Patterned articles containing metal bodies

Abstract

The patterned article includes a polymer layer having opposite first and second major surfaces and defining a plurality of through openings therein. For each through opening of at least the sub-plurality of through openings, a metal body is disposed within the through opening. The metal body has a first outermost surface, an opposite second outermost surface, and at least one lateral sidewall extending therebetween. The first outermost surface of the metal body is substantially coplanar with the first major surface of the polymer layer. Each lateral sidewall extends from the first outermost surface of the metal body toward or up to, but not beyond, the second major surface of the polymer layer. The metal body is substantially coextensive with the through opening in at least one cross section parallel to the polymer layer. The metal bodies can be electrically insulated from one another.

Description

Background Art

[0001] Articles useful as antennas, EMI shields, or touch sensors may include a fine pattern of metal wiring formed on a substrate by photolithography.

Summary of the Invention

[0002] The present disclosure generally relates to a patterned article including a metal body. The metal bodies may be electrically insulated from each other or may include a conductive layer that electrically connects the metal bodies to each other.

[0003] In some aspects of the present specification, a patterned article is provided that includes a polymer layer having opposed first and second major surfaces and defining a plurality of through openings therein. For each of at least a first plurality of lower through openings, a metal body is disposed within the through opening. The metal body has a first outermost surface, an opposite second outermost surface, and at least one lateral sidewall extending therebetween. The first outermost surface of the metal body is substantially flush with the first major surface of the polymer layer. Each lateral sidewall extends from the first outermost surface of the metal body toward or to the second major surface of the polymer layer but does not extend beyond the second major surface. The metal body can have a spread substantially the same as that of the through opening in at least one cross-section parallel to the polymer layer. The metal bodies can be electrically insulated from each other.

[0004] In some aspects of this specification, a patterned article is provided which includes a polymer layer comprising a first structured main surface and a second main surface opposite to it, defining a plurality of through-openings internally. For at least one of the first lower through-openings, a metal body is positioned within the through-opening. The metal body has a first outermost surface adjacent to the first main surface of the polymer layer, a second outermost surface opposite to it, and at least one lateral sidewall extending between them. Each lateral sidewall extends from the first outermost surface of the metal body toward or to the second main surface of the polymer layer, but not beyond the second main surface. The metal body may have substantially the same extent as the through-opening in at least one cross-section parallel to the polymer layer. The metal bodies may be electrically insulated from one another.

[0005] In some aspects of this specification, patterned articles are provided, comprising a single polymer layer disposed on a conductive layer. The single polymer layer comprises a first main surface facing the conductive layer and a second main surface on the opposite side. The single polymer layer defines a plurality of through-openings internally. For each of at least the first lower through-openings, a single metal body is disposed within the through-opening. The single metal body includes at least one lateral sidewall extending between the outermost main surfaces of the single metal body in opposite directions. Each lateral sidewall extends from the conductive layer toward or to the second main surface of the single polymer layer, but not beyond the second main surface. The single metal body may have substantially the same extent as the through-opening in at least one cross-section parallel to the single polymer layer. The single metal body may fill at least 10% of the volume of the through-opening.

[0006] In some aspects of this specification, a method for manufacturing a patterned article is provided. This method includes, in order, the steps of: preparing a conductive layer; forming a polymer layer on the conductive layer having a plurality of through-holes defined therein; depositing metal bodies in each of at least a first plurality of lower through-holes such that the metal bodies are in contact with the conductive layer; and optionally removing the conductive layer to electrically insulate the metal bodies from each other.

[0007] These and other aspects will become apparent from the detailed description below. However, in no case should this brief summary be construed as limiting the subject matter of the claims. [Brief explanation of the drawing]

[0008] [Figure 1A] This is a schematic diagram of the process in an exemplary manufacturing method for patterned articles. [Figure 1B] Figure 1A is a schematic cross-sectional view of an exemplary article that can be manufactured by the method shown. [Figure 1C] Figure 1A is a schematic cross-sectional view of an exemplary article that can be manufactured by the method shown. [Figure 1D] This is a schematic cross-sectional view of a portion of an exemplary patterned article. [Figure 1E] This is a schematic cross-sectional view of a portion of another exemplary patterned article. [Figure 2A] This is a schematic cross-sectional view of an exemplary patterned article. [Figure 2B] This is a schematic cross-sectional view of an exemplary patterned article. [Figure 3A] This is a schematic diagram of exemplary tools and exemplary methods for forming a polymer layer. [Figure 3B] This is a schematic diagram of a continuous manufacturing method for patterned articles. [Figure 4A] This is a schematic diagram of a process in an exemplary method for manufacturing a patterned article containing a polymer layer having a structured surface. [Figure 4B] Figure 4A is a schematic cross-sectional view of an exemplary article that can be manufactured by the method shown. [Figure 4C] Figure 4A is a schematic cross-sectional view of an exemplary article that can be manufactured by the method shown. [Figure 5A] This is a schematic diagram of a process in an exemplary method for manufacturing a patterned article, which may include the step of placing a patterned mask layer on a conductive layer. [Figure 5B] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 5A. [Figure 5C] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 5A. [Figure 5D] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 5A. [Figure 5E] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 5A. [Figure 6A] A schematic diagram of steps in an exemplary method of manufacturing a patterned article that may include the step of disposing a patterned mask layer on a polymer layer. [Figure 6B] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 6A. [Figure 6C] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 6A. [Figure 7A] A schematic diagram of steps in an exemplary method of manufacturing a patterned article that may include the step of utilizing a patterned conductive layer. [Figure 7B] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 7A. [Figure 7C] A schematic cross-sectional view of an exemplary article that can be manufactured by the method of FIG. 7A. [Figure 8] A diagram schematically showing an exemplary method of forming an exemplary patterned article including the placement of a patterned metal body. [Figure 9] A schematic cross-sectional view of a portion of a patterned article showing an exemplary metal body. [Figure 10A] A schematic top view of an exemplary patterned article. [Figure 10B] A schematic top view of an exemplary patterned article. [Figure 10C] A schematic top view of an exemplary patterned article. [Figure 11A]Schematic top view of a portion of an exemplary patterned article including a metal body including metal wiring. [Figure 11B] Schematic cross-sectional view of a portion of a patterned article schematically showing an exemplary metal wiring. [Figure 12] Schematic top view of an exemplary patterned article including a metal body disposed within several through openings. [Figure 13] Schematic cross-sectional view of an exemplary patterned article including a polymer layer disposed on an optical film.

Best Mode for Carrying Out the Invention

[0009] In the following description, reference is made to the accompanying drawings which form a part hereof and in which various embodiments are shown by way of illustration. The drawings are not necessarily to scale. It is to be understood that other embodiments may be contemplated and may be practiced without departing from the scope or spirit of this specification. Accordingly, the following mode for carrying out the invention is not to be construed in a limiting sense.

[0010] In some embodiments, the patterned article includes metal bodies that are electrically insulated from each other. In other embodiments, the patterned article includes metal bodies that are electrically connected to each other only by one conductive layer. The metal bodies can be arranged to provide any suitable function. For example, in some embodiments, the metal bodies can be or include an antenna array, such as a retroreflective antenna array (see, e.g., FIGS. 10A - 10C and FIG. 12), or define an antenna that includes an antenna array. As yet another example, electromagnetic interference (EMI) shields, electrostatic dissipation components, heaters, electrodes, or sensors can be mentioned. Those devices may be provided as an array of those devices, and the array of devices can then be singulated and provided as individual devices.

[0011] In some embodiments, the metal body is patterned. For example, the metal body may include or be formed from a fine pattern of metal wiring (e.g., the wiring may have a width of at least 100 nm and less than 1 mm). In some embodiments, at least some (e.g., at least a majority, or possibly all) of the metal body include a fine pattern of metal wiring. The use of a fine pattern of metal wiring makes it possible to obtain high light transmittance of the patterned article, which may be desired in some applications. In other embodiments, the metal body is formed from an unpatterned metal and may have low light transmittance.

[0012] Conductive elements, such as conductive elements containing fine patterns of conductive wiring, can be formed on a substrate using a photolithography process. According to some embodiments of this specification, processes have been developed that enable the formation of conductive elements (e.g., metallic bodies) at least partially within a substrate without the use of photolithography. In some embodiments, the processes described herein are less expensive and / or easier to implement than conventional photolithography processes. In some embodiments, the process can form wiring having a large aspect ratio (thickness divided by width), for example (e.g., at least 0.8). A large aspect ratio may be desirable in applications where high transparency and high electrical conductance are desired. For example, transparency can be increased by increasing the aperture area ratio, but this reduces electrical conductance if the wiring thickness is fixed. Therefore, the wiring can be made thicker to increase electrical conductance, which can result in a higher aspect ratio. In some embodiments, patterned articles may be used at relatively high operating frequencies (for example, a patterned article may be an antenna designed to operate at microwave frequencies), in which case, for example, the skin depth of the wiring material is smaller than the width of the wiring. By using a high aspect ratio, the surface area of ​​the wiring increases for a given wiring width, resulting in increased conductor usage (and thus increased electrical conductance at operating frequencies) compared to wiring with a lower aspect ratio for the same wiring width (for example, conventionally formed by lithography or printing).

[0013] Conventionally, when metal bodies are electrically insulated from one another, it has been difficult to form metal bodies on a substrate by electroplating because it is difficult to provide a common temporary ground in this case. According to some embodiments of this specification, wiring or metal bodies are formed by plating (e.g., electroplating onto a conductive layer) onto a conductive layer located at the bottom of a through-opening in a substrate (e.g., a polymer layer). The conductive layer can provide a substantially common potential (e.g., a temporary ground plane) for electroplating and can be removed after plating, resulting in an electrically insulated metal body. Plating onto a conductive layer located on the bottom of a through-opening but not on the sidewall has been found to improve control over the profile of the wiring or metal body compared to, for example, plating inside a cavity where the conductive layer is also on the bottom and sidewall of the cavity. For example, if the conductive layer is on the sidewall, the plating will result in the metal being formed on top of the conductive layer on the sidewall, which may result in an excess deposition of metal on the upper surface of the substrate beyond the edge of the cavity or through-opening. Such excessive deposition can reduce light transmittance through patterned articles, for example, and can therefore be problematic for patterned articles manufactured by conventional processes, especially when a high aspect ratio is desired.

[0014] Conductive members (e.g., conductors, conductive layers, conductive wiring, conductive elements, or conductive materials) mean electrically conductive members unless otherwise specified. Conductive members are, for example, less than 1 ohm meter (Ω·m), less than 0.01 ohm meter, 10 -4 Less than ohms or 10 -6 It may have an electrical resistivity of less than ohms. Unless otherwise specified, nonconductive materials refer to electrically nonconductive materials. Nonconductive materials include, for example, those with an electrical resistivity greater than 100 ohms. 4 Larger than an ohm meter, 10 6 Greater than an ohm meter, or 10 8 It may have an electrical resistivity greater than ohms. Unless otherwise specified, electrical resistivity refers to direct current (DC) resistivity.

[0015] Spatial terms, including but not limited to “bottom,” “lower part,” “upper part,” “downward,” “below,” “above,” and “top,” are used herein to facilitate explanations of spatial relationships. Such spatial terms encompass different orientations of an article in use or operation, in addition to the specific orientations depicted in the figures and described herein.

[0016] Figure 1A is a schematic diagram of the steps in a method for manufacturing patterned articles 101, 100, or 100' according to several embodiments. Figures 1B and 1C are schematic cross-sectional views of exemplary articles that can be manufactured by the method of Figure 1A. The method includes, in order, the steps of: preparing a conductive layer 150; forming a polymer layer 110 on the conductive layer 150 that defines a plurality of through-holes 114 inside it; depositing metal bodies 120 in each of at least a first plurality of lower through-holes such that the metal bodies 120 are in contact with the conductive layer 150; and optionally removing the conductive layer 150 to electrically insulate the metal bodies 120 from each other. For example, the plurality of lower through-holes is at least two through-holes but fewer than all of the through-holes. The phrase "at least a plurality of lower through-holes" includes both the plurality of lower through-holes and all of the plurality of through-holes. In Figures 1A to 1C, the metal bodies are located in each through-hole. Embodiments in which metal bodies are placed in a first set of lower through-openings but not in a second set of lower through-openings are schematically shown, for example, in Figures 5A to 7C. The conductive layer 150 can optionally be placed on the substrate 151. The conductive layer 150 provides a substantially common potential plane (e.g., a ground plane) on which the metal bodies 120 can be deposited, for example, by electroplating. In embodiments where a patterned article 100 or 100' is desired, the conductive layer 150 can be removed from the polymer layer 110, for example, by peeling or etching. To help peel the conductive layer 150 from the article, an additional layer or film can optionally be laminated onto the surface 112 of the polymer layer 110. In embodiments where a patterned article 101 is desired, the conductive layer 150, and optionally the substrate 151, may be retained. Regardless of whether the conductive layer 150 is retained, the metal body 120 may partially fill the through-opening 114 as schematically shown in Figures 1A and 1B, or the metal body 120 may fill the through-opening 114 as schematically shown in Figure 1C, or a portion of the metal body 120 may extend beyond the surface 112 as schematically shown in Figure 1D.

[0017] In some embodiments, the patterned article 101 includes a (e.g., single) polymer layer 110 disposed on a conductive layer 150, the polymer layer 110 including a first main surface 111 facing the conductive layer 150 and a second main surface 112 on the opposite side. The polymer layer defines a plurality of through-openings 114 inside. For at least one of the first lower through-openings, a (e.g., single) metal body 120 is disposed within the through-opening, the metal body 120 including at least one lateral sidewall 123 extending between the opposite outermost surfaces 121, 122 of the metal body 120 within the through-opening. Each lateral sidewall 123 extends from the conductive layer 150 toward or to the second main surface 112 of the polymer layer 110, but not beyond the second main surface 112. The metal bodies 120 may have the same or substantially the same extent as the through-openings 114 in at least one cross section parallel to the polymer layer 110, as will be further described elsewhere. In some embodiments, the metal bodies 120 are electrically connected to each other only by the conductive layer 150. In other words, if the conductive layer 150 is removed, the metal bodies 120 will be electrically insulated from each other. The lateral sidewalls are the sidewalls of the metal bodies 120 (the sides along the direction perpendicular to the thickness direction of the patterned article, such as the direction in the xy plane), while the outermost surfaces 121 and 122 may be the bottom and top surfaces of the metal bodies 120 (the surfaces having the smallest and largest z-coordinate values, or the surfaces on both sides along the thickness direction of the patterned article), respectively.

[0018] A single layer or body is a layer or body consisting of one continuous layer. A single layer or body does not have adjacent layers or sections separated by an interface. Alternatively, a single layer or body may also be called a monolithic layer or monolithic body. In some embodiments, a metal body is a single metal body. In other embodiments, a metal body may be a non-single metal body. In some embodiments, a polymer layer is a single polymer layer. In other embodiments, a polymer layer may be a non-single polymer layer. Any of the metal bodies described herein may be a single metal body unless otherwise stated or indicated to be clearly different in context. Any of the polymer layers described herein may be a single polymer layer unless otherwise stated or indicated to be clearly different in context. In some embodiments, a metal body in a through-opening includes a single metal body and one or more metal layers disposed on the single metal body, as further described elsewhere in this specification.

[0019] In some embodiments, as further described elsewhere in this specification, forming the polymer layer 110 involves placing a resin between a structuring tool (see, for example, structuring tools 160 and 260 schematically shown in Figures 3A and 3B) and the conductive layer 150, and curing or solidifying the resin. In some embodiments, curing or solidifying the resin results in a plurality of partial through-openings 114a corresponding to a plurality of through-openings 114, and this process further includes etching (e.g., plasma etching) the cured or solidified resin 110a to remove a portion 115 of the cured or solidified resin 110a adjacent to the conductive layer 150 within the partial through-openings 114a. Etching may also remove the top of the cured or solidified resin 110a, resulting in a reduction in the thickness of the polymer layer 110. The portion 115 may be referred to as a land portion.

[0020] In some embodiments, forming the polymer layer 110 involves compression molding the polymer. For example, tools 160 or 260, as described elsewhere, can be used when compression molding the polymer. A subsequent etching step may be used to remove portions of the compression-molded polymer adjacent to the conductive layer 150 (e.g., corresponding to portion 115).

[0021] Figures 1B and 1C are schematic cross-sectional views of patterned articles 100 and 100' according to several embodiments. Patterned article 100 (corresponding to 100') includes a polymer layer 110 comprising a first main surface 111 and a second main surface 112 facing opposite directions, defining a plurality of through-openings 114 inside. For at least one of the first lower through-openings 114, a metal body 120 (corresponding to 120') is positioned within the through-opening 114. The metal body 120 (corresponding to 120') has a first outermost surface 121 (corresponding to 121'), a second outermost surface 122 (corresponding to 122') on the opposite side, and at least one lateral side wall 123 (corresponding to 123') extending between them. The first outermost surface 121 (corresponding to 121') of the metal body 120 (corresponding to 120') is substantially coplanar with the first main surface 111 of the polymer layer 110 (for example, nominally coplanar or coplanar within about 20%, 10%, or 5% of the smaller of the thickness of the polymer layer and the minimum diameter or width of the metal body). Each lateral side wall 123 (corresponding to 123') extends from the first outermost surface 121 (corresponding to 121') of the metal body 120 (corresponding to 120') toward or to the second main surface 112 of the polymer layer 110, but not beyond the second main surface 112. As will be further explained elsewhere (see, for example, Figure 9), the metal body 120 (corresponding to 120') may have the same or substantially the same extent as the through-opening 114 in at least one cross-section parallel to the polymer layer (e.g., parallel to the xy-plane). In some embodiments, the metal bodies 120 (corresponding to 120') are electrically insulated from each other. In the embodiment of Figure 1B, the side wall 123 of the metal body 120 extends toward the second main surface 112 but does not extend beyond the second main surface 112. In the embodiment of Figure 1C, the side wall 123' of the metal body 120' extends toward the second main surface 112 but does not extend beyond the second main surface 112.The metal body 120 (corresponding to 120') may include one lateral side wall 123 (corresponding to 123') along the circumference of the metal body (for example, one side wall of a cylindrical metal body), or it may include two lateral side walls 123 (corresponding to 123') (for example, the side walls on both sides of a metal body placed in a groove), or it may include more lateral side walls 123 (corresponding to 123') (for example, four side walls of a metal body having a square or rectangular cross-section).

[0022] In some embodiments, the metal bodies 120 and 120' are electrically insulated from each other. For example, the polymer layer 110 is electrically nonconductive, and the metal bodies 120 and 120' can be electrically insulated from it. In some embodiments, the metal bodies 120 and 120' are electrically insulated from the first main surface 111 and the second main surface 112 of the polymer layer 110. That is, the metal bodies 120 and 120' can be electrically insulated from any conductive element placed on either the first main surface 111 or the second main surface 112.

[0023] In some embodiments, for at least a majority of the metal bodies, the second outermost surface 122 of the metal body 120 is located between the first main surface 111 and the second main surface 112 of the polymer layer 110.

[0024] In some embodiments, for at least a majority of the metal bodies, the second outermost surface 122' of the metal body 120' is substantially coplanar with the second main surface 112 of the polymer layer 110.

[0025] In some embodiments, a portion of the metal body extends beyond the second main surface of the polymer layer. Figure 1D is a schematic cross-sectional view of a portion of a patterned article according to some embodiments, showing a metal body 120'' having a first outermost surface 121'' substantially coplanar with the first main surface 111 of the polymer layer 110, and a second outermost surface 122'' at least partially located outside the polymer layer 110. In the illustrated embodiment, a lateral side wall 123'' extends substantially from the first outermost surface 121'' of the metal body 120'' to the second main surface 112 of the polymer layer 110.

[0026] Figure 1E is a schematic cross-sectional view of a portion of a patterned article according to several embodiments, showing a metal body 120''' having a first outermost surface 121''' and a second outermost surface 122''' which are substantially coplanar with the first main surface 111 of the polymer layer 110, the second outermost surface 122''' may be substantially coplanar with the second main surface 112 as shown, or it may be between the first main surface 111 and the second main surface 112 as shown in Figure 1B, for example, or it may be located at least partially outside the polymer layer 110 as shown in Figure 1D, for example. In the illustrated embodiment, the lateral sidewall 123''' of the metal body 120''' extends substantially from the first outermost surface 121''' of the metal body 120''' to the second main surface 112 of the polymer layer 110. The metal body 120''' includes a single metal body 120a including a first outermost surface 121'' and one or more metal layers 120b including a second outermost surface 122''. The single metal body 120a has side walls that extend from the first outermost surface 121'' (or from the conductive layer 150 in embodiments where a conductive layer 150 is present) toward the second main surface of the single polymer layer, but not to the second main surface. In some embodiments, the volume of the single metal body 120a is at least 50%, at least 60%, at least 70%, or at least 80% of the volume of the metal body 120'''. One or more metal layers 120b may be included so that the metal body 120''' has a particular color in order to "hide" the conductor for aesthetic reasons. For example, one or more layers 120b may give black, or in some graphic applications, one or more layers 120b may give white to match the graphic.

[0027] In some embodiments, the metal body within the through-opening (e.g., a single metal body 120a, or a metal body 120'' including one or more metal layers 120b arranged on a single metal body 120a) fills at least 10%, at least 30%, at least 50%, at least 70%, or at least 80% of the volume of the through-opening. For example, the metal body can fill 10% to 100% or 30% to 80% of the volume of the through-opening.

[0028] In some embodiments, the patterned article (e.g., 101, 100, 100') further includes a dielectric layer disposed on a second main surface of the polymer layer and covering a metal body. In some such embodiments, or other embodiments, the metal body is electrically insulated from the second main surface of the polymer layer. In some such embodiments, or other embodiments, the patterned article further includes a dielectric layer disposed on a first main surface of the polymer layer and covering a metal body. In some such embodiments, or other embodiments, the metal body is electrically insulated from the first main surface of the polymer layer. The dielectric layer is an electrically nonconductive layer having a dielectric constant (relative permittivity) higher than air for at least one frequency (e.g., the operating frequency of the patterned article and / or a fixed reference frequency such as 1 GHz). For example, the dielectric constant can be at least 1.1, at least 1.2, or at least 1.5 at 1 GHz.

[0029] Figures 2A and 2B are schematic cross-sectional views of patterned articles 102 and 102' according to several embodiments, respectively. Patterned articles 102 and 102' may correspond to patterned articles 100 and 100', respectively, except that patterned articles 102 and 102' include a first dielectric layer 131 disposed on a first main surface 111 of the polymer layer 110 and a second dielectric layer 132 disposed on a second main surface 112 of the polymer layer 110. In some embodiments, one of the first dielectric layer 131 and the second dielectric layer 132 is omitted. For example, the second dielectric layer 132 may be included on the second main surface 112 of the polymer layer 110 in patterned article 101, while the conductive layer 150 may be retained and the first dielectric layer 131 may be omitted. In some embodiments, the patterned article 102 (corresponding to 102') includes a dielectric layer 132 disposed on a second main surface 112 of the polymer layer 110 and covering a metal body 120 (corresponding to 120'). In some such embodiments, or in other embodiments, the patterned article 102 (corresponding to 102') includes a dielectric layer 131 disposed on a first main surface 111 of the polymer layer 110 and covering a metal body 120 (corresponding to 120').

[0030] The dielectric layers 131 and / or 132 may be polymers (e.g., polymer encapsulants). In embodiments including a second dielectric layer 132, the second dielectric layer 132 can be added to the article at any point after the metal bodies 120, 120', 120'' have been formed. For example, the second dielectric layer 132 may be added before or after the conductive layer 150 has been removed. In some embodiments, the dielectric layer 132 partially fills the through-opening 114.

[0031] In some embodiments, for the majority of each metal body and for each corresponding through-opening, a portion 116 of the through-opening between the second outermost surface 122 of the metal body 120 and the second main surface 112 of the polymer layer 110 is at least partially filled with a material 130 which may be a polymer material. As will be further described elsewhere, an additional film may be placed on one or both sides of the polymer layer 110.

[0032] The conductive layer 150 may be a metal foil, such as copper or aluminum foil. In some embodiments, the metal body is formed from a first metal, and the conductive layer 150 is formed from a second metal having a different composition from the first metal. For example, the metal body 120 may be a copper body, while the conductive layer 150 may be an aluminum layer. In embodiments in which the metal body 120 is plated onto the conductive layer 150, the use of different metals results in relatively low adhesion of the metal body 120 to the conductive layer 150, making it possible to easily peel the conductive layer 150 from the patterned article.

[0033] Any suitable material can be used for the metal body. Suitable materials for the metal body include, for example, elemental metals such as copper or silver. Suitable materials for the dielectric layer include, for example, polymers such as radiation-curable polymers and / or encapsulating materials. Suitable encapsulating materials include, for example, silicone encapsulants, epoxy encapsulants, urethane encapsulants, and fluoropolymers. Fluoropolymers may be preferred depending on the application because they have low dielectric loss at high frequencies. The dielectric layer can be applied, for example, by coating and then curing the coated material. Any suitable polymer material can be used for the polymer layer 110. Suitable materials for the polymer layer 110 will be described further elsewhere.

[0034] Figure 3A is a schematic diagram of forming a polymer layer by placing a resin 110' between the structured tool 160 and the conductive layer 150, which may be a polymer or a polymer precursor, or may contain a polymer or a polymer precursor. The resin 110' is then cured, or otherwise solidified, to form a cured or solidified resin 110a of layer 110 (see, for example, Figure 1A). The structured tool 160 includes a structure 161. The structure 161 may be tapered so that the tool can be easily removed from the resin (see, for example, Figure 11B schematically showing a tapered feature that may be made from a tapered structure of the structured tool). In embodiments in which the structure 161 has a width of at least 100 nm and less than 1 mm, the process of replicating the structured surface (or negative form of the structured surface) of the tool 160 may be called high-resolution. The tool 160 can be manufactured, for example, by diamond grinding, laser processing, photolithography, or additive deposition (e.g., two-photon or digital printing). The tool may be, for example, a metal tool, or a polymer tool formed from a metal tool (for example, by compression molding a polymer against a metal tool). The polymer tool may be permeable to allow curing through the tool.

[0035] Alternatively, tool 160 may be a substantially cylindrical tool, and polymer layers can be manufactured using this cylindrical tool in a roll-to-roll process. This is schematically shown in Figure 3B. A structuring tool 260, which may correspond to structuring tool 160 except having a substantially cylindrical shape, is used in a continuous process for manufacturing a patterned article 103, which may correspond to article 100' except for an additional layer or film 140. In the illustrated embodiment, rollers 138 are provided to guide various layers and films through the process. Polymer layer 110'' (e.g., corresponding to layer 110) is formed by extruding resin 110' from an extruder 137 between the conductive layer 150 and the structuring tool 260 (or layer 110'' can be formed by casting and curing resin against the structuring tool), and then (in the illustrated embodiment, at an etching station 163) by plasma etching to remove land portions (e.g., corresponding to portion 115). Next, a metal body is deposited into the through-openings of the polymer layer 110 by electroplating (at the plating station 164 in the illustrated embodiment). Then, a layer or film 140 is laminated onto the resulting article, and the conductive layer 150 is removed by peeling off the layer. In other embodiments, the layer or film 140 may be omitted and / or the conductive layer 150 may be retained.

[0036] In some embodiments, the process involves placing a polymer or polymer precursor (e.g., corresponding to resin 110') on a structuring tool 160 and solidifying the polymer or polymer precursor to form a polymer layer (e.g., layers 110, 110''). In some embodiments, the polymer or polymer precursor is a molten or thermosoftened polymer, or comprises a molten or thermosoftened polymer, and solidifying the polymer or polymer precursor involves cooling the molten or thermosoftened polymer. For example, the polymer or polymer precursor may be a thermoplastic resin (e.g., polyethylene terephthalate, polypropylene, polycarbonate, or other thermoplastic resins well known in the art) that has been softened by heat (or embossed or otherwise structured), and the thermoplastic resin is applied as a molten material and forms a thermoplastic polymer layer that solidifies upon cooling. In some embodiments, the polymer or polymer precursor is a polymer precursor, or comprises a polymer precursor, and solidifying the polymer or polymer precursor involves polymerizing the polymer precursor. In some embodiments, the polymer or polymer precursor is a resin, and solidifying the polymer or polymer precursor involves curing the resin. Curing a resin may include irradiating it with chemical rays, heating it, and / or catalytic curing. For example, a resin may be cured by irradiating it with radiation (e.g., ultraviolet (UV) rays, electron beams, or other chemical rays), by applying heat, or by using other crosslinking mechanisms known in the art. The resin may be, for example, an acrylate or an epoxy, or other resin chemicals may be used.

[0037] In some embodiments, the materials selected for the dielectric layers 131, 132 and the polymer layer 110 have similar refractive indices. For example, as further described elsewhere in this specification, some of the through-openings formed in the polymer layer 110 do not contain metal bodies. In such embodiments, as further described elsewhere in this specification, it may be desirable to substantially match the refractive index of the dielectric material within the through-openings with that of the polymer material in layer 110.

[0038] Figure 4A is a schematic diagram of the process in a method for manufacturing patterned articles 201, 200, or 202 according to several embodiments. Figures 4B and 4C are schematic cross-sectional views of exemplary patterned articles 200 and 202 that can be manufactured by the method of Figure 4A, respectively. Elements 210, 211, 212, 214, 216, 220, 222, 223, 230, 231, 232, 250, and 251 correspond to elements 110, 111, 112, 114, 116, 120, 122, 123, 130, 131, 132, 150, and 151, respectively, unless otherwise indicated, and may be as described elsewhere. This method includes, in order, the steps of: preparing a conductive layer 250; forming a polymer layer 210 on the conductive layer 250 that defines a plurality of through-holes 214 inside it; depositing metal bodies 220 in each of at least the first plurality of lower through-holes so that the metal bodies 220 are in contact with the conductive layer 250; and optionally removing the conductive layer 250 to electrically insulate the metal bodies 220 from each other. In the illustrated embodiment, the conductive layer 250 is placed on the structured main surface 252 of the substrate 251. This structures the first main surface 211 of the polymer layer 210. The main surface of a layer containing through-holes is structured if the main surface itself that does not contain through-holes is structured. For example, the main surface 111 is not structured in the embodiment shown in Figure 1A, for example, but the main surface 211 is structured. A structured surface may include, for example, a plurality of parts or segments that are not coplanar. The structured surface may include, for example, multiple engineering structures (structures having a predetermined non-random geometric shape). The process in Figure 4A may optionally include an etching step after the polymer layer 210 is initially formed, for example, as described with respect to Figures 1A and 3B. In the embodiments of Figures 4B and 4C, the conductive layer 250 and the substrate 251 are removed (for example, by peeling or etching). In the embodiment of Figure 4C, dielectric layers 231 and 232 are added.

[0039] In some embodiments, patterned articles 200, 202 include a polymer layer 210 having a first structured main surface 211 and a second main surface 212 on the opposite side, defining a plurality of through-openings 214 inside. For at least one of the first lower through-openings, a metal body 220 is positioned within the through-opening. The metal body 220 has a first outermost surface 221 adjacent to the first main surface 211 of the polymer layer 210, a second outermost surface 222 on the opposite side, and at least one lateral sidewall 223 extending between them, each lateral sidewall 223 extending from the first outermost surface 221 of the metal body 220 toward or to the second main surface 212 of the polymer layer 210, but not beyond the second main surface 212. As will be further explained elsewhere (see, for example, Figure 9), the metal bodies 220 may have the same or substantially the same extent as the through-openings 220 in at least one cross-section parallel to the polymer layer 210. In some embodiments, the metal bodies 220 are electrically insulated from each other.

[0040] The sidewall 223 may extend to the second main surface 212 (see, for example, Figures 1C and 2B), and / or a portion of the metal body may extend beyond the second main surface 212 (see, for example, Figure 1D). In some embodiments, for at least a majority of each metal body of the metal body 220, the second outermost surface 222 of the metal body 220 is substantially coplanar with the second main surface 212 of the polymer layer 210. In some embodiments, for at least a majority of each metal body of the metal body 220, the second outermost surface 222 of the metal body 220 is located between the first main surface 211 and the second main surface 212 of the polymer layer 210.

[0041] In some embodiments, the conductive layer 250 is located on the structured main surface 252 of the substrate 251 and substantially conforms to the structured main surface 252 (for example, the conductive layer 250 can nominally conform to the structured main surface 252, or conform to a change of less than about 20 percent, less than about 10 percent, or less than about 5 percent of the height of the structure of the structured main surface 252). The structured main surface 252 may be formed, for example, by fine-tuning (e.g., casting and hardening processes using a structuring tool) and may include a regular array of structures. The substrate 251 may include one or more layers. For example, the substrate 251 may include layers formed by a fine-tuning process located on a carrier layer. In some embodiments, the substrate 251 includes at least one dielectric layer and optionally at least one conductive layer (e.g., an internal conductive layer in addition to the conductive layer 250 located on the substrate 251). In some embodiments, the first structured main surface 211 includes a regular array of structures 213.

[0042] In some embodiments, the metal body is located within a first set of lower through-openings but not within a second set of lower through-openings. A patterned masking layer and / or a patterned conductive layer can be used to select the first set of lower through-openings containing the metal body. In some embodiments, it is desirable to form a regular pattern of through-openings (e.g., using a structuring tool having a regular pattern of structures) and to form the metal body in some through-openings but not in others, so that the metal body is located in a different pattern from the through-openings.

[0043] Figure 5A is a schematic diagram of the steps in a method for manufacturing patterned articles 301, 300, 300', 302, or 302' according to several embodiments. Figures 5B and 5C are schematic cross-sectional views of exemplary patterned articles 300 and 302 that can be manufactured by the method of Figure 5A, respectively. Figures 5D and 5E are schematic cross-sectional views of exemplary articles 300' and 302' that can be manufactured by the method of Figure 5A, respectively. Elements 310, 311, 312, 314, 316, 320, 321, 322, 323, 330, 331, 332, 350, and 351 correspond to elements 110, 111, 112, 114, 116, 120, 121, 122, 123, 130, 131, 132, 150, and 151, respectively, unless otherwise indicated, and may also be as described elsewhere. The first main surface 311 of the polymer layer 310 is structured. In some embodiments, the first main surface 311 of the polymer layer 310 includes a substantially planar first portion 317 and a second portion 318, the first portion 317 and the second portion 318 being parallel to each other but not coplanar.

[0044] In some embodiments, the method for manufacturing a patterned article includes a step of placing a patterned mask layer 370 on the conductive layer 350 between the step of preparing the conductive layer 350 and the step of forming the polymer layer 310, the forming step including the step of forming the polymer layer 310 on the patterned mask layer 370. This method may include depositing a metal body 320 in each of the through-openings 314 of at least the first lower plurality 314a. In some embodiments, the through-openings 314 of the second lower plurality 314b are blocked by the patterned mask layer 370, and as a result, the metal body 320 is not deposited in the through-openings of the second lower plurality 314b. The polymer layer 310 can be formed, for example, using a high-definition process. The process in Figure 5A may optionally include an etching step after the polymer layer 310 has been initially formed, for example, as described with respect to Figures 1A and 3B. In the etching step, a portion of the patterned mask layer 370 may be removed. In embodiments in which a patterned mask layer 370 is included and an etching process is carried out, it is typically preferable that the mask layer does not react to etching and / or has sufficient thickness so that at least a portion of the layer remains after etching.

[0045] The patterned mask layer 370 can be formed by printing (e.g., digital printing, flexographic printing, or other printing processes) or by depositing a material onto the conductive layer 350. Suitable materials can be used for the patterned mask layer 370 or the patterned mask layer 470 described elsewhere. The material for the mask layer may be a polymer material, such as the material described for the polymer layer 110. In some embodiments, epoxy-based materials are used (e.g., SU-8 photoresist).

[0046] In some embodiments, the conductive layer 350 and an optional substrate layer 351 are removed after the metal body 320 is formed. In some such embodiments, the patterned mask layer 370 is also removed, as shown in Figure 5B, leaving a space 371 which may then be filled with dielectric material, or the patterned mask layer 370 may be retained, as shown in Figure 5D. In either case, dielectric layers 331 and / or 332 may be included, as shown in Figures 5C and 5E.

[0047] In some embodiments, the side wall 323 may extend to the second main surface 312 (see, for example, Figures 1C and 2B), and / or a portion of the metal body 320 may extend beyond the second main surface 312 (see, for example, Figure 1D).

[0048] Figure 6A is a schematic diagram of the steps in a process for manufacturing patterned articles 401, 400, or 402 according to several embodiments. Figures 6B and 6C are schematic cross-sectional views of exemplary patterned articles 400 and 402 that can be manufactured by the method of Figure 6A, respectively. Elements 410, 411, 412, 414, 416, 420, 421, 422, 423, 430, 431, 432, 450, and 451 correspond to elements 110, 111, 112, 114, 116, 120, 121, 122, 123, 130, 131, 132, 150, and 151, respectively, unless otherwise shown, and may be as described elsewhere. In the embodiments of Figures 6B and 6C, the conductive layer 450 and the substrate 451 are removed (e.g., by peeling or etching). In the embodiment shown in Figure 6C, dielectric layers 431 and 432 are added.

[0049] In some embodiments, the method for manufacturing a patterned article includes arranging a patterned mask layer 470 over the polymer layer 410 between the steps of forming the polymer layer 410 and depositing a metal body, such that some of the through-openings 414b are at least partially filled with the patterned mask layer 470. This method may include depositing the metal body 420 in each of the through-openings 414 of at least the first lower plurality 414a. In some embodiments, the through-openings 414 of the second lower plurality 414b are blocked by the patterned mask layer 470, and as a result, the metal body 420 is not deposited in the through-openings of the second lower plurality 414b. The polymer layer 410 can be formed, for example, using a high-definition process. The method in Figure 6A may optionally include an etching step after the polymer layer 410 has been initially formed, for example, as described with respect to Figures 1A and 3B. In embodiments in which a patterned mask layer 470 is included and an etching process is carried out, it is typically preferable that the layer does not react to etching and / or has sufficient thickness so that at least a portion of the layer remains after etching.

[0050] In some embodiments, the side wall 423 may extend to the second main surface 412 (see, for example, Figures 1C and 2B), and / or a portion of the metal body 420 may extend beyond the second main surface 412 (see, for example, Figure 1D).

[0051] Figure 7A is a schematic diagram of the process in a method for manufacturing patterned articles 501, 500, or 502 according to several embodiments. Figures 7B and 7C are schematic cross-sectional views of exemplary patterned articles 500 and 502 that can be manufactured by the method of Figure 7A, respectively. Elements 510, 511, 512, 514, 516, 520, 521, 522, 523, 530, 531, 532, 550, and 551 correspond to elements 110, 111, 112, 114, 116, 120, 121, 122, 123, 130, 131, 132, 150, and 151, respectively, unless otherwise shown, and may be as described elsewhere. The conductive layer 550 is patterned (e.g., by etching). The first main surface 511 of the polymer layer 510 is structured. In some embodiments, the first main surface 511 of the polymer layer 510 includes a substantially planar first portion 517 and a second portion 518, the first portion 517 and the second portion 518 being parallel to each other but not coplanar. In the embodiments of Figures 7B and 7C, the conductive layer 550 and the substrate 551 have been removed (e.g., by peeling or etching). In the embodiment of Figure 7C, dielectric layers 531 and 532 have been added.

[0052] A method for manufacturing a patterned article may include depositing a metal body 520 within each through-opening 514 of at least a first lower plurality 514a. For example, the through-openings 514 of the first lower plurality 514a may be covered by a conductive layer 550, which may form a continuous conductive path (e.g., outside the illustrated cross-section), and the conductive path may be used when electroplating a metal body onto the conductive layer 550. In some embodiments, for each through-opening of a second lower plurality 514b, no metal body is placed within the through-opening. For example, there may be no conductive layer covering the through-openings 514 of the second lower plurality 514b, on which a metal body is electroplated. In some embodiments, the through-openings 514b are filled or substantially filled with dielectric layers 531 and / or 532, for example, schematically shown in Figure 7C. The polymer layer 510 can be formed, for example, using a high-definition process. The method shown in Figure 7A may optionally include an etching step after the polymer layer 710 has been initially formed, for example, as described with respect to Figures 1A and 3B.

[0053] In some embodiments, the side wall 523 may extend to the second main surface 512 (see, for example, Figures 1C and 2B), and / or a portion of the metal body 520 may extend beyond the second main surface 512 (see, for example, Figure 1D).

[0054] Figures 5A to 7C schematically illustrate various approaches to providing a patterned arrangement of metal bodies. Figure 8 schematically illustrates another method for forming a patterned article, including a patterned arrangement of metal bodies, according to several embodiments. The patterned article 600 includes a polymer layer 610 defining a plurality of through-openings inside, and for each of at least a first lower plurality of through-openings (all of the through-openings in the illustrated embodiment), a metal body 620 is positioned within the through-opening. The patterned article 600 can be cut to create a desired pattern. Then, the portions 629 can be removed to form a patterned article 600a, and / or the portions 629 can be laminated onto a separate layer or film to retain the portions 629 in the desired pattern to form a patterned article 600b.

[0055] In any of the patterned articles described herein, a metal body may have the same or substantially the same extent as the corresponding through-opening in at least one cross-section parallel to the polymer layer. Figure 9 is a schematic cross-sectional view of a portion of a patterned article showing a metal body 720 having the same extent as the through-opening 714, according to several embodiments. This cross-section is parallel to the polymer layer 710 (for example, parallel to the xy-plane). If the metal body has the same extent in cross-section as at least 80% of the area of ​​the through-opening, the metal body can be considered to have substantially the same extent as the through-opening in cross-section. In some embodiments, the metal body has the same extent in cross-section as at least 90%, or at least 95%, or at least 98%, or 100% of the area of ​​the through-opening.

[0056] In some embodiments, the patterned article is at least one of the following: an antenna, an antenna array, a retrodirective antenna array, a Van Atta array, a retroreflector, a reflective traffic sheet, a conspicuity sheet, a heater, an electromagnetic interference (EMI) shield, an electrostatic dissipation component, a sensor, an electromagnetic wave filter, a building film, or an electrode. In some embodiments, the patterned article is an array of any of these elements or devices, or includes an array of any of these elements or devices. In some embodiments, the patterned article is at least one of the following: an antenna, a sensor, or a retroreflector. In some embodiments, the patterned article is a sensor, such as a touch sensor. In some embodiments, the patterned article is substantially transparent and / or a flexible film. In some embodiments, the antenna, an antenna array, an antenna array, a retrodirective antenna array, a Van Atta array, a heater, an electromagnetic interference shield, an electrostatic dissipation component, a sensor, an electromagnetic wave filter, or an electrode is substantially transparent and / or a flexible film.

[0057] Figures 10A to 10C are schematic top views of patterned articles 800, 800', and 800'', respectively. Patterned article 800 includes a first metal body 820a and a second metal body 820b which are placed within each through-opening of the polymer layer 810 and can be electrically insulated from each other. Patterned article 800' includes an array consisting of pairs of the first metal body 820a and the second metal body 820b. More generally, patterned article 800 may include multiple (e.g., two, three or more) metal bodies which can be electrically insulated from each other, and patterned article 800' may include an array in which each element of the array corresponds to a patterned article 800.

[0058] In some embodiments, the geometric shapes of the first metal body 820a and the second metal body 820b can be characterized as follows. In some embodiments, in the top view, the first metal body 820a is at least partially located inside a minimum rectangle 833 that accommodates the second metal body.

[0059] The metal bodies 820a, 820b in the patterned article 800 or 800' may be solid metal bodies, or may be or contain fine patterns of metal wiring. For example, patterned article 800'' corresponds to patterned article 800', except that the metal bodies 820a, 820b are replaced by metal bodies 820a', 820b' containing fine patterns of metal wiring 826. In some embodiments, it is desirable to use fine patterns of metal wiring such that the patterned article, or a layer of the patterned article containing metal bodies, is substantially transparent. For example, in some embodiments, the patterned article, or a layer of the patterned article containing metal bodies, has an average light transmittance of at least 50%, at least 70%, at least 80%, or at least 90% for normally incident visible light (wavelengths in the range of 400 nm to 700 nm).

[0060] In some embodiments, a metal body (e.g., 820a, 820b, or an array of elements 820a, 820b) defines the antenna. In some embodiments, the antenna is or includes a retrodirective antenna array.

[0061] The patterned article may be, for example, a 5G antenna and / or may be configured to transmit and receive in frequency bands from 0.7, 1, 5, 10, 20, or 30 GHz to 300, 200, or 100 GHz (0.7 to 100 GHz). Useful antenna shapes are described, for example, in U.S. Patent Application Publications 2009 / 0051620 (Ishibashi et al.), 2009 / 0303125 (Caille et al.), and 2013 / 0264390 (Frey et al.), as well as, for example, International Application No. US2020 / 031450, filed on 5 May 2020, titled "PATTERNED ARTICLE INCLUDING ELECTRICALLY CONDUCTIVE ELEMENTS". In some embodiments, the patterned article is a substantially transparent antenna. For example, in some embodiments, the patterned article is used as an antenna and is placed over a window through which it is desired to be visible. In some embodiments, the substantially transparent antenna is an antenna array such as a 5G antenna array or a retrodirective antenna array (e.g., a Van Atta array). In some embodiments, the patterned article includes an array of antennas, which, for example, can then be pieced and provide antennas corresponding to the patterned article 800.

[0062] Figure 11A is a schematic top view of a portion of a patterned article, including metal bodies 920 positioned within through-openings in a polymer layer 910, according to several embodiments. In some embodiments, at least some of the metal bodies (e.g., the illustrated metal bodies 920) include a fine pattern 925 of metal wiring 926. Figure 11B is a schematic cross-sectional view of a portion of a patterned article, schematically showing exemplary metal wiring 926. In some embodiments, each metal wiring 926 of at least a majority of the metal wiring in the fine pattern 925 extends along the longitudinal direction 927 of the metal wiring (or the y' direction, referring to the x'y'z' coordinate system illustrated in Figure 11B), and has a width W along the width direction (x' direction) perpendicular to the longitudinal direction 927 and thickness direction (z' direction) of the polymer layer 910, and a thickness T along the thickness direction. In some embodiments, T / W is at least 0.8, 1, 1.2, 1.5, 2, 5, or 7.

[0063] In some embodiments, the fine patterns 925 of the metal wiring 926 have aperture area ratios in the range of 80% to 99.95%, 80% to 99.9%, 85% to 99.9%, 90% to 99.9%, or 95% to 99.9%. A high aperture area ratio can result in high light transmittance while still providing the desired electrical conductance, for example, when T / W is within the range described elsewhere. In some embodiments, in the top view, the total area of ​​the fine patterns 925 of the metal wiring 926 is less than 50%, less than 20%, less than 10%, less than 5%, less than 3%, less than 2%, or less than 1% of the total surface area of ​​the patterned article.

[0064] The fine patterns of the metal wiring may be mesh patterns, or may include mesh patterns, which may be two-dimensional ordered arrays of wiring (e.g., rectangular, square, triangular, or hexagonal arrays) or two-dimensional irregular arrays. Suitable fine pattern shapes include, for example, those described in U.S. Patent 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).

[0065] In some embodiments, each wire may be a metal body, and for example, the metal bodies (wires) may be electrically connected to each other to form a fine pattern. Each wire may be placed in a groove-shaped through-opening (for example, with a width smaller than its length). The groove-shaped through-openings may be interconnected to form a larger through-opening.

[0066] Figure 12 is a schematic top view of a patterned article 900, which includes metal bodies 820a', 820b' containing a fine pattern of metal wiring 826 as described elsewhere. The patterned article further includes a fine pattern of material 830 placed within a through-opening. For example, material 830 may correspond to material 330 in the through-opening 314b shown in Figures 5C and 5E, or to the material of the patterned mask layer 470 in the through-opening 414b shown in Figure 6C, or to the material of the dielectric layers 531 and 532 in the through-opening 514b shown in Figure 7C. Material 830 is typically nonconductive.

[0067] It may be desirable to form a regular pattern of through-openings (e.g., groove-shaped through-openings) within region 839 of the polymer layer 810, and then deposit metal wiring in only some of the through-openings to form metal bodies 820a' and 820b'. It may be desirable to place material 830 in the remaining through-openings to minimize the optical effects (e.g., light scattering) of those remaining through-openings. In some embodiments, material 830 is substantially refractive index matched with the material of the polymer layer 810. In some embodiments, material 830 has a refractive index within 0.03 or 0.02 of the refractive index of layer 810. The refractive index is measured at a wavelength of 587.6 nm (spectral lines from a helium light source) unless otherwise specified.

[0068] The region 839 of the polymer layer 810 may optionally be the entire polymer layer 810. For example, a layer or film (e.g., layer or film 140) can be laminated onto the polymer layer 810 before removing the conductive layer (e.g., conductive layer 150 shown in Figure 3B). The additional layer or film can provide the desired structural integrity if the fine pattern of material 830 and wiring 826 extends throughout the polymer layer 810.

[0069] Any of the patterned articles described herein may further include additional layers or films. For example, a patterned article may include a polymer layer defining a plurality of through-openings inside, wherein a metal body is disposed within each of at least one of the first lower through-openings, and the patterned article further includes an optical film, with the polymer layer disposed on the optical film.

[0070] Figure 13 is a schematic cross-sectional view of a patterned article 1003 comprising a polymer layer 1010 disposed on an optical film 1040, according to several embodiments. In some embodiments, the patterned article 1003 includes an optional dielectric layer 1031 disposed between the polymer layer 1010 and the optical film 1040. In some embodiments, as further described elsewhere in this specification, the patterned article 1003 includes an optional dielectric layer 1032 disposed on the polymer layer 1010 opposite the optical film 1040. The polymer layer 1010 defines a plurality of through-openings internally, and for at least one of the first lower through-openings, a metal body 1020 is disposed within the through-opening. The metal body 1020 may have sidewalls that extend toward, to, but not beyond, the main surface of the polymer layer 1010 facing toward or away from the optical film 1040 (as schematically shown).

[0071] The optical film 1040 may be laminated onto the polymer layer 1010 or the dielectric layer 1031 using an optically transparent adhesive, or the dielectric layer 1031 may be an optically transparent adhesive. The optical film 1040 may be placed (directly or indirectly) on the main surface 1011 of the polymer layer 1010, as shown in Figure 13, or on the main surface 1012 of the polymer layer 1010, as illustrated in Figure 3B for a layer or film 140 that may be an optical film. In some embodiments, the optical film is placed on both sides of the polymer layer 1010. In some embodiments, the optical film 1040 (and / or layer or film 140) is one or more of a window film, a textured film, a patterned film, a graphic film, an infrared reflective film, or a retroreflector, or includes one or more of these. Useful optical films include, for example, those described in U.S. Patent 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.), 2002 / 0012248 (Campbell et al.), and 2010 / 0103521 (Smith et al.).

[0072] example Separated, patterned metal bodies were formed and transferred to a film.

[0073] These examples are for illustrative purposes only and are not intended to limit the scope of the appended claims. All parts, percentages, ratios, etc., in the examples and elsewhere in this specification are based on weight unless otherwise indicated. The following abbreviations are used herein: mL = milliliter, m = meter, um = micrometer, nm = nanometer, '' = inch, mm = millimeter, m2 = square meter, cm = centimeter, m / min = meters per minute, hrs = hour, lbs = pound, kN = kilonewton, MHz = megahertz, SCCM = standard cubic centimeters per minute, Pa = pascal, mTorr = milliliter, °C = Celsius, min = minute, s = second.

[0074] Preparation of resin A

[0075] [Table 1]

[0076] Resin A was prepared by mixing PHOTOMER 6210, SR238, SR351, and IRGACUR TPO in a weight ratio of 60 / 20 / 20 / 0.5. This mixture was heated to approximately 50°C and blended in a roller mixer for 12 hours. The mixture became homogeneous after mixing and heating.

[0077] Tool preparation A laser-ablated master tool was prepared according to the procedure described in U.S. Patent No. 6,285,001 (Fleming et al.) to form a tool (female) with a negative type of the desired design. The mask pattern used in the laser ablation process was generally as shown in Figures 10A and 10B. The four rectangular pads in Figure 10A each had dimensions of 1.25 mm × 1.74 mm and were spaced 4.236 mm apart from center to center. The lines connecting the rectangular pads were 0.3 mm wide. The elements containing the four rectangular pads were arranged in a two-dimensional array with a pitch of 16.944 mm along the y-direction in Figures 10A and 10B and a pitch of 4.236 mm along the x-direction in Figures 10A and 10B. The master tool was then plated with nickel using conventional techniques for forming negative master tools (male) (for example, generally as described in U.S. Patent No. 9,878,507 (Smithe et al.)). This tool was plated again to create a negative mold of this pattern, and a female nickel tool was created.

[0078] Preparation of UV-transmitting tools A 0.89 mm (0.035 inch) thick sheet of Polypropylene Natural manufactured by Plastics International (Eden Prairie, MN) was compression-formed into a female nickel tool using a Rucker PHI 400-ton (City of Industry, CA) press.

[0079] The female nickel tool measured 12 inches x 12 inches (30.5 cm x 30.5 cm).

[0080] The conditions for Rucker Press were as follows: - Start with low pressure setting of 14,000 lbs (62 kN) and temperature of 27°C. - The platen temperature was raised to 157°C, which took 7 minutes and 50 seconds. - The pressure was increased to 80,000 lbs (356 kN). - Turned on the cooling water 9 minutes and 50 seconds after the start, or 2 minutes at high pressure. -22 minutes and 30 seconds after the start, the press opened.

[0081] Surface coating on UV-transparent tools A silicon-containing layer was applied to the microstructured surface of a UV-transparent tool using a parallel-plate capacitive-coupled plasma reactor. The reactor chamber was 0.34 m². 2It has a cylindrical power supply electrode with a surface area. After attaching the tool to the rotating drum electrode, the reactor chamber was pumped down to a reference pressure of less than 1.3 Pa (1 mTorr). Oxygen was introduced into the chamber at a flow rate of 600 SCCM. The process was carried out by coupling RF power to the reactor at a frequency of 13.56 MHz and an applied power of 500 watts for 60 seconds. The oxygen flow was stopped, and a second step was achieved to deposit a thin film on the microstructure by evaporating hexamethyldisiloxane (HMDSO, available from Sigma-Aldrich) and transporting it into the system at a flow rate of 120 SCCM. The process was carried out using the plasma-excited CVD method by coupling RF power to the reactor at a frequency of 13.56 MHz and an applied power of 600 watts for 80 seconds. After the completion of the second step, a second line of HMDSO was opened to the chamber in addition to 120 SCCM of HMDSO. The combined flow rate resulted in a chamber pressure of 4.1 mTorr. The treatment was carried out by coupling RF power at a frequency of 13.56 MHz and an applied power of 200 watts into the reactor for 40 seconds. The HMDSO flow was stopped. Next, oxygen was introduced into the chamber at a flow rate of 600 SCCM, and the treatment was carried out by coupling RF power at a frequency of 13.56 MHz and an applied power of 500 watts into the reactor for 45 seconds. Under these treatment conditions, a surface coating thickness of less than 200 nm was obtained. After each step, after the specified gas flow had stabilized, RF power (watts) was applied to the electrode to generate plasma. Following the completion of the plasma treatment, the RF power and gas supply were stopped, and the chamber was returned to atmospheric pressure. The tool was removed from the chamber, immersed in 3M NOVEC 2202 (available from 3M Company (St. Paul, MN)) for 30 seconds, removed, the solvent was evaporated, and then it was heat-cured overnight (approximately 20 hours) in an air oven at 60°C.

[0082] Duplication procedure A clean 6-inch x 6-inch (15.2cm x 15.2cm) piece of aluminum foil was placed on a press plate (chrome copper plate), and 0.5 mL of resin A was dispensed into the center of the aluminum foil. Next, a 4.5-inch x 4.5-inch (11.4cm x 11.4cm) surface-coated UV-transparent tool piece was placed with the tool pattern facing the resin. Then, another press plate was placed on top of the UV-transparent tool. Next, this laminate was placed in a press (Devin Mfg., Inc. (Arcade, New York) model LP500). A 13.8cm x 13.8cm, 3.7cm thick metal plate reinforcement was placed on the bottom of the press, and the laminate was placed on top of it so that it was centered. Another 13.8cm x 13.8cm, 3.7cm thick metal plate reinforcement was placed on top of the laminate so that everything was centered under the press piston. A pressure of 9,000 lbs (40 kN) was applied to the laminate for 3 minutes to fluidize resin A and create a very thin land beneath the male feature of the UV-permeable tool. After 3 minutes, the pressure was released and the aluminum foil / resin A / UV-permeable tool was removed as a laminate and immediately passed twice at 16.7 m / min under nitrogen purge through a UV processor (RPC Industries (Hayward, CA (USA)) model QC 120233AN) equipped with two D valves (Heraeus Nobelight Fusion UV Inc (Gaithersburg, MD)). The power setting was "normal". The UV-permeable tool was removed. The cured resin on the aluminum foil was then plasma-etched to expose the aluminum foil in the area where the very thin land of cured resin A created by the male feature of the UV-permeable tool was located. Etching was performed using the following procedure: The reactor chamber was pumped down to a reference pressure of less than 1.3 Pa (1 mTorr). A mixed gas of 800 SCCM of oxygen and 200 SCCM of C6F14 was introduced into the chamber, and etching was performed by coupling RF power into the reactor at a frequency of 13.56 MHz and an applied power of 1000 watts for 3600 seconds.After the plasma etching was completed, the RF power and gas supply were shut off, and the chamber was returned to atmospheric pressure by performing three O2 purging steps (introducing 1000 SCCM into the chamber, running the RF power at 500 watts for 2 minutes, turning off the O2, and returning the pressure to 1 mTorr).

[0083] Next, the etched sample was copper-plated. Only the areas of the pattern where the aluminum was exposed were plated. The copper was 10 μm thick. The remaining areas on the aluminum foil were masked with the remaining resin A. Then, a 75 μm thick polycarbonate film (LUPILON, Mitsubishi Gas Chemical Company, Inc. (Tokyo, Japan)) was laminated to the copper side of the sample using 3M 8146 (3M Company (St. Paul, MN)), an optically transparent adhesive. This laminate was then peeled off from the aluminum foil, resulting in an electrically insulated copper pattern on the adhesive / polycarbonate film surface.

[0084] Terms such as "about" will be understood by those skilled in the art in the context in which they are used and described herein. Where the use of "about" in relation to the size, quantity, and physical properties of a feature is not otherwise obvious to those skilled in the art in the context in which it is used and described herein, "about" will be understood to mean within 10 percent of a particular value. A quantity given as about a particular value may be exactly a particular value. For example, where it is not otherwise obvious to those skilled in the art in the context in which it is used and described herein, a quantity having a value of about 1 means that the quantity has a value between 0.9 and 1.1, and that value may be 1.

[0085] All references, patents, or patent applications cited above are incorporated herein by reference in their entirety. In the event of any inconsistency or contradiction between the incorporated references and this application, the information in the foregoing description shall prevail.

[0086] Descriptions of elements in the figures should be understood to apply equally to corresponding elements in other figures unless otherwise indicated. While specific embodiments are illustrated and described herein, it will be understood by those skilled in the art that these specific embodiments may be replaced by various alternative and / or equivalent embodiments without departing from the scope of this disclosure. This application is intended to encompass any adaptation, modification, or combination of any specific embodiment discussed herein. Therefore, this disclosure is intended to be limited only by the claims and their equivalents. The following are exemplary embodiments. [Item 1] A patterned article comprising a polymer layer having a first main surface and a second main surface facing opposite directions, and defining a plurality of through-openings internally, wherein for at least one of the first lower plurality of through-openings, a metal body is disposed within the through-opening, the metal body having a first outermost surface, a second outermost surface on the opposite side, and at least one lateral sidewall extending between the first outermost surface and the second outermost surface, the first outermost surface of the metal body being substantially coplanar with the first main surface of the polymer layer, each lateral sidewall extending from the first outermost surface of the metal body toward or to the second main surface of the polymer layer, but not beyond the second main surface, the metal body having substantially the same extent as the through-openings in at least one cross-section parallel to the polymer layer, and being electrically insulated from each other. [Item 2] The patterned article according to item 1, wherein for at least a majority of the metal bodies, the second outermost surface of the metal body is substantially coplanar with the second main surface of the polymer layer. [Item 3] The patterned article according to item 1, wherein for at least a majority of the metal bodies, the second outermost surface of the metal body is positioned between the first main surface and the second main surface of the polymer layer. [Item 4] The patterned article according to item 3, wherein for each of the majority of the metal bodies and for each corresponding through-opening, a portion of the through-opening between the second outermost surface of the metal body and the second main surface of the polymer layer is at least partially filled with polymer material. [Item 5] A patterned article according to any one of items 1 to 4, wherein the first main surface of the polymer layer comprises a substantially planar first portion and a second portion, the first portion and the second portion being parallel to each other but not coplanar. [Item 6] The aforementioned metal body defines an antenna, and the patterned article is as described in any one of items 1 to 5. [Item 7] The patterned article described in item 6, wherein the antenna includes a retrodirective antenna array. [Item 8] A patterned article according to any one of items 1 to 7, wherein at least some of the metal bodies include a fine pattern of metal wiring. [Item 9] The patterned article according to item 8, wherein the fine pattern of the metal wiring has an opening area ratio in the range of 80% to 99.95%. [Item 10] A patterned article according to item 8 or 9, wherein at least a majority of the metal wirings in the fine pattern extend along the longitudinal direction of the metal wiring, have a width W along the width direction perpendicular to the longitudinal direction and the thickness direction of the polymer layer, have a thickness T along the thickness direction, and T / W is at least 0.8. [Item 11] A patterned article comprising a polymer layer having a first structured main surface and a second main surface opposite to it, and defining a plurality of through-openings internally, wherein for at least one of the first lower plurality of through-openings, a metal body is disposed within the through-opening, the metal body having a first outermost surface adjacent to the first main surface of the polymer layer, a second outermost surface opposite to it, and at least one lateral sidewall extending between the first outermost surface and the second outermost surface, each lateral sidewall extending from the first outermost surface of the metal body toward or to the second main surface of the polymer layer, but not beyond the second main surface, and the metal body having substantially the same extent as the through-openings in at least one cross-section parallel to the polymer layer and being electrically insulated from each other. [Item 12] The patterned article according to item 11, wherein the first structured main surface includes a regular array of structures. [Item 13] A patterned article comprising a single polymer layer disposed on a conductive layer, the single polymer layer having a first main surface facing the conductive layer and a second main surface on the opposite side, defining a plurality of through-openings therein, and for at least one of the first lower plurality of through-openings, a single metal body is disposed within the through-opening, the single metal body having at least one lateral sidewall, each lateral sidewall extending from the conductive layer toward or to the second main surface of the single polymer layer but not beyond the second main surface, the single metal body having substantially the same extent as the through-opening in at least one cross-section parallel to the single polymer layer, and filling at least 10% of the volume of the through-opening. [Item 14] The patterned article according to item 13, wherein the conductive layer is disposed on the structured main surface of the substrate and substantially conforms to the structured main surface. [Item 15] A method for manufacturing patterned articles, in order, The process of preparing the conductive layer, A step of forming a polymer layer having multiple through-openings defined inside on the conductive layer, A step of depositing the metal body in each of the openings of at least the first lower plurality of through-openings such that the metal body is in contact with the conductive layer, A step of removing the conductive layer and electrically insulating the metal bodies from each other, Methods that include...

Claims

1. A patterned article comprising a polymer layer having a first main surface and a second main surface facing opposite directions, and defining a plurality of through-openings internally, wherein a metal body is disposed within each of all or at least two of the plurality of through-openings, the metal body having a first outermost surface, a second outermost surface on the opposite side, and at least one lateral sidewall extending between the first outermost surface and the second outermost surface, the first outermost surface of the metal body being substantially coplanar with the first main surface of the polymer layer, each lateral sidewall extending from the first outermost surface of the metal body toward or to the second main surface of the polymer layer, but not beyond the second main surface, the metal body having substantially the same extent as the through-opening in at least one cross-section parallel to the polymer layer, and being electrically insulated from each other. At least some of the aforementioned metal bodies include a fine pattern of metal wiring, The fine pattern of the metal wiring has an aperture area ratio in the range of 80% to 99.95%. At least a majority of the metal wirings in the fine pattern extend along the longitudinal direction of the metal wiring, have a width W along the width direction perpendicular to the longitudinal direction and the thickness direction of the polymer layer, have a thickness T along the thickness direction, and have a T / W ratio of at least 0.

8. Patterned items.

2. The patterned article according to claim 1, wherein for at least a majority of the metal bodies, the second outermost surface of the metal body is substantially coplanar with the second main surface of the polymer layer.

3. The patterned article according to claim 1, wherein for at least a majority of the metal bodies, the second outermost surface of the metal body is positioned between the first main surface and the second main surface of the polymer layer.

4. The patterned article according to claim 3, wherein for each of the majority of the metal bodies and for each corresponding through-opening, a portion of the through-opening between the second outermost surface of the metal body and the second main surface of the polymer layer is at least partially filled with polymer material.

5. The patterned article according to claim 1, wherein the first main surface of the polymer layer comprises a substantially planar first portion and a second portion, the first portion and the second portion being parallel to each other but not coplanar.

6. The patterned article according to claim 1, wherein the metal body defines an antenna.

7. The patterned article according to claim 6, wherein the antenna includes a retrodirective antenna array.

8. The patterned article according to claim 1, wherein the T / W ratio is at least 2.

9. A patterned article according to claim 1, wherein the T / W ratio is at least 5.

10. A patterned article comprising a polymer layer having a first structured main surface and a second main surface opposite to it, and defining a plurality of through-openings therein, wherein a metal body is disposed within each of all or at least two of the plurality of through-openings, the metal body having a first outermost surface adjacent to the first main surface of the polymer layer, a second outermost surface opposite to it, and at least one lateral sidewall extending between the first outermost surface and the second outermost surface, each lateral sidewall extending from the first outermost surface of the metal body toward or to the second main surface of the polymer layer, but not beyond the second main surface, and the metal body having substantially the same extent as the through-opening in at least one cross-section parallel to the polymer layer, and being electrically insulated from each other. At least some of the aforementioned metal bodies include a fine pattern of metal wiring, The fine pattern of the metal wiring has an aperture area ratio in the range of 80% to 99.95%. At least a majority of the metal wirings in the fine pattern extend along the longitudinal direction of the metal wiring, have a width W along the width direction perpendicular to the longitudinal direction and the thickness direction of the polymer layer, have a thickness T along the thickness direction, and have a T / W ratio of at least 0.

8. Patterned items.

11. The patterned article according to claim 10, wherein the first structured main surface includes a regular structural array.

12. A method for manufacturing patterned articles, in order, The process of preparing the conductive layer, A step of forming a polymer layer having multiple through-openings defined inside on the conductive layer, A step of depositing the metal body in each of the plurality of through-openings, all or at least two of them, such that the metal body is in contact with the conductive layer, A step of removing the conductive layer and electrically insulating the metal bodies from each other, Includes, At least some of the aforementioned metal bodies include a fine pattern of metal wiring, The fine pattern of the metal wiring has an aperture area ratio in the range of 80% to 99.95%. At least a majority of the metal wirings in the fine pattern extend along the longitudinal direction of the metal wiring, have a width W along the width direction perpendicular to the longitudinal direction and the thickness direction of the polymer layer, have a thickness T along the thickness direction, and have a T / W ratio of at least 0.

8. method.

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