Patterned conductive article

Abstract

The patterned conductive article 200 includes a substrate 210 including a single layer 210-1 and a micropattern of conductive traces 220 at least partially embedded in the single layer. Each conductive trace includes a conductive seed layer 230 extending along the length of the conductive trace (y-direction) and having a top major surface 232 and an opposing bottom major surface 234 in direct contact with the single layer, and a single conductor 240 disposed on the top major surface of the conductive seed layer. The single conductor and the conductive seed layer differ in at least one of composition or crystalline morphology. The single conductor has lateral sidewalls 242, 244, with at least a majority of the total area of ​​the lateral sidewalls in direct contact with the single layer.

Description

[Background technology]

[0001] Articles that serve as antennas, EMI shields, or touch sensors may include fine patterns of conductive traces formed on a substrate by photolithography. Summary of the Invention

[0002] In some aspects herein, a patterned conductive article is provided that includes a substrate including a unitary layer and includes a micropattern of conductive traces at least partially embedded in the unitary layer. Each conductive trace includes a conductive seed layer extending along the length of the conductive trace and having a top major surface and an opposing bottom major surface in direct contact with the unitary layer, and a unitary conductor disposed on the top major surface of the conductive seed layer. The unitary conductor and the conductive seed layer differ in at least one of composition or crystal morphology. The unitary conductor has lateral sidewalls, and at least a majority of the total area of ​​the lateral sidewalls is in direct contact with the unitary layer.

[0003] In some aspects of the present disclosure, a patterned conductive article is provided. The patterned conductive article includes a substrate having a first groove therein, a conductive seed layer disposed in the first groove, and a single conductor disposed at least partially in the first groove. The first groove extends along a longitudinal direction and has a bottom surface and a side surface. In at least one cross section perpendicular to the longitudinal direction of the first groove, the conductive seed layer covers at least a majority of the bottom surface of the first groove, and the single conductor covers the conductive seed layer and at least a majority of the side surfaces of the first groove. Each of the side surfaces and the single conductor define a conductor-insulator interface between each of the side surfaces and the single conductor. The single conductor and the conductive seed layer define a conductor-conductor interface between the single conductor and the conductive seed layer.

[0004] In some embodiments herein, a patterned conductive article includes a substrate having a first groove therein, a conductive seed layer disposed within the first groove, and a single conductor disposed at least partially within the first groove. The first groove has a bottom surface and a side surface. The conductive seed layer covers at least a majority of the bottom surface of the first groove, and the single conductor covers the conductive seed layer and at least a majority of the side surface of the first groove. In a plane through the single conductor that is parallel to and spaced from the seed layer, the single conductor has a first smaller line edge roughness at a first interface with the side surface, and the conductive seed layer has a second larger line edge roughness at an edge of the conductive seed layer.

[0005] In some aspects of the present specification, a method for manufacturing a patterned conductive article is provided. The method includes: preparing a tool having at least one ridge; disposing a conductive layer on a top surface of a first portion of the at least one ridge such that at least half of the total area of ​​the side of the first portion of the at least one ridge does not include the conductive layer; disposing a resin on the tool after the step of disposing the conductive layer; solidifying the resin to form a polymer layer including at least one groove corresponding to the at least one ridge; and removing the polymer layer and the conductive layer from the tool such that the conductive layer is disposed on a bottom surface of the at least one groove. In some embodiments, the method further includes depositing a conductive material (e.g., via electroplating) in the at least one groove such that the conductive material covers the conductive layer. The deposited conductive material can form a single conductor. [Brief description of the drawings]

[0006] [Figure 1] FIG. 2 is a schematic plan view of a patterned conductive article. [Diagram 2] 1 is a schematic cross-sectional view of a portion of a patterned conductive article. [Diagram 3] 1 is a schematic cross-sectional view of a portion of a patterned conductive article. [Figure 4] FIG. 2 is a schematic cross-sectional view of a trace. [Figure 5A] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5B] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5C] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5D] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5E] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5F] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5G] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 5H] 1 is a schematic diagram of steps in a method for making a patterned conductive article. [Figure 6] 1 is a schematic cross-sectional view of a substrate including a groove with a conductive seed layer disposed on the bottom surface of the groove. [Figure 7] 1 is a schematic cross-sectional view of a substrate including a groove with a conductive seed layer disposed on the bottom surface of the groove. [Figure 8] FIG. 2 is a schematic top view of a conductive seed layer. [Figure 9] 2 is a schematic cross-sectional view of a conductive seed layer. [Figure 10] 2 is a schematic cross-sectional view of a conductive seed layer. [Figure 11A] 1 is a schematic cross-sectional view of a single conductor in orthogonal cross section; [Figure 11B] 1 is a schematic cross-sectional view of a single conductor in orthogonal cross section; [Figure 12A] FIG. 2 is a schematic plan view of a patterned conductive article, which may be an antenna. [Figure 12B] FIG. 2 is a schematic plan view of a patterned conductive article, which may be an antenna. [Figure 13] 1 is a schematic cross-sectional view of a patterned conductive article. [Figure 14] 1 is a schematic cross-sectional view of a patterned conductive article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In the following description, reference is made to the accompanying drawings which form a part hereof, and in which are shown by way of illustration various embodiments. The drawings are not necessarily to scale. It is to be understood that other embodiments are contemplated and may be made without departing from the scope or spirit of the specification. Therefore, the following detailed description is not to be taken in a limiting sense.

[0008] The fine pattern of conductive traces may be formed on a substrate using a photolithography process. According to some aspects of the present specification, a process has been developed that allows conductive traces to be formed at least partially in a substrate without the use of photolithography. In some embodiments, the process described herein is cheaper and / or easier to implement than conventional photolithography processes. In some embodiments, the process can form traces with a high aspect ratio (thickness divided by width) (e.g., at least 0.8). A high aspect ratio may be desirable in applications where high transparency and high electrical conductance are desired. For example, increasing the open area ratio can increase transparency, but decrease electrical conductance for a fixed trace thickness. Thus, to increase electrical conductance, the traces can be made thicker, which can result in a high aspect ratio. In some embodiments, the patterned conductive article may be used at a relatively high operating frequency (e.g., the patterned conductive article may be an antenna designed to operate at microwave frequencies), where, for example, the skin depth of the material of the trace is less than the width of the trace. The use of a high aspect ratio increases the surface area of ​​the trace for a given trace width, resulting in increased conductor usage (and therefore increased electrical conductance at operating frequencies) compared to lower aspect ratio traces of the same trace width (e.g., those conventionally formed by lithography or printing). In some embodiments, the traces are formed by plating onto a conductive layer disposed on the bottom of a groove in the substrate (e.g., electroplating onto a conductive seed layer). The sidewalls of the groove can be free or substantially free of the conductive seed layer. Plating onto a conductive seed layer disposed on the bottom of the groove, but not on the sidewalls of the groove, has been found to improve control of the trace profile compared to plating into a groove where the seed layer is also on the sidewalls.For example, if the seed layer is on the sidewalls, plating may result in metal forming on top of the seed layer on the sidewalls, resulting in metal spilling over the edges of the grooves onto the top surface of the substrate. Such spilling may be problematic for patterned articles made by conventional processes, particularly when high aspect ratios are desired, as it may reduce light transmission through the patterned article.

[0009] Additionally, placing the conductive layer at the bottom of the grooves provides protection (e.g., increased durability) for the conductive layer. Some applications may not require high conductance, so in some embodiments, no conductors are plated onto the conductive layer. In some such embodiments, a non-metallic material may be placed in the grooves on the conductive layer. For example, the grooves above the conductive layer may be backfilled with one or more of an adhesive, a polymer, or a dielectric material (e.g., an optically clear polymer adhesive).

[0010] Conductive member (e.g., conductor, conductive layer, conductive trace, or conductive material) means an electrically conductive member, unless otherwise specified. A conductive member may have a resistance of, for example, less than 1 Ω·m, or less than 0.01 Ω·m, or less than 10 -4 Less than Ω·m or 10 -6 A non-conductive material may have an electrical resistivity of less than 100 Ω·m. A non-conductive material refers to an electrically non-conductive material unless otherwise specified. A non-conductive material may have an electrical resistivity of more than 100 Ω·m, or less than 10 4 More than Ω·m or 10 6 More than Ω·m or 10 8 It may have an electrical resistivity of greater than Ω·m. Electrical resistivity refers to direct current (DC) resistivity unless otherwise indicated.

[0011] FIG. 1 is a schematic plan view of a patterned conductive article 100 or a portion of the article 100. The article 100 includes a substrate 110 and a micropattern of conductive traces 120 at least partially embedded in the substrate 110. Each conductive trace 120 extends along a longitudinal direction 122 of the conductive trace 120. Each conductive trace 120 can have a length along the longitudinal direction 122 and a width along an orthogonal direction, where the width is substantially less than the length. In some embodiments, the substrate 110 is a single substrate or includes a single layer. For example, the substrate 110 may be a monolithic polymer substrate and may include a first layer of a monolithic polymer disposed on a second layer of substrate.

[0012] In some embodiments, the substrate 110 is substantially transparent. In some embodiments, the patterned conductive article 100 is substantially transparent. For example, the article 100 can be substantially transparent when it has a sufficiently high open area ratio (the proportion or percentage of the area not covered by traces in a plan view of the article 100). In some embodiments, the article 100 has an open area ratio in the range of 80% to 99.95%, or 80% to 99.9%, or 85% to 99.9%, or 90% to 99.9%, or 95% to 99.9%. In some embodiments, in a plan view, the total area of ​​the pattern of conductive traces 120 is less than 50%, or less than 20%, or less than 10%, or less than 5%, or less than 3%, or less than 2%, or less than 1% of the total surface area of ​​the patterned conductive article 100. In some embodiments, article 100 has an average light transmittance for normally incident visible light (wavelengths ranging from 400 nm to 700 nm) of at least 50%, or at least 70%, or at least 80%, or at least 90%. In some embodiments, the average light transmittance can be less than 70% or less than 50%. For example, article 100 may include additional layer(s) such as a decorative film (e.g., Fasala window film available from 3M Company, St. Paul, MN) that reduces the average light transmittance. The light transmittance can be measured from the top or bottom major surface of article 100. In some embodiments, the average light transmittance of a substrate with conductive traces differs from the average light transmittance of a substrate without conductive traces by 5% or less, or 2% or less, or 1% or less.

[0013] In some embodiments, article 100 is a flexible film (e.g., a flexible film that can be bent 180 degrees around a cylinder having a diameter of 10 cm without cracking). The flexible film can be substantially transparent, as described elsewhere.

[0014] In some embodiments, article 100 is at least one of an antenna, a heater, an electromagnetic interference (EMI) shield, a static dissipative component, or an electrode. In some embodiments, article 100 is an antenna, as further described elsewhere herein. In some embodiments, article 100 is a sensor, such as a touch sensor. In some embodiments, the antenna, heater, electromagnetic interference shield, static dissipative component, sensor, or electrode is a substantially transparent and / or flexible film.

[0015] The micropattern of conductive traces 120 may be or may include a mesh pattern, which may be a two-dimensional regular array of traces (e.g., a rectangular, square, triangular, or hexagonal array) or a two-dimensional irregular array. Suitable micropattern geometries for article 100 include those described in, for example, U.S. Patent Application Publication Nos. 2008 / 0095988 (Frey et al.), 2009 / 0219257 (Frey et al.), 2015 / 0138151 (Moran et al.), 2013 / 0264390 (Frey et al.), and 2015 / 0085460 (Frey).

[0016] In some embodiments, each trace 120 is at least partially disposed within a groove in the substrate 110. A trace at least partially disposed in a substrate is shown generally in FIG.

[0017] FIG. 2 is a schematic cross-sectional view of a portion of a patterned conductive article 200 including a substrate 210 and traces 220 at least partially embedded in the substrate 210. In the illustrated embodiment, the substrate 210 includes a layer 210-1 disposed on a layer 210-2. In some embodiments, the layer 210-1 is a single layer. In such embodiments, the layer 210-1 can be considered a first single substrate disposed on a second substrate (layer 210-2). In some embodiments, the layer 210-2 is a single layer. In some embodiments, the layer 210-1 can be formed by casting and curing a resin on the layer 210-2. In some embodiments, the substrate 210 is substantially transparent and / or polymeric. The traces 220 can be traces in a micropattern of conductive traces. The trace 220 includes a conductive seed layer 230 having a top major surface 232 and an opposing bottom major surface 234 in direct contact with the substrate 210 (e.g., in direct contact with the single layer 210-1 of the substrate 210). The trace 220 further includes a single conductor 240 disposed on the top major surface 232 of the conductive seed layer 230. The conductive seed layer 230 can be, for example, a cured conductive ink or a cured conductive coating, or can include, for example, a transferred layer (e.g., a transferred metal layer). The single conductor 240 can be a metal body formed, for example, by plating. In some embodiments, the single conductor 240 and the conductive seed layer 230 differ in at least one of composition or crystal morphology. The single conductor 240 has lateral sidewalls 242 and 244. In some embodiments, at least a majority (or at least 60%, or at least 70%, or at least 80%, or at least 90%) of the total area of ​​lateral sidewalls 242 and 242 is in direct contact with layer 210-1.

[0018] The patterned conductive article 200 may alternatively or additionally be described as follows. The patterned conductive article 200 includes a substrate 210 including a first groove 212 therein. For example, the substrate 210 may include a micropattern of grooves therein (see, for example, FIG. 1 ), the micropattern of grooves including the first groove 212. In some embodiments, the first groove 212 extends along a longitudinal direction of the first groove 212 (the y-direction in the illustrated xyz coordinate system) and has a bottom surface 218 and side surfaces 214 and 216. A conductive seed layer 230 is disposed within the first groove 212, and a single conductor 240 is at least partially disposed within the first groove 212. In some embodiments, in at least one cross section perpendicular to the longitudinal direction of the first groove 212 (e.g., the cross section shown in the xz plane), the conductive seed layer 230 covers at least a majority (greater than 50% of the area) of the bottom surface 218 of the first groove 212, and the single conductor 240 covers the conductive seed layer 230 and at least a majority (greater than 50% of the area) of the side surfaces 214 and 216 of the first groove 212. In some embodiments, each of the side surfaces 214 and 216 and the single conductor 240 define a conductor-insulator interface (245 and 247, respectively) between each of the side surfaces 214 and 216 and the single conductor 240, and the single conductor 240 and the conductive seed layer 230 define a conductor-conductor interface 235 between the single conductor 240 and the conductive seed layer 230. In some embodiments, the single conductor 240 is a single metal body.

[0019] As further described elsewhere herein, in some embodiments, the single conductor 240 has a smaller first surface roughness at a first interface (245 and / or 247) with the side surfaces (214 and 216) and a larger second surface roughness at a second interface (235) with the conductive seed layer 230.

[0020] As further described elsewhere herein, in some embodiments, in a plane through single conductor 240 that is parallel to and away from conductive seed layer 230, the single conductor has a first, smaller line edge roughness at a first interface with side 214, 216, and conductive seed layer 230 has a second, larger line edge roughness at an edge of conductive seed layer 230.

[0021] In some embodiments, the single conductor 240 may fill or overfill the groove 212. An embodiment in which the top surface of the single conductor extends above the top surface of the substrate is shown diagrammatically in FIG.

[0022] 3 is a schematic cross-sectional view of a portion of a patterned conductive article 300 including a substrate 310 including a first groove 312 therein and further including an optional optical film 380 bonded to the substrate 310. A conductive seed layer 330 is disposed within the first groove 312, and a single conductor 340 is disposed at least partially within the first groove 312. The substrate 310 may include, for example, two or more layers (e.g., layers corresponding to the substrate 210) or may include a single upper layer. The patterned conductive article 300 may correspond to the patterned conductive article 200, except that the single conductor 340 extends beyond the top surface 311 of the substrate 310 at a central portion (in the cross-section shown) of the single conductor 340, and the article 300 includes the optional optical film 380. The top surface 341 of single conductor 340, or of any other single conductor described herein, may be, for example, convex hemispherical (concave downward) as shown, may be concave upward, may be substantially planar, or may have an irregular shape.

[0023] The optical film 380 may be laminated to the substrate 310 using an optically clear adhesive (not shown), or the substrate 310 may be formed directly on the optical film 380. The optical film 380 may be disposed on the bottom surface 313 of the substrate 310 as shown, or on the top surface 311 of the substrate 310. In some embodiments, the optical film 380 is or includes one or more of a window film, a textured film, a patterned film, or an infrared reflective film. Useful optical films include, for example, those described in U.S. Patent Application Publication Nos. 2017 / 0248741 (Hao et al.), 2015 / 0285956 (Schmidt et al.), 2010 / 0316852 (Condo et al.), 2016 / 0170101 (Kivel et al.), 2014 / 0204294 (Lv), 2014 / 0308477 (Derks et al.), 2014 / 0057058 (Yapel et al.), 2005 / 0079333 (Wheatley et al.), and 2002 / 0012248 (Campbell et al.).

[0024] In some embodiments, in at least one cross-section of the first groove 312, the single conductor 340 fills more than half of the cross-sectional area of ​​the first groove 312, and in at least one cross-section of the first groove 212, the single conductor 240 fills more than half of the cross-sectional area of ​​the first groove 312. In some embodiments, the single conductor 340 fills at least 60%, or at least 70%, or at least 80%, or at least 90% of the cross-sectional area of ​​the first groove 312, and the single conductor 240 fills at least 60%, or at least 70%, or at least 80%, or at least 90% of the cross-sectional area of ​​the first groove 212. In some embodiments, the single conductor 340 and the conductive seed layer 330 together fill the cross-sectional area of ​​the first groove 312, and the single conductor 240 and the conductive seed layer 230 together fill the cross-sectional area of ​​the first groove 212.

[0025] FIG. 4 is a schematic cross-sectional view of a trace 420 including a single conductor 440 disposed on a conductive seed layer 430. The trace 420 may have substantially vertical sidewalls as shown generally in FIG. 4, or the sidewalls may be slanted as shown elsewhere herein. In some embodiments, the single conductor 440 and the conductive seed layer 430 differ in at least one of composition or crystal morphology. The composition may differ, for example, when the conductive seed layer 430 and the single conductor 440 include different metals, or when the conductive seed layer 430 is a cured conductive ink or a cured conductive coating and the single conductor 440 is a solid metal. The different cross-hatching in FIG. 4 may, for example, generally represent different compositions. Alternatively or additionally, the different cross-hatching in FIG. 4 may, for example, generally represent different crystal morphologies. The crystal morphology may differ, for example, when the conductive seed layer 430 and the single conductor 440 are formed from the same metal, but the metals have different grain size distributions due to different process conditions in forming the materials. As another example, the composition and crystal morphology may be different when the conductive seed layer 430 is formed from a first metal having a first crystal structure (e.g., one of face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp)) and the single conductor 440 is formed from a different second metal having a different second crystal structure (e.g., a different one of fcc, bcc, or hcp). As yet another example, the crystal morphology may be different when one of the single conductor 440 and the conductive seed layer 430 is amorphous or substantially amorphous and the other of the single conductor 440 and the conductive seed layer 430 is substantially crystalline. In some embodiments, the single conductor 440 and the conductive seed layer 430 have different crystal morphologies that may be characterized in terms of different average grain sizes. The average grain size may be determined, for example, as described in ASTM Standard E112-13 "Standard Test Method for Determining Average Grain Size."

[0026] The single conductor 440 and the conductive seed layer 430 define an interface 435 between the single conductor 440 and the conductive seed layer 430. The interface 435 may be sharp (e.g., when the single conductor 440 and the conductive seed layer 430 have different compositions and there is little diffusion between the two layers) or may be diffuse (e.g., when the single conductor 440 and the conductive seed layer 430 have the same composition but different crystal morphologies and there is a transition region between the different crystal morphologies or there is significant diffusion between the two layers that widens the interface 435). The interface 435 generally has a thickness that is substantially less than the thickness of the single conductor 440. In some embodiments, the interface 435 has a thickness that is less than 5 percent, or less than 2 percent, or less than 1 percent, or less than 0.5 percent of the thickness of the single conductor 440. In some embodiments, interface 435 is a conductor-conductor interface having a thickness less than 1 micrometer, or less than 500 nm, or less than 300 nm, or less than 100 nm, or less than 50 nm.

[0027] In some embodiments, each conductive trace of at least a majority of the conductive traces in the micropattern has a width W along a width direction (x direction) perpendicular to the length direction (y direction) and the thickness direction (z direction) of the substrate, and a thickness T along the thickness direction. If the trace is tapered, the width W can be understood to be the width of the trace at the vertical position where the trace is widest (e.g., proximate the top of the trace). In some embodiments, T / W is at least 0.8, 1, 1.2, 1.5, 2, 5, or 7. In some such embodiments, the patterned conductive article has a light transmission and / or fractional open area in any of the ranges described elsewhere herein.

[0028] 5A-5H show various steps in a method for making a patterned conductive article. In some embodiments, the method includes providing a tool 550 having at least one ridge 555, as illustrated generally in FIG. 5A, which is a schematic cross-sectional view of the tool 550. The tool 550 is shown generally as having a substantially planar bottom surface in the illustrated embodiment. In other embodiments, the tool 550 has a generally cylindrical shape, for example. The tool may be, for example, a metal tool (e.g., made by diamond turning as known in the art) or a polymer tool formed from the metal tool (e.g., by compression molding a polymer against the metal tool). The method includes disposing a conductive layer 530 on a top surface 556 of a first portion 557 of at least one ridge 555 such that at least half of the total area of ​​a side surface 560 of the first portion 557 of the at least one ridge 555 does not include the conductive layer 530, as illustrated generally in FIG. 5B. The conductive layer 530 has a major surface 534 in contact with the tool 550 and an opposing major surface 532. In some embodiments, at least a majority of the total area of ​​the at least one ridge 555 does not include the conductive layer 530. After the conductive layer 530 is disposed on the top surface 556, the conductive material of the conductive layer 530 covers less than half, preferably less than 25%, or less than 10% of the total area of ​​the side surface 560. In some embodiments, the first portion 557 may include all of the at least one ridge 555 and the top surface 556 may be the top surface(s) of all of the ridge(s) of the at least one ridge 555. In other embodiments, the portion of the at least one ridge 555 that receives the conductive layer (e.g., the first portion 557b shown in FIG. 5C) may include less than all of the at least one ridge 555.

[0029] In some embodiments, after disposing the conductive layer 530 on the top surface 556b of the first portion 557b (see FIG. 5C) of the at least one ridge 555, the top surface 558 of the second portion 559 of the at least one ridge 555 does not include the conductive layer 530. This is shown diagrammatically in FIG. 5C, which shows a conductive layer 530b disposed on the top surfaces of only two of the four ridges shown. By providing a conductive layer on only a portion of the top surfaces of the ridges, a tool having a uniform pattern (e.g., a uniform hexagonal pattern) can generate a micropattern of conductors having a non-uniform pattern (e.g., the conductors may be a hexagonal pattern in some areas and absent in other areas). In some embodiments, the first portion 557b of the at least one ridge 555 includes a plurality of first ridges and the second portion 559 of the at least one ridge 555 includes a plurality of second ridges.

[0030] In some embodiments, the conductive layer 530 or 530b is provided as a transfer layer. In some embodiments, disposing the conductive layer 530 (or 530b) on the top surface 556 (or 556b) of the first portion 557 (or 557b) of the at least one ridge 555 includes transferring the conductive layer from a transfer film to the top surface. This is shown generally in FIGS. 5D-5E, which are schematic cross-sectional views of the conductive layer 530 before and after it has been transferred to the top surface 556. The transfer film 590 includes a transfer layer 592 disposed on a substrate 594. When the transfer film 590 contacts the tool 550, a portion of the transfer layer 592 is transferred from the substrate 594 to the top surface 556 to form the conductive layer 530. The transfer layer 592 may include sublayers. For example, the transfer layer 592 may include a metal layer (or other conductive layer) and an adhesive layer for releasably attaching the metal layer to the top surface 556. The metal layer (or other conductive layer) may be a single conductive layer. The transfer layer 592 may further include a crosslinked polymer layer (e.g., acrylic), in which case the metal layer or other conductive layer is disposed on either side of the crosslinked polymer layer. The transfer layer 592 may further include a dielectric layer, which may be disposed between the metal layer or other conductive layer and the crosslinked polymer layer. In some embodiments, the transfer layer 592 includes a dielectric layer between the transferred conductive layer and the top surface 556 after being transferred to the tool 550. In such embodiments, the polymer layer 510 (see FIG. 5G) formed using the tool with the transferred conductive layer may include a dielectric layer at the bottom of the grooves 512 of the polymer layer 510, and the manufacturing method may include removing the dielectric layer (e.g., via reactive ion etching). The transfer layer may be prepared, for example, as described in U.S. Pat. No. 8,658,248 (Anderson et al.) or U.S. Pat. No. 7,018,713 (Padiyath et al.). The substrate 594 may include a release layer disposed on a polymeric substrate layer. The transfer film may be as described, for example, in WO 2018 / 178802 (Gotrik et al.) or WO 2018 / 178803 (Gotrik et al.).

[0031] In some embodiments, the conductive layer 530 or 530b is applied as a conductive ink or as a conductive coating. In some embodiments, disposing the conductive layer 530b (or 530) on the top surface 556b (or 556) of the first portion 557b (or 557) of the at least one ridge 555 includes applying a conductive ink to a tool 550 or coating the tool with a conductive coating such that the conductive ink or coating is disposed on the top surface. In some such embodiments, the conductive ink or coating is cured (e.g., by drying and sintering or by other curing means such as those for curing resin layers described elsewhere herein), and the cured conductive ink or coating is the conductive layer 530b (or 530). The step of curing the conductive ink or coating may be performed before, after, or simultaneously with the step of solidifying the resin. Applying the conductive layer as a conductive ink or coating may result in some wetting of the side surface 560, as shown generally in FIG. 5C.

[0032] The method includes, after the step of disposing the conductive layer, disposing (e.g., casting) a resin 562 on the tool 550, solidifying the resin to form a polymer layer 510 including at least one groove 512 corresponding to the at least one ridge 555, and removing the polymer layer 510 and the conductive layer 530 from the tool 550 such that the conductive layer 530 is disposed on a bottom surface 518 of the at least one groove 512. FIG. 5F is a schematic cross-sectional view of the tool 550 including the resin 562 disposed on the tool 550. FIG. 5G is a schematic cross-sectional view of the polymer layer 510 with the conductive layer 530 disposed on the bottom surface 518 of the at least one groove 512. A major surface 532 of the conductive layer 530 contacts the bottom surface 518 of the at least one groove 518. The conductive layer 530 may cover all or substantially all of the total area of ​​the bottom surface 518 of at least one groove 512, or may cover a first portion 519 of the bottom surface 518 (e.g., corresponding to first portion 557b) while a second portion 515 of the bottom surface 518 is free of the conductive layer 530, as shown generally in FIG. 5H.

[0033] Spatial terms, including but not limited to "bottom," "lower," "top," "below," "down," "upper," "above," and "on top," as used herein, are utilized for ease of description to describe spatial relationships. Such spatial terms encompass different orientations of the article during use or operation in addition to the specific orientation depicted in the figures and described herein. For example, the bottom of a groove is opposite the top of an open groove, regardless of whether the substrate containing the groove is inverted or turned upside down.

[0034] The at least one groove 512 may be described as corresponding to the at least one ridge 555 when each groove of the at least one groove is formed from a ridge of the at least one ridge 555. This correspondence may or may not be one-to-one. For example, in some embodiments, the tool may be generally cylindrical and used in a continuous roll-to-roll process, with the same ridge forming multiple grooves of the at least one groove 512 (e.g., if the tool has a circumference of 20 cm, the same ridge in the tool may be used to form multiple grooves in the polymer layer that are spaced 20 cm apart from one another). In some cases, the tool may include additional ridges that are not coated with resin, and there may be no grooves that correspond to the uncoated ridges (e.g., if resin is not cast on the ends of the tool, any ridges that may be present on the ends will not create grooves in the resulting polymer layer).

[0035] In some embodiments, solidifying the resin includes curing the resin. For example, the resin may be cured by applying radiation (e.g., ultraviolet (UV), or electron beam radiation, or other actinic radiation), or by applying heat, or using other crosslinking mechanisms known in the art. The resin may be, for example, an acrylate or epoxy, or other resin chemistries may be used. In some embodiments, solidifying the resin includes cooling the resin. For example, the resin may be a thermoplastic resin (e.g., polyethylene terephthalate, polypropylene, polycarbonate, or other thermoplastic resins known in the art) that is applied as a melt that cools to form a thermoplastic polymer layer.

[0036] In some embodiments, the method further includes depositing a conductive material (e.g., via electroplating) in the at least one groove 512 such that the conductive material covers the conductive layer 530. This may be done after removing the polymer layer 510 and the conductive layer 530 from the tool 550, as shown in Figures 5G-5H. The conductive material may form a single conductor, as described elsewhere herein. In some embodiments, depositing the conductive material in the at least one groove 512 includes depositing the conductive material in a first portion 512a of the at least one groove corresponding to a first portion of the at least one ridge (e.g., a portion of the at least one groove 512 that includes the conductive layer 530) but not in a second portion 512b of the at least one groove corresponding to a second portion of the at least one ridge (e.g., a portion of the at least one groove 512 that does not include the conductive layer 530).

[0037] In some embodiments, the article shown generally in Figures 5G-5H can be described as including a substrate (e.g., polymer layer 510, or polymer layer 510 plus a substrate layer on which polymer layer 510 can be formed) having a first groove therein (e.g., any of grooves 512 shown in Figure 5G or any of the grooves in first portion 512a shown in Figure 5H), the first groove extending along a longitudinal direction (y-direction) and having a bottom surface 518 and side surfaces 514 and 516, and a single conductive layer (e.g., conductive layer 530 or a single sublayer of conductive layer 530 (e.g., a transferred metal layer)) disposed within the first groove. In at least one cross section perpendicular to the longitudinal direction of the first groove, the conductive layer covers at least a majority of the bottom surface of the first groove, and at least a majority of the side surfaces of the first groove are not in contact with a material having the same composition as the composition of the single conductive layer. For example, in some embodiments, side surfaces 514 and 516 may be in contact with air. In some embodiments, a dielectric material, or a conductive material having a composition different from that of the single conductive layer, or a non-metallic material is at least partially disposed in the first groove, such that in at least one cross-section of the first groove, the material covers at least a majority of the side of the first groove (see, e.g., FIG. 14 ).

[0038] FIG. 6 is a schematic cross-sectional view of a layer 610 (which may be, for example, a single layer of a multi-layer substrate and / or may be a polymer layer) including a groove 612, with a conductive seed layer 630 disposed on a bottom surface of the groove 612. A bottom major surface of the conductive seed layer 630 may be in direct contact with the layer 610. A single conductor may be formed (e.g., by plating) on ​​the conductive seed layer 630 to form a trace that extends along the length of the trace (y-direction). In some embodiments, the conductive seed layer 630 has a central region 638 that extends along the length of the conductive trace and is disposed between a first edge region 637 and a second edge region 639 that extend along the length of the central region 638. In some embodiments, the central region 638 has an average thickness that is greater than the average thickness (unweighted average of the thicknesses) of each of the first edge region 637 and the second edge region 639.

[0039] 7 is a schematic cross-sectional view of a layer 710 (e.g., a single layer of a substrate) including a groove 712, with a conductive seed layer 730 disposed on a bottom surface of the groove 712. Layer 710 may correspond to layer 610, and conductive seed layer 730 may correspond to conductive seed layer 630, except for the thickness of a central region 738 and edge regions 737 and 739. A single conductor may be formed (e.g., by plating) on ​​the conductive seed layer 730 to form a trace that extends along the length of the trace (y-direction). In some embodiments, the conductive seed layer 730 has a central region 738 that extends along the length of the conductive trace and is disposed between a first edge region 737 and a second edge region 739 that extend along the length of the central region 638. In some embodiments, the central region 738 has an average thickness that is less than the average thickness of each of the first edge region 737 and the second edge region 739.

[0040] In some embodiments, the top surface of the ridges of a tool used in forming the conductive seed layer is substantially flat, and the relative thicknesses of the central and edge regions depend on one or more of the surface energy of the material deposited to form the conductive seed layer, the surface energy of the material of the tool, and the surface energy of the material of the substrate. In other embodiments, the top surface of the ridges may be shaped to determine the relative thicknesses of the central and edge regions. In some embodiments, the thicknesses of the central and edge regions are approximately the same (e.g., differing by less than 10% or less than 5%).

[0041] In some embodiments, the conductive seed layer includes an irregular edge or a broken edge. In some embodiments, the conductive seed layer includes a plurality of broken portions. For example, in some embodiments, the conductive seed layer is a transferred layer, and the broken portions arise from the transfer process. The broken portions may extend, for example, from the edge of the conductive seed layer to an interior region. FIG. 8 is a schematic top view of a conductive seed layer 830 including side edges 843 and 846. In some embodiments, the roughness of edges 843 and 846 may be characterized in terms of line edge roughness. A roughness parameter Ra may be used for line edge roughness. For example, edge 846 has a line edge roughness Ra that may be described as the average of the absolute value of the displacement of edge 846 from the average position 849 of the edge. The line edge roughness Ra may be any of the ranges described elsewhere herein. In the illustrated embodiment, the conductive seed layer 830 includes a plurality of broken portions 848, and edges 843 and 846 are broken edges.

[0042] The conductive seed layer may be a single monolayer or may include multiple sublayers. For example, the conductive seed layer may include a conductive sublayer disposed on a non-conductive sublayer, which may be at least one of a tie layer or a crosslinked polymer layer. FIG. 9 is a schematic cross-sectional view of a conductive seed layer 930 including a conductive layer 951 disposed on a crosslinked polymer layer 953. The conductive layer 951 may be, for example, a sputtered or evaporated metal layer. The crosslinked polymer layer 953 may be, for example, a crosslinked acrylic layer. In some embodiments, the conductive seed layer 930 further includes a dielectric layer (e.g., an oxide layer) disposed between the conductive layer 951 and the crosslinked polymer layer 953. FIG. 10 is a schematic cross-sectional view of a conductive seed layer 1030 including a conductive layer 1051 disposed (indirectly) on the crosslinked polymer layer 1053 with a dielectric layer 1052 disposed between the conductive layer 1051 and the crosslinked polymer layer 1053. In some embodiments, the dielectric layer 1052 is or includes an oxide layer (e.g., an aluminum silicon oxide layer). In some embodiments, the crosslinked polymer layer 953 or 1053 has a thickness of less than 500 nm, or less than 300 nm, or less than 100 nm. In some embodiments, the conductive seed layer 951 or 1051 is or includes a metal layer having a thickness of less than 500 nm, or less than 300 nm, or less than 100 nm. The conductive layer 951 and / or the conductive layer 1051 can be a single conductive layer.

[0043] FIG. 11A is a schematic cross-sectional view of a single conductor 1140. The single conductor 1140 may be at least partially disposed within a groove in a substrate (not shown in FIG. 11A), the groove having a bottom surface and a side surface. The single conductor 1140 has an interface 1145 with the side surface, an interface 1147 with the side surface, and an interface 1135 with a conductive seed layer disposed on the bottom surface of the groove. In some embodiments, the single conductor 1140 can have a first, smaller surface roughness at a first interface with the side surface (1145 and / or 1147) and a second, larger surface roughness at a second interface with the conductive seed layer (1135). For example, in some embodiments, the substrate includes a single polymer layer and the single conductor 1140 forms a relatively smooth interface with the single polymer layer, while the seed layer can include a disrupted layer that results in a relatively rough interface with the single conductor 1140. The first and second surface roughnesses may be the arithmetic mean roughness Ra (average of the absolute value of the displacement of the surface from the mean surface height) of the corresponding first and second interfaces. In some embodiments, the first surface roughness is less than 1 micrometer, or less than 500 nm, or less than 200 nm, or less than 100 nm, or less than 50 nm, or less than 30 nm. In some embodiments, the second surface roughness is greater than 0.4 micrometers, or greater than 500 nm, or greater than 1 micrometer, or greater than 2 micrometers, or greater than 5 micrometers. In some embodiments, the second surface roughness is at least 0.5 micrometers, or at least 1 micrometer, or at least 2 micrometers greater than the first surface roughness.

[0044] 11B is a schematic diagram of a single conductor 1140 in cross section in plane P1. In some embodiments, in a plane P1 through the single conductor 1140 that is parallel to and spaced from a seed layer (not shown in FIGS. 11A-11B) (disposed at interface 1135), the single conductor 1140 can have a smaller first line edge roughness at a first interface 1145 or 1147 with a side surface, and the seed layer can have a larger second line edge roughness at an edge of the conductive seed layer (e.g., edge 846 shown in FIG. 8). Plane P1 may be taken, for example, to be approximately halfway between the top and bottom of the conductor 1140. The first line edge roughness and the second line edge roughness may each be the Ra roughness (average of the absolute values ​​of the displacement of the edges from the mean line of the edges). In some embodiments, the first line edge roughness is less than 1 micrometer, or less than 500 nm, or less than 200 nm, or less than 100 nm, less than 50 nm, or less than 30 nm. In some embodiments, the second line edge roughness is greater than 0.4 micrometers, or greater than 500 nm, or greater than 1 micrometer, or greater than 2 micrometers, or greater than 5 micrometers. In some embodiments, the second line edge roughness is at least 0.5 micrometers, or at least 1 micrometer, or at least 2 micrometers greater than the first line edge roughness.

[0045] In some embodiments, the patterned conductive article includes a micropattern of conductive traces disposed at least partially within a micropattern of grooves, the micropattern of grooves including at least one groove filled or substantially filled (e.g., at least 60%, or at least 70%, or at least 80%, or at least 90% filled, or 100% filled, or overfilled) with a non-conductive material. For example, the non-conductive material may be air or a dielectric material, where a dielectric material may be understood to be a non-conductive material having a dielectric constant greater than that of air. FIG. 12A is a schematic plan view of a patterned conductive article 1200a including a micropattern of conductive traces 1220a disposed at least partially within a micropattern of grooves, the micropattern of grooves including at least one groove 1275a (a plurality of grooves in the illustrated embodiment) filled or substantially filled with a non-conductive material. Similarly, FIG. 12B is a schematic plan view of a patterned conductive article 1200b including a micropattern of conductive traces 1220b disposed at least partially within a micropattern of grooves, the micropattern of grooves including at least one groove 1275b (or multiple grooves in the illustrated embodiment) filled or substantially filled with a non-conductive material.

[0046] In some embodiments, the patterned conductive article 1200a or 1200b is an antenna. In some embodiments, the fine pattern of the conductive traces 1220a or 1220b is configured to provide a predetermined spectral response. For example, the fine pattern may have an overall size and shape such that it can efficiently transmit and receive at a predetermined wavelength or frequency range. In some such embodiments, the fine pattern of the conductive traces 1220a or 1220b is configured to provide a predetermined directivity. For example, the fine pattern may have an overall size and shape (e.g., a bowtie antenna as shown diagrammatically in FIG. 12A, or a bowtie slot antenna as shown diagrammatically in FIG. 12B) such that it can efficiently transmit and receive at a predetermined wavelength range with a predetermined directivity (e.g., transmits stronger along a specified direction than in another direction). The patterned conductive article 1200a or 1200b may be, for example, a 5G antenna, and / or may be configured to transmit and receive at a frequency band of, for example, 30-300 GHz. Useful antenna shapes are described, for example, in U.S. Patent Application Publication Nos. 2009 / 0051620 (Ishibashi et al.), 2009 / 0303125 (Caille et al.), and 2013 / 0264390 (Frey et al.). In some embodiments, the patterned conductive article 1200a or 1200b is a substantially transparent antenna. For example, in some embodiments, the patterned conductive article 1200a or 1200b is adapted to be placed on a window, where it is desired to use the article as an antenna and be able to see through the antenna.

[0047] 13 is a schematic cross-sectional view of a patterned conductive article 1300 or a portion of the article 1300, which may correspond, for example, to patterned conductive article 1200a or 1200b. The patterned conductive article 1300 includes a layer 1310 (e.g., a single top layer of a substrate) including a micropattern of grooves including a first groove 1312 and a second groove 1372. The first groove 1312 includes a trace 1320 including a single conductor 1340 disposed on a conductive seed layer 1330. The second groove 1372 may be substantially filled with a material 1375, which may be substantially transparent and / or non-conductive. For example, the micropattern of grooves may be provided with conductive traces in some of the grooves, as further described elsewhere herein, and then a coating 1370 may be applied over the grooves such that the material 1375 of the coating 1370 fills or substantially fills the grooves that do not include the traces. In some embodiments, in at least one cross-section perpendicular to the length of the second groove 1372, the second groove 1372 is substantially filled with a substantially transparent material.

[0048] Material 1375 may be a non-conductive and / or substantially transparent material and may be one or more of an adhesive, a polymer, or a dielectric material (e.g., an optically clear polymer adhesive). In some embodiments, material 1375 has a refractive index within 0.02 of the refractive index of layer 1310. Refractive index is determined at a wavelength of 532 nm unless otherwise specified.

[0049] FIG. 14 is a schematic cross-sectional view of a patterned conductive article 1400 or a portion of the article 1400. The patterned conductive article 1400 includes a layer 1410 (e.g., a single layer of a substrate) including a first groove 1412 (e.g., a groove in a micropattern of grooves) extending along a longitudinal direction (y direction) and having a bottom surface and a side surface. The first groove 1412 includes a single conductive layer 1430 disposed within the first groove. In at least one cross-section perpendicular to the longitudinal direction of the first groove, the conductive layer covers at least a majority of the bottom surface of the first groove, and at least a majority of the side surface of the first groove is not in contact with a material having the same composition as that of the conductive layer. In some embodiments, the single conductive layer 1430 can be used as a trace (e.g., without plating a single conductor on the conductive layer 1430). This may be desirable in applications where the conductive layer 1430 provides sufficient conductivity and the durability of the conductive layer 1430 is improved by disposing a layer on the bottom surface of the groove.

[0050] In some embodiments, the non-metallic material 1470 is at least partially disposed in the first groove 1412. In some embodiments, in at least one cross section of the first groove, the non-metallic material 1470 covers at least a majority of the sides of the first groove 1412. In the illustrated embodiment, the non-metallic material 1470 forms a continuous layer that fills the first groove 1412 (and fills the other grooves). For example, the non-metallic material 1470 may be one or more of an adhesive, a polymer, or a dielectric material (e.g., an optically clear polymer adhesive) that forms a continuous layer that fills each groove. In some embodiments, the material 1470 has a refractive index within 0.02 of the refractive index of the layer 1410. In some embodiments, the material 1470 is substantially transparent. In some embodiments, the material 1470 is substantially disposed only in the grooves in the layer 1410 (e.g., a portion of the coated material above the grooves may be wiped off). In some embodiments, material 1470 is a conductive material (e.g., a transparent conductive polymer such as poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT polystyrenesulfonate (PEDOT:PSS), or poly(4,4-dioctylcyclopentadithiophene)). EXAMPLES

[0051] Preparation of UV-curable resin 75 parts of PHOTOMER 6210 (available from Cognis, Monheim am Rhein, Germany), 25 parts of SARTOMER SR238, a hexanediol diacrylate (available from Sartomer USA, Exton, PA), and 0.5% of LUCIRIN TPO (available from BASF, Ludwigshafen, Germany) were blended in a high speed mixer and then heated in a 160° F. (71° C.) oven for 24 hours. The compounded resin was then cooled to room temperature.

[0052] Example 1 Forming a VISTAMAXX tool containing a linear channel array A layer of VISTAMAXX3588 (available from ExxonMobile Chemical, Houston TX), a 0.47 mm thick sheet, was placed on a metal tool with linear ribs that were 40 μm wide and 81 μm high with a 125 μm pitch. The size of the film was 250 mm x 280 mm. The sample was pressed in a compression molding machine Rucker PHI 400 ton (City of Industry, CA) to form a molded tool. The molding conditions used were as follows: Temperature: 225°F Low pressure: 6,000 lbs, Time: 1 minute Rise Low Pressure: 80,000lbs, Time: 20 minutes Cools to 100°F nominal

[0053] Preparation of silver transfer layer The transferable seed layer film was prepared on a vacuum coater similar to those described in U.S. Patents 8,658,248 (Anderson et al.) and 7,018,713 (Padiyath et al.). The substrate passed through the coater was in the form of an indefinite length roll of 980 microinch (0.0250 mm) thick, 14 inch (35.6 cm) wide aluminum vapor deposited biaxially oriented polypropylene film commercially available under the tradename TorayFAN PMX2 from Toray Plastics (America), Inc. (North Kingstown, RI). The substrate was then advanced at a constant line speed of 32 fpm (9.8 m / min).

[0054] A tricyclodecane dimethanol diacrylate-based acrylate liquid, available from Sartomer USA (Exton, PA) under the trade name SARTOMER SR833S, was applied by ultrasonic spraying and flash evaporation to produce a 12.5 inch (31.8 cm) wide coating to form a first organic layer on the substrate. The monomer coating was then cured immediately downstream with an electron beam curing gun operated at 7.0 kV and 10.0 mA. The liquid monomer flow to the evaporator was 0.67 mL / min, the nitrogen gas flow rate was 100 sccm, and the evaporator temperature was set at 500° F. (260° C.). The processing drum temperature was 14° F. (−10° C.).

[0055] On top of this first organic layer, a silver reflector layer was deposited by DC sputtering of a >99% silver cathode target. The system was operated at 3 kW with a line speed of 30 fpm (9.1 meters per minute). Two subsequent depositions were performed at the same power and line speed to produce a 90 nm silver layer.

[0056] On top of this silver layer, an oxide layer of silicon aluminum oxide was deposited by AC reactive sputtering. The cathode had a target of Si(90%) / Al(10%) obtained from Soleras Advanced Coatings US, Biddeford, ME. The voltage to the cathode during sputtering was controlled by a feedback control loop that monitored the voltage and controlled the oxygen flow rate so that the voltage remained high and did not crash the target voltage. The system was operated at 16 kW power to deposit a 12 nm thick layer of silicon aluminum oxide on the silver reflector.

[0057] Similar to that described in WO 2018 / 178802 (Gotrik et al.) or WO 2018 / 178803 (Gotrik et al.), the aluminum surface of the TorayFAN PMX2 film and the first organic layer are expected to separate with a 180 peel force of about 7.2 g / in (0.28 g / mm).

[0058] Double-layer transfer procedure The equipment and materials used in this process included a compression molded VISTAMAXX tool sample, a roll of the silver transfer film described above, one roll of 2 mil polyethylene terephthalate (PET) film primed on one side, UV curable resin, one rubber hand roller having a diameter of 0.6 inches (1.52 cm) and a length of 9 inches (22.9 cm), a MASTER HEAT GUN model HG-501A, an OMEGA Type J thermocouple, an RPC Industries (Hampton, VA) UV processor (Model QC120233AN), a plastic transfer pipette, and an 11 inch by 15 inch (27.9 cm by 38.1 cm) metal plate.

[0059] The VISTAMAXX tool was supplied in an 8.5" x 9.5" (21.5 cm x 24.1 cm) sheet and placed on a flat surface with the microstructure facing up. The silver transfer layer film was cut into 10" x 11" (25.4 cm x 27.9 cm) pieces. Hot air from a heat gun was distributed evenly over the surface of the sample, heating it to 150°C. A thermocouple was used to monitor the surface temperature, as the sample would deform at high temperatures. When the desired temperature was reached, the hot air was turned off and the silver transfer layer film was placed face down on the heated VISTAMAXX film. The sample was hand laminated in one pass by applying gentle pressure using a rubber hand roller. The silver transfer layer was immediately pulled away from the VISTAMAXX sample. It was then found to be lightly adhered to the tops of the ribs, but not where the open channels between the ribs were located. The quality of the silver transfer layer transfer was evaluated under an optical microscope and found to be electrically conductive.

[0060] The silver transfer layer was transferred to the VISTAMAXX tool and then to the resin layer as follows: The UV processor was turned on according to the instruction manual with the lamps at their normal setting and the conveyor belt speed at 50 RPM. The VISTAMAXX sample with the silver transfer layer was taped onto a metal plate. With a transfer pipette, a line of UV curable resin was dispensed onto one side of the sample. Primed 2 mil PET film was cut into 10" x 11" (25.4 cm x 27.9 cm) pieces and stacked primed side down on top of the VISTAMAXX sample. The sample was slowly laminated with a rubber hand roller to remove any trapped air bubbles between the VISTAMAXX film and the PET film. The sample was then passed through the UV processor twice under inert gas to complete the curing process. The PET film was slowly removed from the VISTAMAXX tool. The quality of the transfer of the silver transfer layer to the polymer film was evaluated under an optical microscope. The silver transfer layer had completely transferred to the bottom of the UV cured film. Samples were stored at ambient conditions for >24 hours before further analysis.

[0061] RIE removal of the dielectric layer from the transferred layer The dielectric layer (aluminum silicon oxide layer) was removed by reactive ion etching (RIE) using a commercial batch plasma system (Plasma-Therm (Petersburg, FL) Model 3032) with a 26-inch low-power electrode and a central gas exhaust. The chamber was evacuated by a Roots blower (Edwards (Burgess Hill, UK) Model EH1200) backed by a dry mechanical pump (Edwards Model iQDP80). RF power was delivered by a 5 kW 13.56 MHz solid-state generator (RF Plasma Products Model RF50S0) through an impedance matching circuit. The system had a nominal base pressure of 5 mTorr. Gas flow rates were controlled by MKS flow controllers (available from MKS Instruments (Andover, MA)).

[0062] The substrate sample was fixed onto the powered electrode of a batch plasma apparatus. After evacuating the chamber to <10 mTorr, the plasma etch was completed by feeding 500 SCCM of oxygen into the chamber. Once the flow rate had stabilized, rf power was applied to the electrode to generate a plasma at 1000 W. The plasma was left on for 15 seconds.

[0063] After the plasma treatment was completed, the chamber was vented to atmosphere and the substrate was removed from the chamber.

[0064] Copper plating in the groove The RIE etched films were rinsed with DI water and placed in a solution made of copper sulfate (29 oz / gal) and sulfuric acid (8 oz / gal). The solution flow rate was 11 gal / min. Plating was performed in potentiostatic mode using a DYNATRONIX (Amery WI), Model DPR20-250-500 power supply. The solution temperature was 21°C. Plating was controlled at 1.6 V for 25 minutes. After plating, the parts were rinsed, dried, and examined under a microscope. It was confirmed that copper was plated onto the silver transfer layer where the dielectric layer had been removed by the RIE etch.

[0065] Examples 2 to 3 Procedure for Seeding Tools with NovaCentrix Conductive Ink The conductive silver ink was applied by hand printing onto the tops of the ribs on a structured nickel tool. The nickel tool had a hexagonal portion and a triangular portion (e.g., corresponding to a busbar portion). The hexagonal portion included a hexagon with a side-to-side width of 1 mm, a rib width of 25 micrometers, and a rib height of 25 micrometers. The triangular portion included a hexagon with the same shape as the hexagonal portion and included additional ribs extending from each vertex of the hexagon to the center of the hexagon. The conductive silver ink was applied as follows: (1) An ink source was prepared by coating a continuous layer of NovaCentrix (Round Rock, TX) DSPI-420 Silver Dispersing Ink onto a PET film with a number 5 bar coater (Mayer Rod) to give a wet film thickness of approximately 10 μm. (2) A flat photopolymer flexographic printing plate was mounted on an approximately 4 inch diameter mandrel with 3M E1120 CUSHION-MOUNT tape (available from 3M Company, St. Paul, MN) and immediately hand-rolled onto the coating of (1), transferring a portion of the silver ink to the surface of the flexographic printing plate before it dried. (3) The flexographic printing plate from (2) was then immediately rolled by hand onto the surface of the nickel tool, transferring the silver ink only to the upper relief surface of the structured nickel tool before the silver ink dried on the printing plate surface.

[0066] The silver ink was then dried and sintered at 240° F. for at least 2 minutes using a Despatch (Minneapolis, MN) solvent-rated oven (Model LFC1-38-1).

[0067] Film formation procedure The equipment and materials used in this process included a Fusion UV Processor running at approximately 10 feet / minute and cured with halogen bulbs, a ChemInstruments (Chester Township, Ohio) laminator (Model: Hot Roll Laminator), and 5 mil PET film that was primed on both sides.

[0068] To begin the process, a piece of PET film was cut to approximately 6.5" x 7.5" (16.5 cm x 19.1 cm) to cover the entire surface of the tool. The UV processor was turned on according to the operating instructions with the lamps at their normal settings and the conveyor belt speed at 50 RPM. Nitrogen gas was also supplied to the UV processor to assist in the curing process.

[0069] Using a plastic transfer pipette, UV-curable resin was dispensed onto the edge of the tool. A PET film was placed over the top of the tool and held in place by taping one end to the tool. The sample was processed through a laminator which spread the resin evenly across the tool.

[0070] The sample was then passed through a UV processor twice to ensure complete curing of the resin. The sample was removed from the tool by gently pulling it at a 90° angle. The resulting film was a reverse image microstructure from the tool, with the sintered silver seed layer at the bottom of the grooves.

[0071] Copper plating procedure The replicated films described above were placed in an acid copper plating solution made of copper sulfate and sulfuric acid. The solution flow rate was 80 liters / min. Plating was performed in potentiostatic mode using a power supply from DYNATRONIX (Amery WI), Model CRS12-200. The solution temperature was 21°C. Plating was controlled at 1.4V for 12.5 minutes and 10 minutes for Examples 2 and 3, respectively. After plating, the parts were rinsed, dried and examined under a microscope. It was confirmed that copper was plated onto the seed layer in the grooves to form a fine pattern of conductive traces.

[0072] In Example 2, in the hexagonal portions, the traces extended approximately 15-22 micrometers above the top surface of the UV-cured layer, and in the triangular portions, the tops of the traces were approximately level with the top surface of the UV-cured layer.

[0073] In Example 3, in the hexagonal portions, the tops of the traces were approximately level with the top surface of the UV-cured layer by about 20 micrometers, and in the triangular portions, the tops of the traces were recessed from the top surface of the UV-cured layer by about 15-21 micrometers.

[0074] All references, patents, or patent applications referenced above are hereby incorporated by reference in their entirety. In the event of any inconsistency or contradiction between any of the incorporated references and this application, the information in the foregoing description shall prevail.

[0075] Descriptions of elements in the figures should be understood to apply equally to corresponding elements in other figures unless otherwise indicated. Although specific embodiments have been illustrated and described herein, those skilled in the art will appreciate that the specific embodiments illustrated and described may be replaced by various alternative and / or equivalent embodiments without departing from the scope of the present disclosure. The present application is intended to cover any adaptations or variations of the specific embodiments discussed herein. Accordingly, the present disclosure is limited only by the claims and their equivalents. In the following, exemplary embodiments are presented. [Item 1] A substrate comprising a single layer; a micropattern of conductive traces at least partially embedded in the single layer, each conductive trace extending along a longitudinal direction of the conductive trace; a conductive seed layer having a top major surface and an opposing bottom major surface in direct contact with said monolayer; a single conductor disposed on the upper major surface of the conductive seed layer, the single conductor and the conductive seed layer differing in at least one of composition or crystal morphology, the single conductor having lateral sidewalls, at least a majority of a total area of ​​the lateral sidewalls being in direct contact with the single layer; a fine pattern of conductive traces comprising: 1. A patterned conductive article comprising: [Item 2] Item 2. The patterned conductive article of item 1, wherein the micropattern of conductive traces has an open area ratio in the range of 80% to 99.95%. [Item 3] 3. The patterned conductive article of item 1 or 2, wherein each conductive trace of at least a majority of the conductive traces in the micropattern has a width W along a width direction perpendicular to the longitudinal direction and a thickness direction of the single layer, and a thickness T along the thickness direction, where T / W is at least 0.8. [Item 4] 4. The patterned conductive article of any one of the preceding claims, wherein the micropattern of conductive traces is at least partially disposed within a micropattern of grooves, the micropattern of grooves comprising at least one groove substantially filled with a non-conductive material. [Item 5] 5. The patterned conductive article of any one of the preceding claims, wherein the conductive seed layer comprises a cured conductive ink or a cured conductive coating. [Item 6] Item 6. The patterned conductive article of any one of the previous items, wherein the conductive seed layer comprises a conductive layer disposed on a crosslinked polymer layer. [Item 7] A patterned conductive article comprising: a substrate having a first groove therein, the first groove extending along a longitudinal direction and having a bottom surface and a side surface; a conductive seed layer disposed within the first groove; a single conductor disposed at least partially within the first groove; A patterned conductive article comprising: A patterned conductive article, in at least one cross section perpendicular to the longitudinal direction of the first groove, the conductive seed layer covers at least half of the bottom surface of the first groove, the single conductor covers the conductive seed layer and at least half of the side surfaces of the first groove, each of the side surfaces and the single conductor define a conductor-insulator interface between each of the side surfaces and the single conductor, and the single conductor and the conductive seed layer define a conductor-conductor interface between the single conductor and the conductive seed layer. [Item 8] Item 8. The patterned conductive article of item 7, wherein the substrate comprises a micropattern of grooves therein, the micropattern of grooves comprising the first groove. [Item 9] Item 9. The patterned conductive article of item 8, wherein the micropattern of grooves comprises second grooves, and in at least one cross-section perpendicular to the length of the second grooves, the second grooves are substantially filled with a substantially transparent material. [Item 10] a substrate having a first groove therein, the first groove having a bottom surface and a side surface; a conductive seed layer disposed within the first groove; a single conductor disposed at least partially within the first groove; Equipped with 1. A patterned conductive article, comprising: a conductive seed layer covering at least half of the bottom surface of the first groove; a single conductor covering the conductive seed layer and at least half of the side surfaces of the first groove; and, in a plane through the single conductor that is parallel to and away from the conductive seed layer, the single conductor has a first smaller line edge roughness at a first interface with the side surfaces and the conductive seed layer has a second larger line edge roughness at an edge of the conductive seed layer. [Item 11] a substrate having a first groove therein, the first groove extending along a longitudinal direction and having a bottom surface and a side surface; a single conductive layer disposed within the first groove; Equipped with A patterned conductive article, wherein in at least one cross section perpendicular to the longitudinal direction of the first groove, the conductive layer covers at least half of the bottom surface of the first groove, and at least half of the side surfaces of the first groove are not in contact with a material having the same composition as the single conductive layer. [Item 12] Item 12. The patterned conductive article of item 11, wherein a non-metallic material is at least partially disposed within the first groove, and in the at least one cross-section of the first groove, the non-metallic material covers at least a majority of the side of the first groove. [Item 13] 13. The patterned conductive article of any one of the preceding claims, which is at least one of an antenna, a heater, an electromagnetic interference shield, a static dissipative component, a sensor, or an electrode. [Item 14] Providing a tool having at least one ridge; disposing the conductive layer on a top surface of the first portion of the at least one ridge such that at least half of a total area of ​​a side surface of the first portion of the at least one ridge does not include the conductive layer; placing a resin on the tool after the step of placing the conductive layer; solidifying the resin to form a polymer layer having at least one groove corresponding to the at least one ridge; removing the polymer layer and the conductive layer from the tool such that the conductive layer is disposed on a bottom surface of the at least one groove; A method for producing a patterned conductive article, comprising: [Item 15] Item 15. The method of claim 14, further comprising depositing a conductive material in the at least one trench such that the conductive material covers the conductive layer.

Claims

1. A substrate comprising a single layer; a micropattern of conductive traces at least partially embedded in the single layer, each conductive trace extending along a longitudinal direction of the conductive trace; a conductive seed layer having a top major surface and an opposing bottom major surface in direct contact with said monolayer; a single conductor disposed on the upper major surface of the conductive seed layer, the single conductor and the conductive seed layer differing in at least one of composition or crystal morphology, the single conductor having lateral sidewalls, at least a majority of a total area of ​​the lateral sidewalls being in direct contact with the single layer; a fine pattern of conductive traces comprising: Equipped with A patterned conductive article for an antenna, a heater, an electromagnetic interference shield, a static dissipative component, or a touch sensor, wherein the fine pattern of conductive traces has an open area percentage in the range of 80% to 99.95%.

2. 10. The patterned conductive article of claim 1, wherein the micropattern of conductive traces has an open area percentage in the range of 90% to 99.9%.

3. 3. The patterned conductive article of claim 1 or 2, wherein each conductive trace of at least a majority of the conductive traces in the micropattern has a width W along a width direction perpendicular to the longitudinal direction and the thickness direction of the single layer, and a thickness T along the thickness direction, where T / W is at least 0.

8.

4. 4. The patterned conductive article of any one of claims 1 to 3, wherein the micropattern of conductive traces is at least partially disposed within a micropattern of grooves, the micropattern of grooves comprising at least one groove substantially filled with a non-conductive material.

5. 5. The patterned conductive article of claim 1, wherein the conductive seed layer comprises a cured conductive ink or a cured conductive coating.

6. 6. The patterned conductive article of claim 1, wherein the conductive seed layer comprises a conductive layer disposed on a crosslinked polymer layer.

7. A patterned conductive article comprising: a substrate having a first groove therein, the first groove extending along a longitudinal direction and having a bottom surface and a side surface; a conductive seed layer disposed within the first trench; a single conductor disposed at least partially within the first groove; A patterned conductive article comprising: in at least one cross section perpendicular to the longitudinal direction of the first groove, the conductive seed layer covers at least a majority of the bottom surface of the first groove, the single conductor covers the conductive seed layer and at least a majority of the side surfaces of the first groove, each of the side surfaces and the single conductor define a conductor-insulator interface between each of the side surfaces and the single conductor, and the single conductor and the conductive seed layer define a conductor-conductor interface between the single conductor and the conductive seed layer; A patterned conductive article for an antenna, a heater, an electromagnetic interference shield, a static dissipative component, or a touch sensor, wherein the patterned conductive article has an open area ratio in the range of 80% to 99.95%.

8. 8. The patterned conductive article of claim 7, wherein the substrate comprises a micropattern of grooves therein, the micropattern of grooves comprising the first groove.

9. 9. The patterned conductive article of claim 8, wherein the micropattern of grooves comprises second grooves, and in at least one cross-section perpendicular to the length of the second grooves, the second grooves are substantially filled with a substantially transparent material.

10. a substrate having a first groove therein, the first groove having a bottom surface and a side surface; a conductive seed layer disposed within the first trench; a single conductor disposed at least partially within the first groove; A patterned conductive article comprising: the conductive seed layer covers at least half of the bottom surface of the first trench, the single conductor covers the conductive seed layer and at least half of the side surfaces of the first trench, and is parallel to and spaced from the conductive seed layer, in a plane through the single conductor, the single conductor has a first smaller line edge roughness at a first interface with the side surfaces, and the conductive seed layer has a second larger line edge roughness at an edge of the conductive seed layer; A patterned conductive article, wherein said patterned conductive article has an open area percentage in the range of 80% to 99.95%.

11. a substrate having a first groove therein, the first groove extending along a longitudinal direction and having a bottom surface and a side surface; a single conductive layer disposed within the first groove; A patterned conductive article comprising: In at least one cross section perpendicular to the longitudinal direction of the first groove, the single conductive layer covers at least a majority of the bottom surface of the first groove, and at least a majority of the side surface of the first groove is not in contact with a material having the same composition as a composition of the single conductive layer; A patterned conductive article for an antenna, a heater, an electromagnetic interference shield, a static dissipative component, or a touch sensor, wherein the patterned conductive article has an open area ratio in the range of 80% to 99.95%.

12. 12. The patterned conductive article of claim 11, wherein a non-metallic material is at least partially disposed within the first groove, and in the at least one cross-section of the first groove, the non-metallic material covers at least a majority of the side of the first groove.

13. 13. The patterned conductive article of any one of claims 1 to 12, which is at least one of an antenna, a heater, an electromagnetic interference shield, a static dissipative component, a sensor, or an electrode.

14. Providing a tool having at least one ridge; disposing the conductive layer on a top surface of the first portion of the at least one ridge such that at least half of a total area of ​​a side surface of the first portion of the at least one ridge does not include the conductive layer; placing a resin on the tool after the step of placing the conductive layer; solidifying the resin to form a polymer layer having at least one groove corresponding to the at least one ridge; removing the polymer layer and the conductive layer from the tool such that the conductive layer is disposed on a bottom surface of the at least one groove; Including, the patterned conductive article having an open area percentage in the range of 80% to 99.95%; A method for making a patterned conductive article for an antenna, a heater, an electromagnetic interference shield, a static dissipative component, or a touch sensor.

15. The method of claim 14 , further comprising depositing a conductive material in the at least one trench such that the conductive material covers the conductive layer.

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