Ionic liquids for multi-material printing

Abstract

Disclosed are methods for producing articles, including multi-material articles, articles produced by such methods, and systems for producing such articles.

Description

IONIC LIQUIDS FOR MULTI-MATERIAL PRINTINGCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 631,432, filed April 8, 2024, and U.S. Provisional Application No. 63 / 631,692, filed April 9, 2024, the entire contents of both of which are incorporated herein by reference.TECHNICAL FIELD

[0002] The present disclosure pertains to synthetic processes for forming articles.BACKGROUND

[0003] A major drawback of particle-based photopolymer additive manufacturing is poor selectivity deposition and of course the simultaneous shrinkage rate variability found in low-temperature or high-temperature cofired ceramic (LTCC or HTCC) parts.SUMMARY

[0004] Provided herein are methods for producing multi-material articles, articles produced by such methods, and systems for producing multi-material articles. Also provided are methods for producing single-material articles, wherein the single material is selected from the group consisting of ceramic, glass, and polymer, and does not include metal.BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 provides a schematic of a process according to the present disclosure involving the use of two different stimuli in order to produce a multi-material article from a single ionic liquid.

[0006] FIG. 2A is a top perspective view of an electrical connector constructed in accordance with one example.

[0007] FIG. 2B is a bottom perspective view of the electrical connector of FIG. 2A.

[0008] FIG. 3 is a schematic perspective view of a printed circuit board (PCB).

[0009] FIG. 4A is a cross-sectional view of a substrate having holes in accordance with one embodiment.

[0010] FIG. 4B is a cross-sectional view' of the substrate of Fig. 4A including metallized vias.DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0011] The presently disclosed inventive subject matter may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that these inventions are not limited to the specific products, methods, conditions or parameters described and / or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed inventions.

[0012] The entire disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference. U.S. Patent No. 9,034,568 is attached hereto as Appendix A and therefore represents part of the present disclosure. U.S. Patent No. 10,162,264 is attached hereto as Appendix B and therefore represents part of the present disclosure. U.S. Pub. No. 2021 / 01229364 is attached hereto as Appendix C and therefore represents part of the present disclosure. U.S. Pub. No. 2023 / 0139931 is attached hereto as Appendix D and therefore represents part of the present disclosure. Additional information relating to the inventive subject matter is provided in Appendix E, attached hereto, which therefore represents part of the present disclosure.

[0013] As employed above and throughout the disclosure, the following terms and abbreviations, unless otherwise indicated, shall be understood to have the following meanings.

[0014] In the present disclosure the singular forms “a,” “an / ’ and “the” include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “an anchor” is a reference to one or more of such anchors and equivalents thereof know n to those skilled in the art, and so forth. Furthermore, when indicating that a certain element “may be” X, Y, or Z, it is not intended by such usage to exclude in all instances other choices for the element.

[0015] When values are expressed as approximations, by use of the antecedent “about.” it will be understood that the particular value forms another embodiment. As used herein, “about X” (where X is a numerical value) preferably refers to ±10% of the recited value, inclusive. For example, the phrase “about 8” preferably refers to a value of 7.2 to 8.8, inclusive; as another example, the phrase “about 8%” preferably refers to a value of 7.2% to8.8%, inclusive. Where present, all ranges are inclusive and combinable. For example, when a range of “1 to 5” is recited, the recited range should be construed as optionally including ranges “1 to 4”, “1 to 3”, “1-2”, “1-2 & 4-5”, “1-3 & 5”, and the like. In addition, when a list of alternatives is positively provided, such a listing can also include embodiments where any of the alternatives may be excluded. For example, when a range of “1 to 5” is described, sucha description can support situations whereby any of 1, 2, 3. 4, or 5 are excluded; thus, a recitation of “1 to 5” may support “1 and 3-5, but not 2”, or simply “wherein 2 is not included.” The phrase “at least about x” is intended to embrace both “about x” and “at least

[0016] In situ, solution-based synthesis routes for metals, alloys, and ceramics have been effectively non-existent through non-particulate means. As noted, a major drawback of particle-based photopolymer additive manufacturing is poor selectivity deposition and of course the simultaneous shrinkage rate variability found in low-temperature or high- temperature cofired ceramic (LTCC or HTCC) parts. Indeed, fabrication of certain parts, including electrical components, has been a challenge. For example, metal lining of vias through a glass or silicon wafer can be difficult to accomplish. To satisfy such ongoing needs, the present inventors have developed solution-based synthetic methods and systems for the production of multi-material articles. The inventive methods and systems are compatible with all three-dimensional printing techniques, including layer-by-layer, volumetric, two-photon, and stereolithography (SLA) printing.

[0017] Accordingly, provided herein are methods for making a multi -material article comprising exposing to stimulation an ionic liquid comprising tw o or more of solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors, wherein the stimulation includes a first stimulation that is effective to induce formation of a solid material from one of the respective solvated ionic precursors e.g., to induce formation of a polymer from any solvated ionic monomers or oligomers, to induce formation of solid conductive material from any solvated metal ions, to induce formation of a solid ceramic material from any solvated ionic ceramic precursors, or to induce formation of a glass from any solvated ionic glass precursors), and at least one further stimulation that is effective to induce formation of a solid material from another one of the respective solvated ionic precursors (e.g., to induce formation of a polymer from solvated ionic monomers or oligomers, to induce formation of solid conductive material from solvated metal ions, to induce formation of a solid ceramic material from solvated ionic ceramic precursors, or to induce formation of a glass from solvated ionic glass precursors).thereby forming the multi-material article comprising two or more of the polymer, the solid conductive material, the solid ceramic material, and the glass.

[0018] In some embodiments, the provided herein are methods for making a multimaterial article comprising exposing to stimulation an ionic liquid comprising (i) solvated ionic monomers or oligomers, and (ii) solvated metal ions, ionic ceramic precursors, ionic glass precursors, or any combination thereof, wherein the stimulation includes a first stimulation that is effective to induce formation of a polymer from the solvated ionic monomers or oligomers, and at least one further stimulation that is effective to induce formation of solid conductive material from the solvated metal ions, to induce formation of a solid ceramic material from the solvated ionic ceramic precursors, to induce formation of a glass from the solvated ionic glass precursors, or any combination thereof, thereby forming the multi-material article comprising the polymer and the solid conductive material, the solid ceramic material, the glass, or any combination thereof.

[0019] Also provided herein are methods for making a multi-material article comprising exposing to stimulation an ionic liquid comprising (i) solvated ionic glass precursors, and (ii) solvated metal ions, ionic ceramic precursors, or both, wherein the stimulation includes a first stimulation that is effective to induce formation of a glass from the solvated ionic glass precursors, and at least one further stimulation that is effective to induce formation of solid conductive material from the solvated metal ions, to induce formation of a solid ceramic material from the solvated ionic ceramic precursors, or both, thereby forming the multi-material article comprising the glass and the solid conductive material, the solid ceramic material, or both.

[0020] In certain embodiments of the present methods for making a multi-material article, the first stimulation, the further stimulation, or both includes light or heat. For example, the first stimulation, the further stimulation, or both includes light, such as ultraviolet light. In certain embodiments, the first stimulation comprises a first wavelength of light, and the further stimulation comprises a second wavelength of light that is different from the first wavelength. In certain embodiments, the first stimulation, the further stimulation, or both includes heat, and the heat is induced by microwave or induction. In some embodiments, the stimulation includes an electrical current. In certain embodiments, the stimulation is in the absence of an electrical current.

[0021] The ionic liquid may be exposed to the first stimulation simultaneously or substantially simultaneously with the further stimulation, or the ionic liquid may be exposed to the first stimulation and the further stimulation sequentially.

[0022] The ionic liquid may be housed in a container during the present synthetic process, and the orientation of the container (e.g., relative to the source of the stimulation) may be kept constant, or the orientation of the container may be changed relative to the source of the stimulation. When two or more sources of stimulation are used, then the orientation of the container may be kept constant with respect to one or both of the sources of stimulation, may be kept constant only with respect to one of the sources of stimulation, or may be changed relative to both sources of stimulation. Changing the orientation of the container relative to a source of stimulation can include rotating the container, moving the container up or dow n relative to the source of stimulation, moving the container in side-to- side fashion relative to the source of stimulation, or any combination the thereof.

[0023] Preferably, the ionic liquid represents both a solvent for the solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors, and a source of the solvated ionic monomers or oligomers.

[0024] The monomers or oligomers may be complexed with a photoinitiator that induces polymerization of the monomers or oligomers when exposed to the first stimulation. Additionally or alternatively, the ionic liquid may comprise metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

[0025] The ionic liquid may comprise a single metal ion, or two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the stimulation produces a solid metal representing a single metal, or representing an alloy of two or more different metal alloys are present. For example, the ionic liquid may comprise one or more of ions of silver, aluminum, iron, copper, gold, platinum, palladium, tantalum, lithium, zinc, silver, nickel, tungsten, rhenium, cadmium, molybdenum, titanium, or other metals, such as those that may be used in metal parts, such as electrical components. The respective metal ions may be present in the ionic liquid in a concentration of about 50 mM or greater, such as about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140. 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260. 270, 280, 290, 300, 325, 350. 375, 400, 425. 450, 475. 500, 550, 600, 650, 700. 750, 800. 850, 900, 950. 1000 mM or greater.

[0026] In some embodiments, during the course of exposing the ionic liquid to stimulation that is sufficient to convert the moieties within the ionic liquid to solid material, the ionic liquid (which is typically housed within a container during the process) can be monitored in order confirm that the respective concentrations of the moieties within the ionicliquid (the monomer or oligomers, the metal ions, the ionic ceramic precursor, the ionic glass precursor) are sufficiently high for the synthetic process to be carried out. As needed, any one of the moieties having a concentration approaching the minimal amount required for the process (e.g., 300 mM for silver ions) can be replenished within the ionic liquid using methodologies that can readily be appreciated among those skilled in the art.

[0027] The glass precursors may comprise, for example, silicate or potassiumsilicate glasses. In some embodiments, the ionic glass component may be accompanied by or replaced with an ionic sapphire component. In the present disclosure, all references to an ionic glass precursor or to a glass can be substituted with an ionic sapphire component or sapphire, respectively.

[0028] The ionic liquid may additionally or alternatively comprise ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation. The ionic liquid may additionally or alternatively comprise ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

[0029] In certain embodiments, the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulation that is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors. For example, if the ionic liquid includes both metal ions and ionic ceramic precursors, then the further stimulation may include one that is effective to induce formation of conductive material from the metal ions, and one that is effective to induce formation of solid ceramic material from the ionic ceramic precursors.

[0030] In certain embodiments of the present methods in which the ionic liquid comprises solvated metal ions, following exposure of the ionic liquid to the further stimulation in order to induce formation of conductive material from the metal ions, the conductive material may be exposed to inductive heating in order to pulse a current through the conductive material.

[0031] As noted, the present methods may involve the techniques and equipment for any type of three-dimensional printing, including layer by layer, volumetric, two photon, or stereolithography (SLA) printing.

[0032] The present methods may be used to produce any type of article that includes polymeric elements, elements that comprise metal, elements that comprise ceramic, elements that comprise glass, or any combination thereof.

[0033] It should be appreciated that any number of electrical components and / or their components, housings, or the like can be fabricating using the methods described herein. For instance, referring to Figs. 2A-2B. an electrical connector 22 can be made with any of the methods described herein. The electrical connector 22 configured to mate with a complementary electrical component, such as a second electrical connector, and mounted to an electrical device which can be configured as a substrate or as one or more electrical cables. The substrate can be configured as a printed circuit board (PCB). PCBs may be constituted of, for example, FR-4. When the electrical connector 22 is mated with the complementary electrical component and mounted to the electrical device, the electrical connector 22 places the complementary electrical component in electrical communication with the electrical device.

[0034] The electrical connector 22 can include a dielectric or electrically insulative connector housing 30 and a plurality of electrical contacts 32 that are supported by the connector housing 30. In other examples, the connector housing 30 can be electrically conductive. The connector housing 30 defines a mating interface 34 at a front end of the connector housing 30. The connector housing 30 can define a mounting interface 36 at a rear end of the connector housing opposite the mating interface 34 along the longitudinal direction L. Further, the mating interface 34 can be aligned with the mounting interface 36 along the longitudinal direction L. The electrical contacts 32 can define respective mating ends at the mating interface 34, and mounting ends at the mounting interface 36. Thus, the electrical contacts 32 can be configured as vertical contacts whose mating ends and mounting ends are opposite each other with respect to the longitudinal direction L. The electrical connector 22 can similarly be referred to as a vertical connector. The mating ends can be configured to mate with the complementary electrical component, for instance along the longitudinal direction L, and the mounting ends can be configured to be mounted to the electrical device. In other examples, the electrical contacts 32 can be configured as right-angle contacts whose mating ends and mounting ends are oriented perpendicular to each other. The electrical connector 22 can similarly be referred to as a right-angle connector.

[0035] The electrical contacts 32 can be arranged in respective linear arrays 47. The linear arrays 47 can be oriented parallel to each other. The electrical connector 22 can include any number of linear arrays as desired. For instance, the electrical connector 22 caninclude two or more linear arrays 47. The electrical connector 22 can include ground shields disposed between respective adjacent ones of the linear arrays 47.

[0036] The electrical contacts 32 can include a plurality of signal contacts 48 and a plurality of electrical grounds 50 disposed between respective ones of the signal contacts 48. For instance, the adjacent ones of the signal contacts 48 that are adjacent each other along the linear array 47 can define a differential signal pair. While the signal contacts 48 and the grounds 50 can be said to extend along a linear array, it is recognized that at least a portion up to an entirety of the signal contacts and the grounds 50 can be offset with respect to each other along a lateral direction A that is perpendicular to the longitudinal direction.

[0037] The mating ends 48a of adjacent differential signal pairs along the linear array can be separated by at least one ground mating end 54a. In one example, the mating ends 48a of adjacent differential signal pairs can be separated by a plurality of ground mating ends 54a. The mounting ends 48b of adjacent differential signal pairs can be separated by at least one ground mounting end 54b. In one example, the mounting ends 48b of adjacent differential signal pairs can be separated by a plurality of ground mounting ends 54b. For instance, the mounting ends 48b of the signal contacts 48 can be separated by a pair of ground mounting ends 54b. The mounting ends 48b and the ground mounting ends 54b can be configured in any manner as desired, including but not limited to solder balls, press-fit tails, j-shaped leads. Alternatively, and as described above, the mounting ends 48b and the ground mounting ends 54b can be configured as cable mounts that attach to respective electrical conductors and electrical grounds of an electrical cable.

[0038] It is recognized that the grounds 50 can be defined by respective discrete ground contacts. Alternatively, the grounds 50 can be defined by a respective one of a plurality of ground plates. In one example the electrical connector 22 can include a plurality of leadframe assemblies 62 that are supported by the connector housing 30. Each of the leadframe assemblies 62 can include a dielectric or electrically insulative leadframe housing 64, and a respective linear array 47 of the plurality of first electrical contacts 32. Thus, it can be said that each leadframe assembly 62 is oriented along one of the linear arrays 47 of the first electrical connector 22. The respective signal contacts 48 can be insert molded in the leadframe housing 64. Alternatively, the signal contacts 48 can be stitched into the leadframe housing 64. Further, the grounds of the respective linear array 47 can be defined by a ground plate as described above. The ground plate can include a plate body 68 that is supported by the leadframe housing 64, such that the ground mating ends 54a and the ground mounting ends 54b extend out from the plate body 68. Thus, the plate body 68, the ground mating ends54a, and the ground mounting ends 54b can all be monolithic with each other. Respective ones of the ground plate bodies 68 can be disposed between respective adjacent linear arrays of the intermediate regions of the electrical signal contacts 48.

[0039] The ground plate can be configured to electrically shield the signal contacts 48 of the respective first linear array 47 from the signal contacts 48 of an adjacent one of the first linear arrays 47 along the lateral direction A. Thus, the ground plates can also be referred to as electrical shields. Further, it can be said that an electrical shield is disposed between, along the lateral direction A, adjacent ones of respective linear arrays of the electrical signal contacts 48. In one example, the ground plates can be made of any suitable metal. In another example, the ground plates can include an electrically conductive lossy material. In still another example, the ground plates can include an electrically nonconductive lossy material.

[0040] In another example, referring to Fig. 3, another electrical component that can be fabricated using the methods described herein can be configured as a printed circuit board (PCB) 220. PCB 220 can include a PCB body 225 having a first major surface 222 and a second major surface 224 opposite the first major surface 222. The PCB 220 can include one or more electrical contact locations 226 to which electrical components such as electrical connectors or other electrical components can be mated or mounted. The electrical contact locations 226 can be disposed at the first major surface 222, the second major surface 224, or each of the first and second major surfaces. As shown, the electrical contact locations 226 can be configured as electrical contact pads, but can be alternatively configured as desired. The PCB 220 can further include electrical traces at either or both of the first and second major surfaces 222 and 224. The electrical traces 228 can be in electrical communication with respective ones of the electrical contact locations 226. In some examples, the electrical traces 228 can be disposed between the first and second major surfaces 224. While the PCB body 225 can be made from FR4 material, the PCB body 225 can be alternatively made from any suitable dielectric material. In one example, the dielectric material can be a polymer.

[0041] In another example, referring to Figs. 4A-4B, another electrical component that can be fabricated using the methods described herein can be configured as a wafer having electrically conductive vias. The wafer can include a substrate 120 that defines opposed outer surfaces including a first surface 122 and a second surface 124 opposite the first surface. The substrate 120 can be a glass substrate. The glass substrate can be made from borosilicate. In another example, the glass substrate can be made of quartz. Alternatively still, the glass substrate can be made from one or more up to all of borosilicate.aluminasilicate, and quartz including single-crystal quartz, and synthetic quartz. The glass substrate can alternatively be made of any suitable alternative glass substrate materials or combinations thereof. Alternatively still, the substrate can be made of sapphire, silicon, zinc oxide, zirconium oxide, including yttria-stabilized zirconium oxide, ceramic, or combinations thereof. In certain examples, the glass substrate can be lead-free, meaning that the glass substrate can be free of lead including lead oxides, lead alloys, lead compounds, and all lead constituents.

[0042] The substrate 120 can include a plurality of holes 126. The holes 126 extend from the first surface 122 toward the second surface 124 along a central axis. For instance, the holes can extend from the first surface 122 to the second surface 124 along the central axis. The substrate 120 can be cut into wafers of 150 mm, 200 mm, or 300 mm in diameter, but it is recognized that the substrate 120 can define any suitable diameter or other maximum dimension as desired. Thus, the term “diameter” can be used interchangeably with the term “maximum cross-sectional dimension” to denote that the structure of reference need not be circular unless otherwise indicated.

[0043] The holes 126 can have any suitable diameter as desired. For instance, the holes 126 can have a diameter or other cross-sectional dimension that range from 10 pm to 25 pm. The holes 126 can have a depth along their respective central axes that ranges from 100 pm to 500 pm. The diameter requirements have no upper limit. The aspect ratio between hole diameter and hole depth are unlimited for this process. Additionally, a plurality of different hole diameters may be placed in the same substrate. The holes 126 can be conical in shape, cylindrical in shape, hourglass shaped, or can define any suitable shape along their length. The holes 126 can be arranged in one or more hole arrays 127 as desired. While glass substrates can have particular applicability to certain end-use applications, it should be appreciated that substrate 120 can be a glass substrate, a silicon substrate, a ceramic substrate, or any organic substrate or any other substrate of any suitable alternative material as desired. When the substrate 120 is a glass substrate, the glass can be substantially lead-free, including lead-free, in one example. In other examples, the glass can include lead.

[0044] The term substantially “lead-free,” derivatives thereof, and phrases of like import as used herein can refer a quantity of lead is in accordance with the Restriction of Hazardous Substances Directive (RoHS) specifications. In one example, the term “lead-free,” “free of lead,” and derivatives thereof can mean that means that the quantity of lead is less than . 1% by weight, including 0% by weight. Alternatively or additionally, the term “lead- free,” derivatives thereof, and phrases of like import as used herein can mean that thequantity of lead is less than 0.1% by volume. In another example, the term “lead-free,’' derivatives thereof, and phrases of like import as used herein can mean that the quantity of lead is less than 100 parts per million (ppm).

[0045] At least one or more of the holes 126 can be configured as a through hole 128 that extends through the substrate 120 from the first surface 122 to the second surface 124. Thus, the first surface 122 defines a first opening 123 to the through hole 128, and the second surface 124 defines a second opening 125 to the through hole 128. Otherwise stated, the through hole 128 defines a first end at the first opening 123, and a second end at the second opening 125. Thus, both the first and second ends of the through holes 128 are open to the outer perimeter of the substrate 120. The through hole 128 can be straight and linear from the first opening 123 to the second opening 125. Alternatively, one or more portions of the through hole 128 can be angled, bent, or define any suitable alternative non-straight shape.

[0046] Alternatively or additionally, at least one or more of the holes 126 can be configured as a blind hole 130 that can extend from one of the first and second surfaces 122 and 124 toward the other one of the first and second surfaces 122 and 124. Further, the blind hole can terminate at a location spaced from the other of the first and second surfaces 122 and 124. Thus, the blind hole 130 is open to one surface of the substrate 120 at a first end, and internally closed by the substrate 120 at a second end opposite the first end. Otherwise stated, the first terminal end of the blind hole 130 extends to one of the first and second openings 123 and 125 at the first and second surfaces 122 and 124, respectively, and the second terminal end of the blind hole 130 is disposed between the first and second surfaces 122 and 124. It is recognized, however, that the second terminal end of the blind hole 130 can terminate at another hole 26, and thus can be in fluid communication with both the first and second openings 123 and 125. Further, the blind hole 130 can be linear, or can have one or more segments that are angled with respect to each other. One or more of the segments can include a lateral component. The substrate 120 can include a sacrificial hole that extends from the blind hole 130 to an outer surface of the substrate 120. For instance, when the blind hole 130 is open, either directly or through another hole, to the first surface 122 of the substrate 120, the sacrificial hole can extend from the closed end of the blind hole 130 to the second surface 124. Alternatively still, the hole can be a buried hole that is entirely encapsulated in the substrate at a location spaced from each of the first and second surfaces 122 and 124.

[0047] One or more up to all of the holes 126 can be contain an electrically conductive material 135 so as to define an electrically conductive via 134. The electrically conductive material 135 can coat an internal surface that defines the hole 126 without filling the hole 126, in one example. In another example, the electrically conductive material 135 can include an electrically conductive fill that fills at least a portion up to an entirety of the holes 126. In some examples, a first at least one electrically conductive material coats along the internal surface of the hole, and a second electrically conductive material fills a remainder of the hole 126. The hole arrays 127 including the electrically conductive material illustrated in Figs. 4A-4B can define via arrays. In this regard, it will be appreciated that the substrate 120 having electrically conductive vias 134 can be referred to as an electrical component. The electrically conductive material 135 can thus include at least one electrically conductive material that coats the internal surface that defines the hole alone or in combination with an electrically conductive material that fills at least a portion up to an entirety of the hole. In still other examples, the electrically conductive material 135 can be a single electrically conductive material that fills the hole. In still other examples, the electrically conductive material can define end caps that are spaced from each other and fill opposed ends of the hole. The electrically conductive material 135 can include any one or more up to all of a coating, a fill material, a first end cap, and a second end cap. The coating, fill material, end caps can be made from the same material or different respective materials as desired. In one example, the electrically conductive material 135 can be a metal. For instance, the electrically conductive material can be made from one or more up to all of copper, silver, gold, titanium, any suitable alternative metals, and alloys thereof. Thus, in certain examples, the electrically conductive vias 134 can be referred to as metallized vias 34. Similarly, the substrate 120 can be referred to as a metallized substrate. Alternatively, one or more up to all of the electrically conductive material 135 can be non-metallic, for instance an electrically conductive polymer. The electrically conductive material can further include any suitable metal or electrically conductive polymer coated onto particles of any suitable different metal or nonmetal, which can be electrically conductive or electrically nonconductive. Either or both of the end caps can define a hermetic seal. In other examples, one or both of the end caps can be porous. In still other examples, one or both of the end caps can be dielectric, such as polymeric. In some examples, the hole can define a vacuum between the end caps.

[0048] The through hole 128 that contains the electrically conductive material 135 can be said to define a through via 136. The blind hole 130 that contains the electrically conductive material 135 can be said to define a blind via. The buried hole that contains theelectrically conductive material 135 can be said to define a buried via. Thus, the term ‘‘via” and derivatives thereof as used herein can refer to one or both of the through via 136, the blind via, and the buried via. The electrically conductive material 135 can extend continuously from the first end of the via 134 to the second end of the via 134. Thus, the electrically conductive material 135 can define an electrically conductive path along the via 134 in a direction that extends between first end of the via to the second end of the via. For instance, the electrically conductive path can be defined from the first end of the via 134 to the second end of the via 134. In this regard, it is appreciated that the first and second ends of the via 134 can be defined by the first and second openings 123 and 125 when the via 134 is a through via 136. As will be appreciated from the description below, in some examples the material 135 can include only the electrically conductive material, and air. The air can include one or both of ambient air and an inert gas. For instance, the air can be partial or pure argon. In another example, the air can be pure nitrogen.

[0049] The substrate 120 can include at least one or more electrically conductive redistribution layers 137. The redistribution layers can be applied to one or both of the first surface 122 and the second surface 124. The redistribution layers 137 extend over at least one of the electrically conductive vias 134, and are thus in electrical communication with the electrically conductive material 135. In one example, the substrate 120 can be configured as an electrical interposer configured to make electrical connections at each of the first surface 122 and the second surface 124 at electrical contacts that are in electrical communication with each other through the electrically conductive via 134.

[0050] The electrically conductive material 135 can be defined by any suitable highly conductive electrically conductive material as desired so as to create the electrically conductive via 134. As will be appreciated from the description below, the electrically conductive vias 134 can be suitable for conducting both direct current (DC) and radiofrequency (RF) current. The electrically conductive material 35 can extend in the via 134 from the first end of the via to the second end of the via, such that the electrically conductive material defines an electrically conductive path from the first end to the second end. Thus, when the via 134 is a through via 136. the electrically conductive material 135 can define an electrically conductive path from the first surface 122 of the substrate 120 to the second surface 124.

[0051] Also disclosed herein are systems for producing a multi-material article comprising an ionic liquid comprising (i) solvated ionic monomers or oligomers, and (ii) solvated metal ions, ionic ceramic precursors, ionic glass precursors, or any combinationthereof; and, wherein the stimulation includes a source of a first stimulation that is effective to induce formation of a polymer from the solvated ionic monomers or oligomers, and a source of at least one further stimulation that is effective to induce formation of solid conductive material from the solvated metal ions, to induce formation of a solid ceramic material from the solvated ionic ceramic precursors, to induce formation of a glass from the solvated ionic glass precursors, or any combination thereof.

[0052] Also provided herein are systems for producing a multi-material article comprising an ionic liquid comprising (i) solvated ionic glass precursors, and (ii) solvated metal ions, ionic ceramic precursors, or both; and, wherein the stimulation includes a source of a first stimulation that is effective to induce formation of a glass from the solvated ionic glass precursors, and a source of at least one further stimulation that is effective to induce formation of solid conductive material from the solvated metal ions, to induce formation of a solid ceramic material from the solvated ionic ceramic precursors, or both.

[0053] The contents of the ionic liquid may be in accordance with any of the embodiments described supra in connection with the inventive methods.

[0054] The source of the first stimulation may be the same as or different from the source of the further stimulation. For example, the source of the first stimulation may be an objective lens that omits ultraviolet light, and the source of the second stimulation may be the same objective lens or may be a further objective lens that is able to project the desired form of further stimulation, such as ultraviolet light.

[0055] The present systems may further include an inductive heating coil for delivering induction energy to the ionic liquid or a solid structure formed therefrom following stimulation, e.g., in order to pulse a current through conductive material that is formed from the metal ions following exposure to a further stimulation that is effective to induce nucleation and growth of solid metal from the metal ions.

[0056] Also provided herein are methods for making an article comprising stimulating an ionic liquid having a solvated ionic precursor, so as to induce formation of only a single solid material from the ionic liquid, thereby forming the article comprising the single solid material. With respect to these particular methods, the solvated ionic precursor is selected from the group consisting of solvated ionic monomers or oligomers, solvated ionic ceramic precursors, and solvated ionic glass precursors. In specific embodiments, the solvated ionic precursor is not a solvated metal ion. The present methods are thereby used to make a solid polymeric material, a solid glass material, or a solid ceramic material ("solid'’ referring to the state of matter of the material, and not necessarily excluding solid materialsthat include hollow or void spaces, as desired). In these methods, a single stimulation is used, depending on the type of solvated ionic precursor that is present in the ionic liquid. The stimulation may be selected from any of the types of stimulation otherwise disclosed throughout the present disclosure, as appropriate according to the identity of the solvated ionic precursor. For example, the stimulation may include light or heat. Moreover, the other particular parameters of the ionic liquid, the solvated ionic precursor, the stimulation, the techniques and equipment, and of the method in general, may be selected from the embodiments described elsewhere in the present application, with the caveat that this embodiment involves forming a solid material from a solvated ionic precursor that is selected from the group consisting of solvated ionic monomers or oligomers, solvated ionic ceramic precursors, and solvated ionic glass precursors.

[0057] Also provided herein are systems for producing an article, the system comprising an ionic liquid comprising a solvated ionic precursor; and a source of stimulation that is effective to induce formation of only a single solid material from the solvated ionic precursor. The contents of the ionic liquid in such systems may be in accordance with any of the embodiments described supra in connection with the inventive methods, with the caveat that this embodiment involves a system forming a solid material from a solvated ionic precursor that is selected from the group consisting of solvated ionic monomers or oligomers, solvated ionic ceramic precursors, and solvated ionic glass precursors.

[0058] A general description of aspects of the inventive methods and systems is as follows. The ionic liquid (precursor material) should ideally contain metal, polymer, and / or ceramic precursors as solvated ions to achieve the necessary tolerances, rates of production, and simultaneity of synthesis. Ionic liquids (IL) are molten, molecular salts which are liquid at temperatures below 100 °C notably having high polarity, low vapor pressures, thermal and environmental stability, and wide-ranging inorganic and ionic compounds. While slightly different, ILs are referred to herein as including so-called deep eutectic solvents (DES) [1] as functionally identical in use and application. IL (and DES) properties stem from the IL structure having large organic cationic with smaller inorganic / organic anionic structures. With an estimated >1018[2] possible IL formulations the properties of ILs can be tailored to meet specific needs including lubricity, hydrogen bonding tunability, thermal stability, polarizability, electrical conductivity', metal loading capacity, metal binding specificity', polymerization, and the ability to serve as a redox reaction medium wherein metal ions can be reduced, oxidized, selectively chelated, and selectively deposited. Further, their application and use for additive manufacturing of polymeric ILs (PIL), formation of coatings,and selective dissolution and extraction of metals and oxides have rapidly expanded. The multifunctional nature, provided by adding functional groups to the ILs to form task-specific ILs (TSIL) [3], [4], [5] provides multi-material, simultaneous synthesis and manufacture for additive manufacturing. The TSILs described herein can include a UV sensitive polymeric IL (PIL) along with another TSIL aimed at maximizing solubility of metal (e.g., silver) ions in a photoactive complex. The solution need not contain bulky nanoparticles or fillers which would require significant post-treatment, shrinkage accommodation, and / or local confinement methodologies. The PIL is designed to be photoactive in a different range of wavelengths than the silver TSIL, providing simultaneous polymerization of the dielectric and nucleation and growth of pure silver structures may be achieved. In certain embodiments, some in situ or possible post-treatment thermal treatment may be necessary to achieve the highest achievable polymer strengths and metal conductivities. Essentially, this is a vat photopolymerization route providing highly tunable polymer and metal printing.

[0059] Dielectric materials - Ionic Liquids as solvents and / or monomers. The methodologies described herein are applicable to a wide range of dielectric materials including ceramics and glasses. With respect to polymer dielectric materials, these may be characterized by dielectric permittivities and losses in the 3-5 and 0.05 ranges, respectively. ILs can function both as the solvent as well as the monomer / oligomer source to achieve polymerization[6], [7]. [8], [9], IL can function as a solvent for known, well-understood monomers such as tris[2-(acryloyloxy)ethyl] isocyanurate to achieve acceptably high mechanical and thermal properties, along with understood polymerization behaviors. Polymerization reactions within ILs have been demonstrated to produce equivalent polymers in comparison to reactions in more ty pical volatile organic carbon (VOC). This includes UV- curable methacrylates solvated in the IL l-butyl-3-methylimidazolium phosphorus hexafluoride ([bmim]PFg) or 1 -alky 1-3 -methyl imidazolium tosyl ate

[0010] ,

[0011] ILs. Importantly, w ork by Harrison et al

[0012] ,

[0013] has demonstrated enhanced kinetics in ILs helping satisfy the production rate needs targeted by this disclosure. PIL monomers and structures can be used to provide customizable polymer / dielectric structures. The polymer dielectric can use commercially available photoiniators in the high UV to visible range (405nm-480nm) such as the IL soluble Irgacure 907 or camphorquinone-based chemistries.

[0060] Metal TSILs. For the simultaneous nucleation and grow th of conductive material, UV-catalyzed (355nm and lower are targeted wavelengths) TSILs at the highest possible concentrations can be used. For example, this can correspond to equal to or greater than 300mM of silver ions. Complexed metal or metal salts produce printable solutions withsufficient concentrations can achieve the needed metal trace volumes. High concentrations of metal in ILs for electroless deposition have been demonstrated using aqueous ILs such as imidazolium

[0014] , though the ILs for use here may be anhydrous silylamide / silylamine substituted ILs or reverse ILs (RIL)

[0015] , In fact, RILs have demonstrated highly controllable electroless gold depositions

[0015] . In the case of complexed metal ions, photoinitiators react with the organic complex to allow local precipitation of the metal. Alternatively, use of a complexing species that is itself light sensitive will provide an electron to reduce the positive metal ion to the neutral metal. In situ heating of the silver traces may be necessary to achieve the maximum conductivity of pure silver, however this is not technically a sintering process. Heating can be achieved by use of induction or microwave fields, and can also provide thermal treatment to the adjacent dielectric polymer with attendant increases in mechanical and thermal stability of the polymers.

[0061] Glass and Ceramics. Ceramics, when used, may include be gamma-alumina (permittivity —3.4) or alpha-alumina (permittivity is higher though at ~9), however the dielectric losses will be much lower in the 0.005 range. Glass may be, for example, be silicate or potassium-silicate glasses with possible permittivity 3 and 0.001 loss. All may be stimulated by UV (355-405nm), for example, or lower wavelengths. Heating, particularly microwave, may be used to produce the best dielectric materials. Heating, as described supra, may also be provided by thermal conduction due to the inductive or microwave heating of the conductive traces.Examples

[0062] The present invention is further defined in the following Examples. It should be understood that the examples, while indicating preferred embodiments of the invention, are given by way of illustration only, and should not be construed as limiting the appended claims. From the above discussion and the examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.Example 1 - Polymer and Metal Multi-Material Article From Ionic Liquid

[0063] An imidazolium cation IL solvating silver nitrate(targeting greater than 300mM concentrations) and tris[2-(acryloyloxy)ethyl] isocyanurate are used for polymer precursors. The polymer precursor is mixed with lwt% Irgacure 907 photoinitiators while the silver ions is complexed with lwt% Sartomer Speedcure BDMB photoinitiators (aminioacetophenone family of photoinitiators). Using two objective lenses, one for eachwavelength of light, volumetric printing techniques are used to simultaneously print metal and dielectric traces into particular geometries of interest. These geometries are PCB-like structures. Immediately following printing, an inductive heating coil is used to pulse a current through the silver traces to achieve metallurgically intimate grain boundary contacts between the printed metallic structures. This localized heating is then used to thermally cure the polymer dielectric adjacent to the metal traces. The articles are then complete and removed from the printing solvent / resin tank.Example 2 - Glass and Metal Multi-Material Article From Ionic Liquid

[0064] For a glass / metal component a methylimidazolium cation IL solvating silver nitrate (targeting greater than 300mM concentrations) and silicon-containing precursors. The silicon precursors are prepared by pre-reacting silica powders and sodium metasilicate with a methylimidazolium cation to solvate the silicon, then mixed with lwt% Irgacure 907 photoinitiators while the silver ions are complexed with lwt% Sartomer Speedcure BDMB photoinitiators (aminioacetophenone family of photoinitiators). Using two objective lenses, one for each wavelength of light, volumetric printing is used to simultaneously print metal and dielectnc traces into particular geometries of interest. These geometries are PCB-like structures. Immediately following printing an inductive heating coil is used to pulse a current through the silver traces to achieve metallurgically intimate grain boundary' contacts between the printed metallic structures. This localized heating is used to thermally cure the glass dielectric adjacent to the metal traces. Alternatively, since glasses can have microwave susceptibility’ microwave heating can be used to provide intimate metallurgical contacts. The components are then considered complete and removed from the printing solvent / resin tank. Alumina precursor powders can be used in place of the silicon powders to achieve similar outcomes to achieve gamma-alumina dielectric materials.

[0065] References[1] L. I. N. Tome, V. Baiao, W. Da Silva, and C. M. A. Brett, “Deep eutectic solvents for the production and application of new materials,” Appl. Mater. Today, vol. 10, pp. 30-50, Mar. 2018, doi: 10.1016 / j.apmt.2017.11.005.[2] I. A. Berezianko and S. V. Kostjuk, “Ionic liquids in cationic polymerization: A review,” J. Mol. Liq., vol. 397, p. 124037, Mar. 2024, doi: 10. 1016 / j.molliq.2024.124037.[3] L. Chen et al., “Applying basic research on a dialkylphosphoric acid based taskspecific ionic liquid for the solvent extraction and membrane separation of yttrium,” Sep. Purif. Technol., vol. 207, pp. 179-186, Dec. 2018, doi: 10. 1016Zj.seppur.2018.06.042.[4] P. Nockemann et al. , “Task-Specific Ionic Liquid for Solubilizing Metal Oxides,” J. Phys. Chem. B, vol. 110. no. 42, pp. 20978-20992, Oct. 2006, doi: 10.1021 / jp0642995.[5] P. Nockemann et al. , “Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides,” Inorg. Chem., vol. 47, no. 21, pp. 9987-9999, Nov. 2008, doi: 10.1021 / ic801213z.[6] G. Durga, P. Kalra. V. Kumar Verma, K. Wangdi. and A. Mishra, “Ionic liquids: From a solvent for polymeric reactions to the monomers for poly(ionic liquids),” J. Mol. Liq., vol. 335, p. 116540, Aug. 2021, doi: 10.1016 / j.molliq.2021.116540.[7] J. Lemus, A. Eguizabal, and M. P. Pina, “UV polymerization of room temperature ionic liquids for high temperature PEMs: Study of ionic moieties and crosslinking effects,” Int. J. Hydrog. Energy, vol. 40, no. 15, pp. 5416-5424, Apr. 2015, doi:10.1016 / j.ijhydene.2015.01.078.[8] K. R. Hossain, P. Jiang, X. Yao, X. Yang, D. Hu, and X. Wang, “Ionic liquids for 3D printing: Fabrication, properties, applications,” J Ion. Liq., vol. 3, no. 2, p. 100066, Dec. 2023, doi: 10. 1016 / j.jil.2023. 100066.[9] A. R. Schultz et al., “3D Printing Phosphonium Ionic Liquid Networks with Mask Projection Microstereolithography,” ACS Macro Lett., vol. 3, no. l l, pp. 1205-1209, Nov. 2014, doi: 10.1021 / mz5006316.

[0010] P. Kubisa, “Kinetics of radical polymerization in ionic liquids,” Eur. Polym. J., vol. 133, p. 109778, Jun. 2020. doi: 10. 1016 / j.eurpolymj.2020. 109778.

[0011] V. Strehmel, “Selection of Ionic Liquids for Free Radical Polymerization Processes,” Macromol. Symp., vol. 254, no. 1, pp. 25-33, Aug. 2007, doi: 10.1002 / masy.200750804.

[0012] S. Harrisson, S. R. Mackenzie, and D. M. Haddleton, “Unprecedented solvent- induced acceleration of free-radical propagation of methyl methacrylate in ionic liquids,” Chem Commun, no. 23, pp. 2850-2851, 2002, doi: 10.1039 / B209479G.

[0013] S. Harrisson, S. R. Mackenzie, and D. M. Haddleton, “Pulsed Laser Polymerization in an Ionic Liquid: Strong Solvent Effects on Propagation and Termination of Methyl Methacrylate,” Macromolecules, vol. 36, no. 14, pp. 5072-5075, Jul. 2003. doi: 10.1021 / ma034447e.

[0014] K. Riaz et al., “Ionic liquid based electroless silver plating bath for Printable circuit boards (PCBs) finishing,” J Mol. Liq., vol. 394, p. 123704, Jan. 2024, doi: 10.1016 / j.molliq.2023.123704.

[0015] Z. Sun. E. Hammond-Pereira, X. Zhang. D. Wu. and S. R. Saunders, “Reversible ionic liquids (RevILs) for the preparation of thermally stable SBA-15 supported goldnanoparticle catalysts,'’ Appl. Catal. Gen., vol. 643, p. 118725, Aug. 2022, doi: 10.1016 / j . apcata.2022. 118725.

Claims

What is claimed:

1. A method for making a multi -material article comprising: exposing to stimulation an ionic liquid comprising (i) solvated ionic monomers or oligomers, and (ii) solvated metal ions, ionic ceramic precursors, ionic glass precursors, or any combination thereof, wherein the stimulation includes a first stimulation that is effective to induce formation of a polymer from the ionic monomers or oligomers, and at least one further stimulation that is effective to induce formation of solid conductive material from the metal ions, to induce formation of a solid ceramic material from the ionic ceramic precursors, to induce formation of a glass from the ionic glass precursors, or any combination thereof, thereby forming the multi-material article comprising the polymer and the solid conductive material, the solid ceramic material, the glass, or any combination thereof.

2. The method according to claim 1, wherein the first stimulation, the further stimulation, or both includes light or heat.

3. The method according to claim 2, wherein the first stimulation, the further stimulation, or both includes heat, and the heat is induced by microwave or induction.

4. The method according to any preceding claim, wherein the first stimulation comprises a first wavelength of light, and the further stimulation comprises a second wavelength of light that is different from the first wavelength.

5. The method according to any preceding claim, wherein ionic liquid is exposed to the first stimulation simultaneously with the further stimulation.

6. The method according to the preceding claim, comprising exposing the ionic liquid to the first stimulation and the further stimulation sequentially.

7. The method according to any preceding claim, wherein the ionic liquid represents both a solvent for the solvated metal ions, ionic ceramic precursors, or ionic glass precursors, and a source of the ionic monomers or oligomers.

8. The method according to any preceding claim, wherein the monomers or oligomers are complexed with a photoinitiator that induces polymerization of the monomers or oligomers when exposed to the first stimulation.

9. The method according to any preceding claim, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

10. The method according any preceding claim, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation produces a solid metal representing an alloy.

11. The method according to any preceding claim, wherein the ionic liquid comprises ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation.

12. The method according to any preceding claim, wherein the ionic liquid comprises ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

13. The method according to any preceding claim, wherein the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulation that is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors.

14. The method according to any preceding claim, wherein the ionic liquid comprises metal ions, and following exposure of the ionic liquid to the further stimulation in order to induce formation of conductive material from the metal ions, the conductive material is exposed to inductive heating in order to pulse a current through the conductive material.

15. The method according to any preceding claim, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article layer by layer.

16. The method according to any one of claims 1-14, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article by volumetric printing.

17. The method according to any one of claims 1-14, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi -material article by two photon printing.

18. The method according to any one of claims 1-14, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi-material article by stereolithography (SLA) printing.

19. The method according to any preceding claim, wherein the multi-material article comprises a connector.

20. The method according to any one of claims 1-18, wherein the multi -material article comprises a printed circuit board (PCB).

21. The method according to any one of claims 1-18, wherein the multi-material article comprises a silicon or glass wafer with a via.

22. A multi-material article that is produced according to the method according to any one of claims 1-18.

23. A system for producing a multi-material article comprising an ionic liquid comprising (i) solvated ionic monomers or oligomers, and (ii) solvatedmetal ions, ionic ceramic precursors, ionic glass precursors, or any combination thereof; and, wherein the stimulation includes a source of a first stimulation that is effective to induce formation of a polymer from the ionic monomers or oligomers, and a source of at least one further stimulation that is effective to induce formation of solid conductive material from the metal ions, to induce formation of a solid ceramic material from the ionic ceramic precursors, to induce formation of a glass from the ionic glass precursors, or any combination thereof.

24. The system according to claim 23, wherein the ionic liquid represents both a solvent for the solvated metal ions, ionic ceramic precursors, or ionic glass precursors, and a source of the ionic monomers or oligomers.

25. The system according to claim 23 or claim 24, wherein the monomers or oligomers are complexed with a photoinitiator that induces polymerization of the monomers or oligomers when exposed to the first stimulation.

26. The system according to any one of claims 23-25, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

27. The system according any one of claims 23-26, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation produces a solid metal representing an alloy.

28. The system according to any one of claims 23-27, wherein the ionic liquid comprises ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation.

29. The system according to any one of claims 23-28. wherein the ionic liquid comprises ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

30. The system according to any one of claims 23-29, wherein the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulation that is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors,31. The system according to any one of claims 23-30, wherein the source of a first stimulation is the same as the source of the further stimulation.

32. The system according to any one of claims 23-30, wherein the source of a first stimulation is different from the source of the further stimulation.

33. The system according to any one of claims 23-32. further comprising an inductive heating coil.

34. A method for making a multi-material article comprising exposing to stimulation an ionic liquid comprising (i) ionic glass precursors, and (ii) solvated metal ions, ionic ceramic precursors, or both, wherein the stimulation includes a first stimulation that is effective to induce formation of a glass from the ionic glass precursors, and at least one further stimulation that is effective to induce formation of solid conductive material from the metal ions, to induce formation of a solid ceramic material from the ionic ceramic precursors, or both, thereby forming the multi-material article comprising the glass and the solid conductive material, the solid ceramic material, or both.

35. The method according to claim 34, wherein the first stimulation, the further stimulation, or both includes light or heat.

36. The method according to claim 35, wherein the first stimulation, the further stimulation, or both includes heat, and the heat is induced by microwave or induction.

37. The method according to any one of claims 34-36, wherein the first stimulation comprises a first wavelength of light, and the further stimulation comprises a second wavelength of light that is different from the first wavelength.

38. The method according to any one of claims 34-37, wherein ionic liquid is exposed to the first stimulation simultaneously with the further stimulation.

39. The method according to any one of claims 34-38, comprising exposing the ionic liquid to the first stimulation and the further stimulation sequentially.

40. The method according to any one of claims 34-39, wherein the ionic liquid represents both a solvent for the solvated metal ions, ionic ceramic precursors, or ionic glass precursors, and a source of the ionic monomers or oligomers.

41. The method according to any one of claims 34-40, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

42. The method according to any one of claims 34-41, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation produces a solid metal representing an alloy.

43. The method according to any one of claims 34-42, wherein the ionic liquid comprises ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation.

44. The method according to any one of claims 34-43, wherein the ionic liquid comprises ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

45. The method according to any one of claims 34-44, wherein the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulationthat is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors.

46. The method according to any one of claims 34-45, wherein the ionic liquid comprises metal ions, and follow ing exposure of the ionic liquid to the further stimulation in order to induce formation of conductive material from the metal ions, the conductive material is exposed to inductive heating in order to pulse a cunent through the conductive material.

47. The method according to any one of claims 34-46, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article layer by layer.

48. The method according to any one of claims 34-46, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article by volumetric printing.

49. The method according to any one of claims 34-46, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi-material article by two photon printing.

50. The method according to any one of claims 34-46, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi-material article by stereolithography (SLA).

51. A system for producing a multi-material article comprising an ionic liquid comprising (i) ionic glass precursors, and (ii) solvated metal ions, ionic ceramic precursors, or both; and, wherein the stimulation includes a source of a first stimulation that is effective to induce formation of a glass from the ionic glass precursors, and a source of at least one further stimulation that is effective to induce formation of solid conductive material from the metal ions, to induce formation of a solid ceramic material from the ionic ceramic precursors, or both.

52. The system according to claim 51, wherein the ionic liquid represents a solvent for the solvated metal ions, ionic ceramic precursors, or ionic glass precursors.

53. The system according to claim 51 or claim 52. wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and grow th of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

54. The system according any one of claims 51-53, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation produces a solid metal representing an alloy.

55. The system according to any one of claims 51-54, w herein the ionic liquid comprises ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation.

56. The system according to any one of claims 51-55, wherein the ionic liquid comprises ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

57. The system according to any one of claims 51-56, wherein the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulation that is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors,58. The system according to any one of claims 51-57, wherein the source of a first stimulation is the same as the source of the further stimulation.

59. The system according to any one of claims 51-57, wherein the source of a first stimulation is different from the source of the further stimulation.

60. The system according to any one of claims 51-59, further comprising an inductive heating coil.

61. A method for making an article comprising: stimulating an ionic liquid having a solvated ionic precursor, so as to induce formation of only a single solid material from the ionic liquid, thereby forming the article comprising the single solid material.

62. The method according to claim 61, wherein the stimulation includes an electrical current.

63. The method according to claim 61 or claim 62, wherein the stimulation includes light or heat.

64. The method according to any one of claims 61 to 63, wherein the stimulation includes heat, and the heat is induced by microwave or induction.

65. The method according to any one of claims 61 to 64, wherein the ionic liquid represents a solvent for the ionic precursor.

66. The method according to claim 65, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the stimulation.

67. The method according to claim 61 or claim 66, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the stimulation produces a solid metal representing an alloy.

68. The method according to claim 61, wherein the ionic liquid comprises metal ions, and following exposure of the ionic liquid to stimulation in order to induce formation of conductive material from the metal ions, the conductive material is exposed to inductive heating in order to pulse a current through the conductive material.

69. The method according to any one of claims 61 to 68, wherein exposing the ionic liquid to the stimulation produces the article layer by layer.

70. The method according to any one of claims 61 to 69, wherein exposing the ionic liquid to the stimulation produces the article by volumetric printing.

71. The method according to any one of claims 61 to 70, wherein exposing the ionic liquid to the stimulation produces the article by two photon printing.

72. The method according to any one of claims 61 to 71, wherein exposing the ionic liquid to the stimulation produces the article by stereolithography (SLA) printing.

73. The method according to any one of claims 61 to 72, wherein the article comprises a connector.

74. An article that is produced according to the method according to any one of claims 61 to 72.

75. A system for producing an article, the system comprising: an ionic liquid comprising a solvated ionic precursor; and a source of stimulation that is effective to induce formation of only a single solid material from the solvated ionic precursor.

76. The system according to claim 75, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the stimulation.

77. The system according to claim 75 or claim 76, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the stimulation produces a solid metal representing an alloy.

78. The system according to any one of claims 75-77, further comprising an inductive heating coil.

79. A method for making a multi-material article comprising: exposing to stimulation an ionic liquid comprising two or more of solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors, wherein the stimulation includes a first stimulation that is effective to induce formation of a solid material from one of the solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors, and wherein the stimulation includes at least one further stimulation that is effective to induce formation of a solid material from another one of the solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors. thereby forming the multi-material article comprising two or more of a polymer, a solid conductive material, a solid ceramic material, and a glass.

80. The method according to claim 79, wherein the first stimulation, the further stimulation, or both includes light or heat.

81. The method according to claim 80, wherein the first stimulation, the further stimulation, or both includes heat, and the heat is induced by microwave or induction.

82. The method according to any one of claims 79-81, wherein the first stimulation comprises a first wavelength of light, and the further stimulation comprises a second wavelength of light that is different from the first wavelength.

83. The method according to any one of claims 79-82, wherein ionic liquid is exposed to the first stimulation simultaneously with the further stimulation.

84. The method according to any one of claims 79-83, comprising exposing the ionic liquid to the first stimulation and the further stimulation sequentially.

85. The method according to any one of claims 79-84, wherein the ionic liquid represents both a solvent for the solvated metal ions, ionic ceramic precursors, or ionic glass precursors, and a source of the ionic monomers or oligomers.

86. The method according to any one of claims 79-85, wherein the monomers or oligomers are complexed with a photoinitiator that induces polymerization of the monomers or oligomers when exposed to the first stimulation.

87. The method according to any one of claims 79-86, wherein the ionic liquid comprises metal ions that are complexed with a photoinitiator that induces nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation.

88. The method according any one of claims 79-87, wherein the ionic liquid comprises two or more different metal ions, and nucleation and growth of solid metal from the metal ions when the ionic liquid is exposed to the further stimulation produces a solid metal representing an alloy.

89. The method according to any one of claims 79-88, wherein the ionic liquid comprises ionic ceramic precursors that are complexed with a photoinitiator that induces formation of solid ceramic material when the ionic liquid is exposed to the further stimulation.

90. The method according to any one of claims 79-89, wherein the ionic liquid comprises ionic glass precursors that are complexed with a photoinitiator that induces formation of solid glass material when the ionic liquid is exposed to the further stimulation.

91. The method according to any one of claims 79-90, wherein the ionic liquid comprises two or more of metal ions, ionic ceramic precursors, and ionic glass precursors, and the further stimulation includes at least two of (i) a first further stimulation that is effective to induce formation of conductive material from the metal ions, (ii) a second further stimulation that is effective to induce formation of solid glass material from the ionic glass precursors, and (iii) a third further stimulation that is effective to induce formation of solid ceramic material from the ionic ceramic precursors.

92. The method according to any one of claims 79-91, w herein the ionic liquid comprises metal ions, and following exposure of the ionic liquid to the further stimulation in order to induce formation of conductive material from the metal ions, the conductive material is exposed to inductive heating in order to pulse a cunent through the conductive material.

93. The method according to any one of claims 79-92, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article layer bylayer.

94. The method according to any one of claims 79-92, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article by volumetric printing.

95. The method according to any one of claims 79-92, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi-material article by two photon printing.

96. The method according to any one of claims 79-92, wherein exposing the ionic liquid to the first stimulation and the further stimulation produces the multi-material article produces the multi-material article by stereolithography (SLA) printing.

97. The method according to any one of claims 79-96, wherein the multi -material article comprises a connector.

98. The method according to any one of claims 79-96, wherein the multi -material article comprises a printed circuit board (PCB).

99. The method according to any one of claims 79-96, wherein the multi-material article comprises a silicon or glass wafer with a via.

100. A multi-material article that is produced according to the method according to any one of claims any one of claims 79-96.

101. A system for producing a multi-material article comprising an ionic liquid comprising two or more of solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors,; and, wherein the stimulation includes a source of a first stimulation that is effective to induce formation of a solid material from one of the solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors, anda source of a further stimulation that is effective to induce formation of a solid material from another one of the solvated ionic monomers or oligomers, solvated metal ions, solvated ionic ceramic precursors, or solvated ionic glass precursors.

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