Fabrication of Three-Dimensional Materials Gradient Structures by In-Flight Curing of Aerosols
20170348903 · 2017-12-07
Inventors
Cpc classification
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B29C64/112
PERFORMING OPERATIONS; TRANSPORTING
B29C64/129
PERFORMING OPERATIONS; TRANSPORTING
B33Y80/00
PERFORMING OPERATIONS; TRANSPORTING
G02B6/02123
PHYSICS
B33Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B29C64/20
PERFORMING OPERATIONS; TRANSPORTING
International classification
B29C64/112
PERFORMING OPERATIONS; TRANSPORTING
B29D11/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y80/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method for fabricating three-dimensional structures. In-flight heating, evaporation, or UV illumination modifies the properties of aerosol droplets as they are jetted onto a target surface. The UV light at least partially cures photopolymer droplets, or alternatively causes droplets of solvent-based nanoparticle dispersions to rapidly dry in flight, and the resulting increased viscosity of the aerosol droplets facilitates the formation of free standing three-dimensional structures. This 3D fabrication can be performed using a wide variety of photopolymer, nanoparticle dispersion, and composite materials. The resulting 3D shapes can be free standing, fabricated without supports, and can attain arbitrary shapes by manipulating the print nozzle relative to the target substrate. Multiple materials may be mixed and deposited to form structures with compositionally graded material profiles, for example Bragg gratings in a light pipe or optical fiber, optical interconnects, and flat lenses.
Claims
1. A method for fabricating a three-dimensional structure on a substrate, the method comprising: aerosolizing a first material and a second material; mixing droplets comprising the first material with droplets comprising the second material to form a mixed aerosol; propelling droplets of the mixed aerosol from a deposition head toward the substrate; partially modifying a property of the mixed aerosol droplets in-flight; and fully modifying the property of the mixed aerosol droplets once they have been deposited as part of the three-dimensional structure.
2. The method of claim 1 wherein the aerosol droplets comprise a photocurable polymer and modifying a property comprises curing or solidifying using electromagnetic radiation.
3. The method of claim 2 wherein the fabricated three-dimensional structure comprises a light pipe or an optical fiber.
4. The method of claim 3 wherein the first and second materials have different refractive indices.
5. The method of claim 4 wherein the mixing step comprises varying the relative amounts of the first and second materials.
6. The method of claim 5 wherein the light pipe or optical fiber comprises a periodic variation of the relative compositions of the two materials along a length of the light pipe or optical fiber.
7. The method of claim 6 wherein the light pipe or optical fiber comprises a Bragg grating.
8. The method of claim 7 wherein one of the materials is reflective or fluorescent.
9. The method of claim 3 wherein an exterior surface of the light pipe or optical fiber comprises optical cladding.
10. The method of claim 9 wherein a roughness of the exterior surface and/or the optical cladding is less than one micron.
11. The method of claim 9 wherein the optical cladding has a lower refractive index than both a refractive index of the first material and a refractive index of the second material.
12. The method of claim 1 wherein the three-dimensional structure comprises an optical interconnect.
13. The method of claim 1 wherein the mixing step comprises varying the relative amounts of the first and second materials.
14. The method of claim 6 wherein the three-dimensional structure comprises compositionally graded material profiles and/or materials gradients.
15. The method of claim 14 wherein the three-dimensional structure comprises a flat lens comprising a first refractive index at an edge of the lens and a second refractive index at a center of the lens.
16. The method of claim 1 wherein the aerosol droplets comprise a solvent and modifying a property comprises evaporating the solvent.
17. The method of claim 16 wherein the aerosol droplets comprise metal nanoparticles, the method further comprising: irradiating the aerosol droplets with UV radiation; heating the metal nanoparticles; and heating the aerosol droplets sufficiently to at least partially evaporate the solvent; and continuing to irradiate the metal nanoparticles after they have been deposited, thereby at least partially sintering the metal nanoparticles.
18. The method of claim 1 further comprising tilting or translating the deposition head with respect to the substrate.
19. The method of claim 1 comprising fabricating an overhanging structure without requiring a sacrificial support or tilting the deposition head or the substrate.
20. The method of claim 1 wherein the standoff distance between the deposition head and the substrate is at least 1 mm.
21. The method of claim 20 wherein the standoff distance between the deposition head and the substrate is between 2 mm and 5 mm.
22. The method of claim 1 comprising increasing the viscosity of the aerosol droplets in-flight.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating a preferred embodiment of the invention and are not to be construed as limiting the invention. In the drawings:
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DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0032] The present invention is a method of making three-dimensional structures, such as structures comprising high aspect ratio features, using in-flight curing of aerosols and inks, and direct printing of liquid materials to fabricate three-dimensional, free standing, complex structures. Specifically, embodiments of the present invention combine patented Aerosol Jet® dispensing technology, such as that described in U.S. Pat. Nos. 7,674,671, 7,938,079, and 7,987,813, with an in-flight materials processing mechanism that enables liquid droplets to partially solidify before depositing on a surface. After the in-flight processing, the droplets can be deposited to form free standing structures. Some of the advantages of this approach include ultra-high resolution three-dimensional (3D) printing, with feature sizes down to 10 microns, lateral feature resolution to 1 micron, and vertical resolution to 100 nm. The aspect ratio of the free-standing structures can be more than 100, and the structures can be printed on nearly any surface and surface geometry by manipulating the tilt and location of the print head relative to those surfaces. Overhangs and closed cells can be printed directly, without using sacrificial support materials. Both metal and insulating materials can be processed, which enables the co-deposition of electronic materials for fabricating circuits in 3D. Furthermore, composite materials can be printed, which allow for the tailoring of the mechanical and electrical properties of the 3D structures. Ultraviolet (UV) polymers can be cured in-flight as they are impacting on the target, and low sintering temperatures enable metallization of plastics. Using an Aerosol Jet® process, practically any type of material and/or solvent can be printed. The large standoff from the substrate (typically a few millimeters) for this process enables high aspect printing without any z-axis motion. Sub-10 micron focusing of the aerosol jet enables creation of ultrafine features.
[0033] Aerosol Jet® printing is a non-contact, aerosol-based jetting technology. The starting inks are formulated with low viscosity (0.5 to 1000 cP) and in the typical process they are first aerosolized into a fine droplet dispersion of 1-5 μm diameter droplets. Preferably nitrogen gas entrains the droplets and propels them through a fine nozzle (0.1-1 mm inner diameter) to a target substrate for deposition. A co-flowing, preferably nitrogen sheath gas focuses the droplet jet down to a 10 μm diameter, which allows features of this size to be printed. The jetting technology is notable for the large standoff distance between the nozzle and substrate (several mm), the fine resolution (feature width 10 μm), volumetric dispense accuracy (10 femtoliter), and wide range of material compatibility. Because of the large standoff distance, it is possible to dry and/or otherwise cure the droplets during their flight to the substrate. In doing so, the viscosity of the droplets can be increased much beyond the starting viscosity. With higher viscosity, the printed inks are self-supporting and can be built up into free standing columns and other high aspect ratio features. In order to increase the viscosity, UV light from either a lamp or a UV LED is preferably applied to the interstitial region between the nozzle exit and the target substrate, as shown in
[0034] An embodiment of an apparatus of the present invention is shown in
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[0037] In-flight processing is also possible when solid particles, such as ceramics, metals, or fibers, are dispersed in the photopolymer ink. In this case, the cured photopolymer serves as a 3D mechanical support for the solid particles. The mechanical and electrical properties of this composite material can be optimized by, for example, providing wear and abrasion resistance, as well as forming 3D electrical conductors.
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[0043] In the case of solvent based inks, such as metal nanoparticle dispersions, the droplet viscosity can be increased by partially or fully drying the droplet during flight. Since metal nanoparticles are known to be highly absorbing to UV light, exposing the droplets to UV illumination will heat the nanoparticles and accelerate the solvent evaporation.
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[0045] In embodiments of the present invention, UV illumination modifies the properties of aerosol droplets as they are jetted onto a target surface. In some embodiments the UV light at least partially cures photopolymer droplets, and the resulting increased viscosity facilitates the formation of free standing structures. In other embodiments the UV light rapidly dries droplets of solvent-based nanoparticle dispersions in flight, likewise enabling 3D fabrication. Thus 3D fabrication in accordance with the present invention can be performed using a wide variety of photopolymer, nanoparticle dispersion, and composite materials. The resulting 3D shapes can be free standing, without supports, and arbitrary shapes can be created by manipulating the print nozzle relative to the target substrate. The feature size is primarily determined by the jetting process, and can go down to 10 μm or even lower.
[0046] In the embodiment of the present invention shown in
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[0048] In one embodiment of the present invention, a light pipe or optical fiber can comprise modulations of the index of refraction of the polymer to make optical filters. These modulations reflect light at the point where the refractive index changes, and can preferably be used to create Bragg filters. Printed fibers fabricated in accordance with the present invention can be as small as 10 μm in diameter with or without material gradients.
[0049] Material gradients along the fiber length preferably comprise a lower limit of spatial variance, or spacing between the filters, of 10 nm. For some optical Bragg filters 64, 66, 68, 70, 72, 74, 76 the optimal spatial variance is preferably 250 nm, approximately one-half the wavelength of visible light. The material gradient along the length of the fiber can vary sinusoidally if the materials are mixed by varying the aerosol gas flows. Alternatively, the material gradient can occur in discrete steps if the materials are mixed by pulsing the flows. The material gradient amplitude can vary from 0 to 100% depending on the relative amounts of material fed from each atomizer.
[0050] Optional optical cladding 78 can be applied to the outside of the optical fiber to improve light containment inside core 62 of the optical fiber. The optical cladding preferably has a lower refractive index than the two (or more) materials used for the core. For example, optical cladding 78 could be printed in a spiral to make a hollow cylinder followed by printing the core 62 with one or more material gradients along the fiber axis. The roughness of the fiber sidewall and optical cladding 78 is preferably below 1 micron, facilitating containment of light within the core via total internal reflection. Optical fiber materials preferably comprise transparent photopolymers that have differing refractive indices necessary for controlled optical reflection, yet similar chemistries; for example, they are preferably miscible and/or have similar UV curing properties.
[0051] In another embodiment of the present invention, optical interconnects for data transmission, for example in integrated circuits, can be fabricated. Optical interconnects are essentially optical fibers and may comprise graded or ungraded material that optically connect electronic chips. Data transmission in CMOS submicron chip technology is limited by the standard on-chip communication via interconnects. Chip-to-chip data transmission can be greatly increased by using optical interconnects instead of the traditionally used metal interconnects. For example, a vertical cavity surface emitting laser (VCSEL) can be used as an optical interconnect. The on-chip light source can optionally be connected to an on-chip light detector via printed light pipe or optical fiber as described in the present invention.
[0052] Another embodiment of the present invention is a flat lens that has the ability to bend and focus light using materials gradients. Traditionally, lenses are not flat and require their shape to be convex or concave in order to bend light. A flat lens that focuses light preferably comprises a relatively high refractive index material at the edge and a relatively low refractive index material at the center. This radial refractive index material grading from low at the center to high at the edge bends light even though the lens maintains a flat shape.
[0053] In another embodiment of the present invention, acoustic gradients can be printed. Graded acoustic fibers, for example ultrasound sensors, can be connected with 3D interconnects. Ultrasonic transducers preferably allow sound to travel into tissue and not be reflected. For example, acoustic impedance matching can be achieved by physically grading a high-density transducer, for example a Positive Temperature Coefficient (PTC) ceramic, with a low-density transducer, for example a material with a density similar to that of tissue.
[0054] Alternatives to Electromagnetic Radiation Curing of Polymers
[0055] Aerosol Jet® fabricated, high aspect ratio 3D structures can be obtained using any rapidly solidifying materials. A material that is rapidly solidifying preferably has a dry time that is shorter than the time for mixing or dissolving, t.sub.dry<t.sub.dissolve. For example, quick evaporating solvents can be used in place of a curable polymer as the suspension medium.
[0056] Another alternative is pseudoplastic fluids, for example shear thinning fluids. Shear thinning fluids are fluids where the shear viscosity decreases with applied shear strain. Shear viscosity, ηq, is related to the applied shear rate through the equation:
η=kΓ.sup.n-31
where η is the viscosity, K is a material based constant, Γ is the applied shear rate, and n is the flow behavior index. Shear thinning behavior occurs when n is less than 1. Shear thinning fluids have lower viscosities (more liquid like) when sheared and immediately become more viscous once the shearing ceases. This immediate change in viscosities makes it suitable for printing high aspect ratio 3D structures using the Aerosol Jet® technology described within.
[0057] Although the invention has been described in detail with particular reference to the disclosed embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover all such modifications and equivalents. The entire disclosures of all patents and publications cited above are hereby incorporated by reference.