.

[0070] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. When describing with reference to the drawings, identical or corresponding components are given the same reference numerals, and redundant descriptions thereof will be omitted.

[0071] In the following embodiments, terms such as first, second, etc. are used not in a limiting sense, but for the purpose of distinguishing one component from another component.

[0072] In the following examples, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0073] In the following embodiments, terms such as "include" or "have" mean that the features or components described in the specification are present, and do not preclude the possibility that one or more other features or components may be added.

[0074] In the following embodiments, when a part such as a film, region, or component is described as being on or above another part, it includes not only cases where it is directly on top of another part, but also cases where another film, region, or component is interposed in between.

[0075] In the drawings, the size of components may be exaggerated or reduced for convenience of explanation. For example, the size and thickness of each component shown in the drawings are depicted arbitrarily for convenience of explanation, so the present invention is not necessarily limited to what is illustrated.

[0076] Where an embodiment can be implemented differently, a specific process sequence may be performed differently from the order described. For example, two processes described consecutively may be performed substantially simultaneously or proceed in the reverse order of the description.

[0077] In this specification, "A and / or B" indicates the case where it is A, B, or both A and B. And, "at least one of A or B" indicates the case where it is A, B, or both A and B.

[0078] In the following embodiments, when a membrane, region, component, etc. is described as being connected, it includes cases where the membrane, region, component, etc. are directly connected, or / or cases where other membranes, regions, components, etc. are interposed between the membranes, regions, and components to be indirectly connected. For example, when a membrane, region, component, etc. is described as being electrically connected in this specification, it indicates cases where the membrane, region, component, etc. are directly electrically connected, and / or cases where other membranes, regions, components, etc. are interposed between them to be indirectly electrically connected.

[0079] The x-axis, y-axis, and z-axis are not limited to the three axes of an orthogonal coordinate system but can be interpreted in a broader sense that includes them. For example, the x-axis, y-axis, and z-axis may be orthogonal to each other, but they may also refer to different directions that are not orthogonal to each other.

[0080] (Relief patterning)

[0081] FIG. 1 is a flowchart schematically illustrating the sequence of a metal pattern formation method according to one embodiment. FIGS. 2a to 2e are schematic cross-sectional views illustrating the metal pattern formation method according to one embodiment in sequence. A metal pattern formation method according to one embodiment will be described with reference to FIGS. 1 and FIGS. 2a to 2e.

[0082] Referring to FIGS. 1 and FIGS. 2a, a method for forming a metal pattern according to one embodiment first prepares a substrate (S110).

[0083] The substrate (110) may comprise a polymer resin such as polyethersulfone, polyarylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyimide, polycarbonate, cellulose triacetate, and / or cellulose acetate propionate. In one embodiment, the substrate (110) may be a single layer comprising the aforementioned polymer resin. In another embodiment, the substrate (110) may be a multilayer structure comprising a base layer comprising the aforementioned polymer resin and a barrier layer comprising an inorganic insulator. The substrate (110) comprising the polymer resin may have flexible, rollable, and / or bendable properties. In one embodiment, the substrate (110) may further comprise a layer comprising any suitable component of the device.

[0084] Referring to FIGS. 1 and FIGS. 2b, a metal adhesion inhibition layer (120) is formed on the substrate (110) (S120).

[0085] The metal adhesion inhibiting layer (120) may include a water-soluble polymer and a cellulose material. The metal adhesion inhibiting layer (120) may be formed by methods such as printing, coating, and / or dispensing a composition containing a water-soluble polymer and a cellulose material. In one embodiment, the composition containing a water-soluble polymer and a cellulose material may be prepared by mixing a dispersion of a water-soluble polymer and a dispersion of a cellulose material.

[0086] In one embodiment, the water-soluble polymer has a surface energy of 40 mJ / m² 2 It may be a water-soluble polymer with less than 40 mJ / m². 2 By having a low surface energy of less than [amount], the difference in interfacial energy with the metal increases, and the wettability of the metal to the metal adhesion inhibition layer (120) can be reduced. In one embodiment, since the water-soluble polymer dissolves in water, the metal adhesion inhibition layer (120) can be easily removed by washing with water after forming the metal pattern.

[0087] The above water-soluble polymer may include, for example, polyvinyl alcohol or polyacrylic acid.

[0088] The cellulosic material may include, for example, cellulose, methylcellulose, ethylcellulose, or a combination thereof. In one embodiment, the cellulosic material may have the form of nanofibers, nanocrystals, microfibers, microcrystals, or a combination thereof. Since the size of the cellulosic material may affect the resolution when forming a metal pattern, the form of nanofibers and / or nanocrystals may be suitable when forming a high-resolution pattern.

[0089] The above cellulose material can provide nanometer or size roughness on the surface of the metal adhesion inhibition layer (120). By having such roughness on the surface of the metal adhesion inhibition layer (120), the wettability of the metal to the metal adhesion inhibition layer (120) can be further reduced.

[0090] In one embodiment, the weight ratio of the cellulose material to the water-soluble polymer may be in the range of about 0.1:1 to 4:1, 1:1 to 4:1, or 1.5:1 to 4:1. When the weight ratio of the cellulose material to the water-soluble polymer is in the above range, the wettability of the metal adhesion inhibition layer (120) to the metal is lowered, so that a metal layer is not formed on the metal adhesion inhibition layer (120). The viscosity of the composition can be controlled by adjusting the weight ratio of the cellulose material to the water-soluble polymer, and the weight ratio can be adjusted to satisfy the viscosity of the composition required according to the application method. In one embodiment, the viscosity of the composition may be controlled using a viscosity modifier, etc. In one embodiment, the weight ratio of the cellulose material to the water-soluble polymer may be appropriately adjusted according to the application method of the metal material or metal of the metal pattern to be formed.

[0091] In one embodiment, the step of forming the metal adhesion inhibitor layer (120) may further include the step of treating the surface of the metal adhesion inhibitor layer (120) with a hydrophobic material. The hydrophobic material may include, for example, perfluorooctyltrichlorosilane (FOTS), perfluorodecyltrichlorosilane (FDTS), methacryloxypropyltrimethoxysilane (MPTMS), undecenyltrichlorosilane (UTS), vinyltrichlorosilane (VTS), decyltrichlorosilane (DTS), octadecyltrichlorosilane (OTS), dimethyldichlorosilane (DDMS), dodecyltrichlorosilane (DDTS), perfluorooctyldimethylchlorosilane, aminopropylmethoxysilane (APTMS), or a combination thereof. By treating the surface of the metal adhesion inhibition layer (120) with a hydrophobic material, the surface energy of the metal adhesion inhibition layer (120) is lowered, thereby further reducing the wettability of the metal to the metal adhesion inhibition layer (120).

[0092] Referring to FIGS. 1 and 2c, a metal adhesion pattern (130) is formed on a metal adhesion inhibition layer (120) (S130). The metal adhesion pattern (130) may include a flexible polymer. The metal adhesion pattern (130) may be formed by patterning after thin film formation or by inkjet printing, etc. The metal adhesion pattern (130) may be formed uniformly (e.g., substantially uniformly) on the metal adhesion inhibition layer (120). Additionally, a metal pattern may be formed uniformly (e.g., substantially uniformly) on the metal adhesion pattern (130). Polymers that can be used for the metal adhesion pattern (130) may include, for example, polydimethylsiloxane (PDMS), polyurethane (PU), acrylic elastomer, etc. The metal adhesion pattern (130) may be formed following the shape of the metal pattern to be formed.

[0093] Referring to FIGS. 1 and 2d, a metal is applied and / or deposited (S140) over a substrate (110) on which a metal bonding pattern (130) is formed. In one embodiment, the metal may include a liquid metal (e.g., a low-melting point metal). As specified herein, a liquid metal refers to a metal that is in a liquid state at room temperature because its melting point is lower than room temperature (e.g., 25°C). The liquid metal may include, for example, a gallium-indium eutectic alloy (EGaIn) and / or a gallium-indium-tin eutectic alloy (Galinstan), but is not limited thereto. The liquid metal may be used for metal wiring and / or electrodes of a flexible device to contribute to the flexibility of the device. The liquid metal may be applied to the substrate by, for example, roller application, stamp application, spray and / or dipping processes. The liquid metal is formed on the metal bonding pattern (130) but not on the metal suppression layer (120). Although the present specification is not limited to a specific mechanism or theory, this is believed to be because the wettability of the metal suppression layer (120) to the liquid metal is poor due to the difference in surface energy between the metal suppression layer (120) and the liquid metal and the surface roughness of the metal suppression layer (120). In another embodiment, the metal may include silver (Ag). The metal suppression pattern (120) has low wettability to silver (Ag) as well, so that a metal pattern (140) made of silver (Ag) can be formed only on the metal bonding pattern (130). Silver (Ag) may be applied, for example, to a substrate (110) on which the metal bonding pattern (130) is formed by deposition.

[0094] Referring to FIGS. 1 and 2e, in one embodiment, the portion of the metal adhesion inhibition layer (120) exposed by the metal pattern (140) is removed (S150). Since the metal adhesion inhibition layer (120) contains a water-soluble polymer, the exposed metal adhesion inhibition layer (120) can be removed by washing the substrate (110) with water. In another embodiment, the metal adhesion inhibition layer (120) may not be removed. Since the metal adhesion inhibition layer (120) is an insulating layer, it may not affect the characteristics of the device even if it is not removed.

[0095] In one embodiment, although not illustrated, when a metal pattern (140) is formed with liquid metal, a sealing layer may be formed over the metal pattern (140) to prevent flow of the metal pattern (140).

[0096] (Intaglio patterning)

[0097] FIG. 3 is a flowchart schematically illustrating the sequence of a metal pattern formation method according to one embodiment. FIGS. 4a to 4d are schematic cross-sectional views illustrating the metal pattern formation method according to one embodiment in sequence. A metal pattern formation method according to one embodiment will be described with reference to FIGS. 3 and FIGS. 4a to 4d.

[0098] Referring to FIG. 3 and FIG. 4a, a metal pattern forming method according to one embodiment first prepares a substrate (S210). For a description of the substrate (110), refer to the above.

[0099] Referring to FIGS. 3 and FIGS. 4b, a metal adhesion inhibition pattern (220) is formed on the substrate (110) (S220). The metal adhesion inhibition pattern (220) may include a water-soluble polymer and a cellulose material. The weight ratio of the water-soluble polymer, the cellulose material, and the water-soluble polymer to the cellulose material is as described above.

[0100] The metal adhesion inhibition pattern (220) can be formed by patterning or inkjet printing, etc., after forming the metal adhesion inhibition layer. The metal adhesion inhibition pattern (220) can be formed to expose the substrate in the portion where the metal pattern is to be formed. In one embodiment, the step of forming the metal adhesion inhibition pattern (220) may further include the step of treating the surface of the metal adhesion inhibition layer or the metal adhesion inhibition pattern (220) with a hydrophobic material. Refer to the above description for the hydrophobic material.

[0101] Referring to FIGS. 3 and 4c, a metal is applied and / or deposited over a substrate (110) on which a metal adhesion inhibition pattern (220) is formed to form a metal pattern (240) between the metal adhesion inhibition patterns (220) (S230). Refer to the above for the metal, the application and deposition of the metal for forming the metal pattern (240).

[0102] When the metal is applied over a substrate (110) on which a metal adhesion inhibition pattern (220) is formed, the wettability of the metal with respect to the metal adhesion inhibition pattern (220) is low, so a metal layer is not formed on the metal adhesion inhibition pattern (220), and the metal is filled between the metal adhesion inhibition patterns (220) to form a metal pattern (240).

[0103] Referring to FIGS. 3 and FIGS. 4d, the metal adhesion inhibition pattern (220) is selectively removed (S240). Since the metal adhesion inhibition pattern (220) contains a water-soluble polymer, the exposed metal adhesion inhibition pattern (220) can be removed by washing the substrate (110) with water.

[0104] In one embodiment, when a metal pattern (240) is formed with liquid metal, a sealing layer may be formed over the metal pattern (240) to prevent flow of the metal pattern (240).

[0105] The method for forming a metal pattern according to the embodiments described above may be applied to the formation of flexible wiring and / or flexible electrodes of a flexible device, for example, a flexible light-emitting device or a flexible display device. For example, an electronic device may include a substrate comprising a metal pattern (for example, the metal pattern may be flexible wiring and / or flexible electrodes of the electronic device). In one embodiment, the method for forming a metal pattern according to the embodiments described above may be applied to the formation of flexible wiring for a flexible device, for example, a wearable electronic device, and a thermal interface for thermal management within the device.

[0106] Test example

[0107] Comparative Test Example 1

[0108] A PVA substrate was formed by applying a polyvinyl alcohol (PVA) layer with a thickness of about 10 μm on a PDMA substrate.

[0109] Test Example 1

[0110] A PVACF substrate was formed by applying a polyvinyl alcohol (PVA) layer containing cellulose nanofibers to a thickness of about 10 µm on a PDMA substrate. The diameter of the cellulose nanofibers is in the range of about 3 to 10 nm, and the length of the cellulose nanofibers is in the range of about 0.6 to 3 µm. The weight ratio of cellulose nanofibers to polyvinyl alcohol (PVA) in the polyvinyl alcohol (PVA) layer containing cellulose nanofibers is 1:1.

[0111] Figure 5a shows 100x optical microscope images of the upper surfaces of the PVA substrate of Comparative Test Example 1 and the PVACF substrate of Test Example 1, and Figure 5b is a graph showing the roughness measured by scanning the upper surfaces of the PVA substrate and the PVACF substrate of Figure 5a in the direction of the arrow using a scratch test device.

[0112] Referring to Fig. 5a, the upper surface of the PVA substrate is smooth, whereas the upper surface of the PVACF substrate shows a pattern of mixed material, and referring to Fig. 5b, the roughness graph of the PVA substrate is flat, whereas the roughness graph of the PVACF substrate shows irregular irregularities.

[0113] Comparative Test Example 2

[0114] EGaIn was applied by rolling a roller coated with a gallium-indium eutectic alloy (hereinafter EGaIn) onto the PVA substrate of Comparative Test Example 1.

[0115] Test Example 2

[0116] EGaIn was roller-coated onto the PVACF substrate of Test Example 1 in the same manner as in Comparative Test Example 2.

[0117] Figure 6 shows optical photographs of the PVA substrate of Comparative Test Example 2 and the PVACF substrate of Test Example 2. Referring to Figure 6, EGaIn is deposited on the transparent PVA substrate of Comparative Test Example 2, whereas no EGaIn is deposited on the opaque PVACF substrate of Test Example 2. From this, it can be confirmed that an EGaIn layer is not formed on the PVACF substrate.

[0118] Comparative Test Example 3

[0119] A PDMA-PVA substrate was formed by applying a polyvinyl alcohol layer (PVA layer) with a thickness of 10 μm to only half of the area on the PDMA substrate.

[0120] Test Examples 3 to 9

[0121] A PDMA-PVACF substrate was formed in substantially the same manner as Comparative Test Example 3, except that a polyvinyl alcohol layer (PVACF layer) containing cellulose nanofibers was formed instead of a PVA layer, and the weight ratio of cellulose nanofibers (CF) to polyvinyl alcohol (PVA) had the value shown in Table 1. A PVACF layer having the CF to PVA weight ratio of Table 1 was formed using a mixture of 15 wt% PVA solution and 20 wt% cellulose nanofiber dispersion in an appropriate ratio.

[0122] CF to PVA Weight Ratio Comparison Test Example 30:1 Test Example 30.1:1 Test Example 40.67:1 Test Example 51:1 Test Example 61.33:1 Test Example 72:1 Test Example 83:1 Test Example 94:1

[0123] FIG. 7 shows photographs of EGaIn patterns formed by rolling a roller coated with EGaIn on the substrates of Comparative Test Example 3 and Test Examples 3 to 9, respectively.

[0124] Referring to FIG. 7, Comparative Test Example 3 failed to pattern because EGaIn remained not only in the PDMA region but also on the PVA layer. In Test Examples 3 to 9, where the weight ratio of CF to PVA in the PVACF layer is in the range of 0.1:1 to 4:1, EGaIn is formed only in the PDMA region and no EGaIn remains on the PVACF layer, so it appears that all patterns were formed well.

[0125] Test Example 10

[0126] A PDMA-PVACF substrate was formed in substantially the same manner as in Test Example 3, except that ethylcellulose nanofibers were used instead of cellulose nanofibers.

[0127] Test Example 11

[0128] A PDMA-PVACF substrate was formed in substantially the same manner as in Test Example 3, except that methylcellulose nanofibers were used instead of cellulose nanofibers.

[0129] Figure 8 shows photographs of EGaIn patterns formed by rolling a roller coated with EGaIn on the substrates of Test Examples 10 and 11, respectively.

[0130] Referring to FIG. 8, it is shown that EGaIn patterns are formed well on the substrates of Test Examples 10 and 11, in which ethylcellulose and methylcellulose were used instead of cellulose.

[0131] Test Example 12

[0132] A PDMA-PACF substrate was formed in substantially the same manner as in Test Example 3, except that polyacrylic acid (PA) was used instead of polyvinyl alcohol as the polymer.

[0133] Comparative Test Example 4

[0134] A PDMA-PVPCF substrate was formed in substantially the same manner as in Test Example 3, except that polyvinylpyrrolidone (PVP) was used instead of polyvinyl alcohol as the polymer.

[0135] Figure 9 shows photographs of EGaIn patterns formed by rolling a roller coated with EGaIn on the substrates of Test Example 12 and Comparative Test Example 4, respectively.

[0136] Referring to FIG. 9, in Test Example 12 using polyacrylic acid (PA), EGaIn is formed only in the PDMA region, and no EGaIn remains on the PACF layer, indicating that the pattern was formed well. On the other hand, in Comparative Test Example 12 using polypyrrolidone (PVP), EGaIn remains significantly not only in the PDMA region but also on the PVPCF layer, indicating that EGaIn patterning failed.

[0137] The surface energies of polyvinyl alcohol, polyacrylic acid, and polypyrrolidone are shown in Table 2.

[0138] Surface energy (mJ / m²) 2 Polyvinyl alcohol 37 Polyacrylic acid 38 Polypyrrolidone 43

[0139] Referring to Table 2, among the polymers in Table 2, polypyrrolidone has the highest surface energy, while polyvinyl alcohol and polyacrylic acid have a surface energy of 40 mJ / m². 2 Although smaller, the surface energy of polypyrrolidone is 40 mJ / m² 2 It is larger. The higher surface energy of polypyrrolidone is believed to improve wettability with EGaIn.

[0140] Test Example 13 (Relief Patterning)

[0141] A polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = (1:1)) was applied to the entire surface of a 4 cm × 4 cm glass substrate to a thickness of 10 µm. A PDMS layer was applied to only a portion of the PVACF layer to a thickness of 50 µm to form a PDMS-PVACF substrate. An optical microscope image of the upper surface of the PDMS-PVACF substrate is shown in FIG. 10a. In FIG. 10a, it can be seen that the smooth surface of the PDMS layer and the mottled surface of the PVACF layer are distinguishable.

[0142] An EGaIn pattern was selectively formed only on the PDMS layer by rolling a roller coated with EGaIn over the above PDMS-PVACF substrate. An optical microscope image of the upper surface of the PDMS-PVACF substrate with the formed EGaIn pattern is shown in FIG. 10b. In FIG. 10b, it can be seen that EGaIn is formed only on the PDMS layer, and not on the PVACF layer.

[0143] The PDMS-PVACF substrate on which EGaIn was formed was washed with water to remove the PVACF layer on which EGaIn was not formed. An optical microscope image of the upper surface of the PDMS-PVACF substrate from which the PVACF layer was removed is shown in FIG. 10c.

[0144] Test Example 14 (Embossing LM Patterning)

[0145] A polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = (1:1)) was applied to the entire surface to a thickness of 10 μm on a 4 cm × 4 cm glass substrate, and the PVACF layer was surface-treated by vacuum vaporization using FOTS. PDMS was printed in an LM shape with a thickness of 50 μm on the surface-treated PVACF layer. EGaIn was roller-coated to a thickness of 50 μm on the substrate with PDMS printed in an LM shape.

[0146] Figure 11 is a photograph of the upper surface of a substrate in which EGaIn is patterned in an LM shape following the shape of PDMS. In Figure 11, it can be seen that EGaIn is applied only on the PDMS and not on the PVACF layer. From this, it can be seen that EGaIn can be formed on the substrate in various suitable patterns.

[0147] Test Example 15 (Embossing line patterning)

[0148] A polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = (1:1)) was applied to the entire surface of a 4 cm × 4 cm glass substrate to a thickness of 10 µm, and the PVACF layer was surface-treated with FOTS. PDMS was printed in a straight line shape with a line width (d) of 500 µm and a thickness of 20 µm on the surface-treated PVACF layer. EGaIn was roller-coated to a thickness of 50 µm on the substrate printed with PDMS.

[0149] Test Example 16 (Embossing line patterning)

[0150] EGaIn was patterned in substantially the same way as in Test Example 15, except that the line width (d) of PDMS on the surface-treated PVACF layer was changed to 150 μm.

[0151] Test Example 17 (Embossing line patterning)

[0152] EGaIn was patterned in substantially the same way as in Test Example 15, except that the line width (d) of PDMS on the surface-treated PVACF layer was changed to 100 μm.

[0153] FIG. 12 shows top-side optical microscope images of EGaIn line patterns formed in Test Examples 15 to 17. Referring to FIG. 12, it can be seen that lines with line widths of 500 μm, 150 μm, and 100 μm are neatly formed.

[0154] Test Example 18 (Intaglio Patterning)

[0155] A PDMS-PVACF substrate was formed by applying a polyvinyl alcohol (PVACF) layer (CF:PVA weight ratio = (1.33:1)) containing cellulose in only a portion of the area to a thickness of 10 μm on a 4 cm × 4 cm PDMS substrate. An optical microscope image of the upper surface of the PDMS-PVACF substrate is shown in FIG. 13a. In FIG. 13a, it can be seen that the smooth surface of the PDMS layer and the mottled surface of the PVACF layer are distinguishable.

[0156] An EGaIn pattern was selectively formed only on the PDMS layer by rolling a roller coated with EGaIn over the above PDMS-PVACF substrate. An optical microscope image of the upper surface of the PDMS-PVACF substrate with the formed EGaIn pattern is shown in FIG. 13b. In FIG. 13b, it can be seen that EGaIn is formed only on the PDMS layer, and not on the PVACF layer.

[0157] The PDMS-PVACF substrate on which EGaIn was formed was washed with water to remove the PVACF layer on which EGaIn was not formed. An optical microscope image of the upper surface of the PDMS-PVACF substrate from which the PVACF layer was removed is shown in FIG. 13c.

[0158] Test Example 19 (Intaglio LM Patterning)

[0159] A polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = (1:1)) was printed in an intaglio LM shape with a thickness of 10 µm on a 4 cm × 4 cm PDMS substrate. That is, PVACF was printed so that the PVACF layer was formed in the area excluding the LM shape. Subsequently, the PVACF layer was surface-treated with FOTS. EGaIn was roller-coated to a thickness of 50 µm onto the substrate with the intaglio LM-shaped PVACF layer printed thereon. After EGaIn coating, the substrate was washed with water to remove the PVACF layer, thereby forming an LM pattern of EGaIn.

[0160] Figure 14 is a photograph of the upper surface of a substrate patterned with an LM shape following the shape of a PVACF with EGaIn printed in intaglio. In Figure 14, the EGaIn pattern formed along the intaglio pattern can be seen. From this, it can be seen that EGaIn can be formed on the substrate with various suitable patterns.

[0161] Test Example 20 (Intaglio line patterning)

[0162] A 10 µm thick polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = (1.33:1)) was printed in a straight line shape on a 4 cm × 4 cm glass substrate with a line space of 450 Å between adjacent straight lines. Subsequently, the PVACF layer was surface-treated with FOTS. EGaIn was roller-coated to a thickness of 50 µm onto the substrate having the surface-treated PVACF layer. After EGaIn coating, the substrate was washed with water to remove the PVACF layer, thereby forming an EGaIn line pattern.

[0163] Test Example 21 (Intaglio line patterning)

[0164] EGaIn was patterned in substantially the same way as Test Example 20, except that the line spacing between adjacent lines of the PVACF layer was changed to 200㎛.

[0165] Test Example 22 (Intaglio line patterning)

[0166] EGaIn was patterned in substantially the same way as Test Example 20, except that the line spacing between adjacent lines of the PVACF layer was changed to 150㎛.

[0167] Test Example 23 (Intaglio line patterning)

[0168] EGaIn was patterned in substantially the same way as Test Example 20, except that the line spacing between adjacent lines of the PVACF layer was changed to 100㎛.

[0169] FIG. 15 shows top-side optical microscope images of EGaIn line patterns formed in Test Examples 20 to 23. Referring to FIG. 15, it can be seen that EGaIn lines with line widths of 450 μm, 200 μm, 150 μm, and 100 μm are neatly formed.

[0170] Test Example 24 (Resistance during stretching)

[0171] A PDMS / EGaIn strap was fabricated by roller-coating EGaIn to a thickness of 50㎛ on the front surface of a PMDS strap with a width of 5mm and a length of 20mm.

[0172] Test Example 25 (Resistance during stretching)

[0173] A PDMS / EGaIn strap was fabricated by patterning EGaIn with a width of 300㎛ and a thickness of 50㎛ onto a PMDS strap with a width of 5mm and a length of 20mm.

[0174] For the PDMS / EGaIn strap of Test Example 24, changes in resistance (e.g., electrical resistance) were measured while performing 50% stretching (stretching up to 30 mm) and 100% stretching (stretching up to 40 mm) in the longitudinal direction for 1,000 cycles, and the results were shown in the graph of FIG. 16. For the PDMS / EGaIn strap of Test Example 25, changes in resistance (e.g., electrical resistance) were measured while performing 50% stretching and 100% stretching in the longitudinal direction for 1,000 cycles, and the results were shown in the graph of FIG. 17.

[0175] Referring to FIG. 16, the PDMS / EGaIn strap of Test Example 24 exhibited a constant resistance value (e.g., electrical resistance value) in the range of about 0.8Ω to about 1Ω for 1000 cycles when stretched by 50%, and a constant resistance value (e.g., electrical resistance value) in the range of about 1.2Ω to about 1.6Ω for 1000 cycles when stretched by 100%.

[0176] Referring to FIG. 17, the PDMS / EGaIn strap of Test Example 25 exhibited a constant resistance value (e.g., electrical resistance value) in the range of about 4Ω to about 5Ω for 1000 cycles when stretched by 50%, and a constant resistance value (e.g., electrical resistance value) in the range of about 5Ω to about 11Ω for 1000 cycles when stretched by 100%.

[0177] From the graphs in FIGS. 16 and FIGS. 17, it can be seen that the EGaIn pattern fabricated by the embodiments of the present invention can be stably used as an electrode.

[0178] Test Example 26 (Ag deposition patterning)

[0179] A glass-PVACF substrate was formed by applying a polyvinyl alcohol (PVACF) layer containing cellulose (CF:PVA weight ratio = 1.33:1) to a thickness of 10 μm to a portion of a 2 cm × 2.4 cm glass substrate. An optical microscope image of the upper surface of the glass-PVACF substrate is shown in FIG. 18 (left).

[0180] Ag was deposited on the glass-PVACF substrate to selectively form an Ag layer only on the glass. An optical microscope image of the upper surface of the glass-PVACF substrate with the formed Ag layer is shown in FIG. 18 (right). In FIG. 18, it can be seen that Ag is deposited only on the glass and not on the PVACF layer. From this, it can be seen that the PVACF layer according to the embodiments of the present invention can be used to selectively form an Ag layer in a specific region.

[0181] Comparative Test Example 5 (Ag deposition patterning)

[0182] Ag was patterned in substantially the same way as in Test Example 26, except that the weight ratio of CF:PVA was changed from 1.33:1 to 0.5:1 when forming the PVACF layer, but Ag patterning failed.

[0183] Comparative Test Example 6 (Ag deposition patterning)

[0184] Ag was patterned in substantially the same way as in Test Example 26, except that the weight ratio of CF:PVA was changed from 1.33:1 to 0:1 when forming the PVACF layer, but Ag patterning failed.

Claims

1. Step of preparing the substrate; A step of forming a metal adhesion inhibition layer on the above substrate; A step of forming a metal adhesion pattern on the metal adhesion inhibition layer; A step of forming a metal pattern on the metal adhesive pattern by applying and / or depositing a metal over the substrate; A method for forming a metal pattern, wherein the metal adhesion inhibition layer comprises a water-soluble polymer and a cellulose material.

2. Step of preparing the substrate; A step of forming a metal adhesion inhibiting pattern on the substrate; A step of applying and / or depositing a metal over the substrate to form a metal pattern between the metal adhesion inhibition patterns; and The step of selectively removing the metal adhesion inhibition pattern; comprising The above metal adhesion inhibition pattern is a metal pattern forming method comprising a water-soluble polymer and a cellulose material.

3. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the above-mentioned water-soluble polymer comprises polyvinyl alcohol, polyacrylic acid, or a combination thereof.

4. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the cellulose material comprises cellulose, methyl cellulose, ethyl cellulose, or a combination thereof, nanofiber, nanocrystal, microfiber, microcrystal, or a combination thereof.

5. In Paragraph 1, A method for forming a metal pattern, further comprising the step of removing the metal adhesion inhibitor layer exposed by the metal pattern.

6. A method for forming a metal pattern, wherein the step of selectively removing the metal adhesion inhibition pattern of claim 2 or the step of removing the metal adhesion inhibition layer of claim 5 includes the step of washing with water.

7. In Paragraph 1, A method for forming a metal pattern, wherein the step of forming the metal adhesion inhibition layer further includes the step of treating the surface of the metal adhesion inhibition layer with a hydrophobic material.

8. In Paragraph 2, A method for forming a metal pattern, wherein the step of forming the metal adhesion inhibition pattern further includes the step of treating the surface of the metal adhesion inhibition petan with a hydrophobic material.

9. In Paragraph 7 or 8, A method for forming a metal pattern, wherein the above-mentioned hydrophobic material comprises perfluorooctyltrichlorosilane (FOTS), perfluorodecyltrichlorosilane (FDTS), methacryloxypropyltrimethoxysilane (MPTMS), undecenyltrichlorosilane (UTS), vinyltrichlorosilane (VTS), decyltrichlorosilane (DTS), octadecyltrichlorosilane (OTS), dimethyldichlorosilane (DDMS), dodecyltrichlorosilane (DDTS), perfluorooctyldimethylchlorosilane, aminopropylmethoxysilane (APTMS), or a combination thereof.

10. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the substrate is a flexible substrate.

11. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the above metal includes a liquid metal (low melting point metal).

12. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the metal comprises silver (Ag), gold (Au), aluminum (Al), copper (Cu), magnesium (Mg), or a combination thereof.

13. In Paragraph 11, A method for forming a metal pattern, wherein the liquid metal is a gallium-indium eutectic alloy (EGaIn), a gallium-indium-tin eutectic alloy (Gainstan), or a combination thereof.

14. In Paragraph 1, The above metal adhesive pattern is a metal pattern forming method comprising a flexible polymer.

15. In Paragraph 1 or 2, A method for forming a metal pattern, wherein the application of the metal comprises roller application, stamp application, or a combination thereof.

16. In Paragraph 1 or 2, A method for forming a metal pattern, further comprising the step of forming a sealing layer over the metal pattern.

17. In Paragraph 11, A method for forming a metal pattern, wherein the weight ratio of the cellulose material to the water-soluble polymer is in the range of 0.1:1 to 4:

1.

18. Substrate; A metal adhesion inhibitor layer on the above substrate; and Metal pattern structure on the metal adhesion inhibition layer; comprising The metal adhesion inhibitor layer comprises a composition of a cellulose material and a water-soluble polymer, and A substrate comprising a metal pattern structure, the metal pattern structure comprising a metal adhesive pattern; and a metal pattern on the metal adhesive pattern.

19. In Paragraph 18, The above metal pattern is a substrate comprising a metal pattern that includes a liquid metal.

20. An electronic device comprising a substrate according to paragraph 18.

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