3D printing high-performance piezoelectric materials with extreme properties

Abstract

A photosensitive resin for 3d printing, method of printing a piezoelectric textured ceramic containing piezoelectric elements, and application incorporating one or more piezoelectric textured ceramics are disclosed. In embodiments, the photosensitive resin for 3D printing includes a photo monomer, a matrix ceramic, and a plurality of template seeds. In embodiments, the piezoelectric textured ceramic is printed by the steps including: (a) providing, in a vat, the photosensitive resin (b) applying an alternating electric field to the vat, (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure, (d) removing the cured resin structure from the vat. and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace. In embodiments, applications include transducers, hypersonic radomes, sonar systems, and seafloor mapping devices.

Description

3D Printing High-Performance Piezoelectric Materials with Extreme PropertiesSTATEMENT OF GOVERNMENT SUPPORT

[0001] The invention was made with government support under Award Number N00014- 24-1-2294 awarded by the DOD Office of Naval Research and Grant Number 2309828 awarded by the National Science Foundation. The government has certain rights in the invention.REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 550,145, filed February 6, 2024, the contents of which is hereby incorporated by reference.FIELD

[0003] The present invention generally relates to 3D printing of piezoelectric materials.BACKGROUND

[0004] It is known that ceramics with a high degree of texturing, or grain alignment, can exhibit enhanced properties compared to traditionally manufactured ceramics with randomly oriented gains, such as improved piezoelectric performance of ceramics used for sonar sensor applications. As laid out by the US Naval Sea Systems Command’s request for proposal SBIR 24. 1 - Topic N241-040 (‘‘the Navy’s Request’'), which was pre-released on November 29, 2023 and opened in January 2024. (accessible at https: / / www.navysbir.com / n24_l / N241- 040.htm#qa), current manufacturing techniques to produce highly textured ceramics involve using an expensive and complex tape casting technique to properly align the material seed crystals.

[0005] Per the Navy’s Request, “[a]dditive manufacturing (AM) could provide a solution by improving the Manufacturing Readiness Level of these new textured ceramic materials and enabling technology insertion at a scalable, cost-effective rate” in part because “cunent stereolithography (SLA) [which uses a laser or other light source to trace the shape of a layer] and digital light processing (DLP) [which projects a mask of a whole cross-sectional layer at a time] 3D printers create parts by using a light source to polymerize a liquid photo monomer resin to create a high resolution 3D printed part with minimal need for additional post processing.”

[0006] However, as the Navy’s Request discusses, the current art does not allow for additive manufacturing in the w ay that the Navy requires in a cost effective and efficient matter.

[0007] Accordingly, as the Navy’s Request states, there is “a need to modify existing 3D printing hardware to incorporate the ability to properly align high aspect ratio seed particles within each print layer to produce grain alignment during sintering of the ceramic.”SUMMARY

[0008] In view of the above, it is an object of the present invention to provide a technological solution to address the long felt need and technological challenges faced in creating high-performing piezoelectric ceramics, as exemplified by the Navy’s Request. The present invention improves upon existing additive manufacturing techniques by disclosing a photosensitive resin comprising a photo monomer, a matrix ceramic, and high-aspect ration template seeds, and a method and related systems of fabricating a piezoelectric textured ceramic by' conducting additive manufacturing using the photosensitive resin in an alternating electric field, which promotes grain grow th during the sintering of the ceramic.

[0009] As a result of these, and other improvements described herein, the present invention further enhances the performance of piezoelectric transducers in bandwidth, sensitivity, and energy conversion efficiency, enlarging the electromechanical coupling factors by tailoring the inherently associated crystallographic orientation is a widely adapted pathway. The present invention demonstrates that growing into single crystals or textured ceramics is an effective approach to enhance the electromechanical coupling factor of perovskite ferroelectrics using a relaxor-PbTiO? system, Pb(Mgi 3Nb2 / s) -PbTiOs (PMN-PT), that can be grown into textured ceramic cry stals for enhanced piezoelectric performance.

[0010] The resulting textured piezoelectric ceramics may be used for, and provide improvements to, a variety of applications, including undersea sensor applications, such as piezoelectric transducers, hypersonic radomes, commercial and recreational sonar systems (e.g., fish finders and navigation devices), high resolution seafloor mapping devices, communications and data transfer applications, and imaging devices in the medical field, to name a few examples.

[0011] In exemplary embodiments, a photosensitive resin for 3D printing includes a photo monomer, a matrix ceramic, and a plurality of template seeds.

[0012] In embodiments, the photo monomer includes one or more acry lates selected from the group consisting of: polyethylene glycol diacrylate (PEGDA) polyethylene glycol diacr late (PEGDA), trimethylolpropane tn acrylate (TMPTA), 1,6-hexanediol diacrylate(HDDA), triethylene glycol dimethacrylate (TEGDMA), bisphenol A-glycidyl methacrylate (Bis-GMA), urethane dimethacrylate (LJDMA). and bisphenol A ethoxylate diacrylate (Bis- EDA).

[0013] In embodiments, the photo monomer includes a photo initiator.

[0014] In embodiments, the photo initiator includes a photo initiator selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irg819), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6- trimethylbenzoylphosphinate (LAP), 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- methylpropiophenone (Irgl 173), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Li), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086), benzophenone, or 2- hydroxy-4'-(2 -hydroxy ethoxy)-2 -methylpropiophenone (Irg2959).

[0015] In embodiments, the matrix ceramic includes a PMN-PT (lead magnesium niobate- lead titanate, Pb(Mgi / 3Nb23)-PbTiO3) composite.

[0016] In embodiments, the PMN-PT composite has a PMN:PT molar ratio of 65:35.

[0017] In embodiments, the PMN-PT composite comprises 30% of the volume of the photosensitive resin.

[0018] In embodiments, the plurality of template seeds include a plurality of microcrystal platelets including barium titanate (BaTiCE).

[0019] In embodiments, each of the plurality of template seeds have a lateral dimension of approximately 7 pm and a thickness of approximately 600 nm.

[0020] In embodiments, each of the plurality of template seeds have an orientation of <100>.

[0021] In embodiments, the plurality of template seeds include 1% of the volume of the matrix ceramic.

[0022] In embodiments, the photosensitive resin further includes a liquid phase sintering regent.

[0023] In embodiments, the liquid phase sintering regent includes lead nitrite.

[0024] In embodiments, the liquid phase sintering regent includes lead nitrite at 5% of the weight percentage of the matrix ceramic.

[0025] In embodiments, the photosensitive resin further includes a sintering aid.

[0026] In embodiments, the sintering aid includes copper oxide at .2% of the weight percentage of the matrix ceramic and boric oxide at .2% of the weight percentage of the matrix ceramic..

[0027] In exemplary embodiments a method of fabricating a piezoelectric textured ceramic containing piezoelectric elements includes the steps of: (a) providing, in a vat. a photosensitive resin including a photo monomer, a matrix ceramic, and a plurality of template seeds; (b) applying an alternating electric field to the vat; (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; (d) removing the cured resin structure from the vat; and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the piezoelectric textured ceramic containing piezoelectric elements. In embodiments, applying the alternating electric field includes: (i) applying, using a first plurality7of electrodes, a first electric field oriented in a first direction; and (ii) applying, using a second plurality of electrodes, a second electric field oriented in a second direction. In embodiments, the piezoelectric textured ceramic containing piezoelectric elements exhibits a crystal grain with a uniformity of at least 60%.

[0028] In embodiments, the first plurality of electrodes includes a first electrode pair.

[0029] In embodiments, the second plurality of electrodes includes a second electrode pair.

[0030] In embodiments, the first temperature is between 1215°C and 1250°C.

[0031] In embodiments, the first period of time is 15 hours.

[0032] In embodiments, the first direction is orthogonal to the second direction.

[0033] In embodiments, the photo monomer the photo monomer comprises one or more acrylates selected from the group consisting of: polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDD A), tri ethylene glycol dimethacrylate (TEGDMA), bisphenol A-glycidyl methacrylate (Bis-GMA), urethane dimethacrylate (UDMA), and bisphenol A ethoxylate diacrylate (Bis-EDA).

[0034] In embodiments, the photo monomer includes a photo initiator.

[0035] In embodiments, the photo initiator includes a photo initiator selected from the group consisting of: bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irg819),diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6- trimethylbenzoylphosphinate (LAP), 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- methylpropiophenone (Irgl 173), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Li), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086), benzophenone, or 2- hydroxy-4'-(2 -hydroxy ethoxy)-2 -methylpropiophenone (Irg2959).

[0036] In embodiments, the matrix ceramic includes a PMN-PT (lead magnesium niobate- lead titanate, Pb(Mgi / 3Nb23)-PbTiO3) composite.

[0037] In embodiments, the PMN-PT composite has a PMN:PT molar ratio of 65:35.

[0038] In embodiments, the PMN-PT composite comprises 30% of the volume of the photosensitive resin.

[0039] In embodiments, the plurality' of template seeds include a plurality of microcrystal platelets including barium titanate (BaTiOs)

[0040] In embodiments, each of the plurality of template seeds have a lateral dimension of approximately 7 pm and a thickness of approximately 600 nm.

[0041] In embodiments, each of the plurality of template seeds have an orientation of <100>.

[0042] In embodiments, the plurality of template seeds include 1% of the volume of the matrix ceramic.

[0043] In embodiments, the photosensitive resin further includes a liquid phase sintering regent.

[0044] In embodiments, the liquid phase sintering regent includes lead nitrite.

[0045] In embodiments, the liquid phase sintering regent includes lead nitrite at 5% of the weight percentage of the matrix ceramic.

[0046] In embodiments, the photosensitive resin further includes a sintering aid.

[0047] In embodiments, the sintering aid includes copper oxide at .2% of the weight percentage of the matrix ceramic and boric oxide at .2% of the weight percentage of the matrix ceramic.

[0048] Exemplary embodiments include a transducer including at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by thesteps including: (a) providing, in a vat, a photosensitive resin including a photo monomer, a matrix ceramic, and a plurality of template seeds; (b) applying an alternating electric field to the vat; (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; (d) removing the cured resin structure from the vat; and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic. In embodiments, applying the alternating electric field includes: (i) applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and (ii) applying, using a second plurality of electrodes, a second electric field oriented in a second direction. In embodiments, the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

[0049] Exemplary embodiments include a hypersonic radome including at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps including: (a) providing, in a vat, a photosensitive resin including a photo monomer, a matrix ceramic, and a plurality of template seeds; (b) applying an alternating electric field to the vat; (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; (d) removing the cured resin structure from the vat; and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic. In embodiments, applying the alternating electric field includes: (i) applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and (ii) applying, using a second plurality of electrodes, a second electric field oriented in a second direction. In embodiments, the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity’ of at least 60%.

[0050] Exemplary embodiments include a sonar system including at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps including: (a) providing, in a vat, a photosensitive resin including a photo monomer, a matrix ceramic, and a plurality of template seeds: (b) applying an alternating electric field to the vat; (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; (d) removing the cured resin structure from the vat; and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric texturedceramic. In embodiments, applying the alternating electric field includes: (i) applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and (ii) applying, using a second plurality' of electrodes, a second electric field oriented in a second direction. In embodiments, the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

[0051] Exemplary embodiments include a seafloor mapping device including at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps including: (a) providing, in a vat, a photosensitive resin including a photo monomer, a matrix ceramic, and a plurality of template seeds; (b) applying an alternating electric field to the vat; (c) applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; (d) removing the cured resin structure from the vat; and (e) sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic. In embodiments, applying the alternating electric field includes: (i) applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and (ii) applying, using a second plurality' of electrodes, a second electric field oriented in a second direction. In embodiments, the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

[0052] Other features and advantages of the present invention will become readily apparent from the following detailed description and the accompanying drawings.BRIEF DESCRIPTION OF THE DRAWINGS

[0053] The above and related objects, features and advantages of the present invention will be more fully understood by reference to the following, detailed description of the preferred, albeit illustrative, embodiment of the present invention when taken in conjunction with the accompanying figures, wherein:

[0054] FIG. 1 depicts a schematic illustration of a resin formulation to be used during 3D printing of textured ceramics in accordance with exemplary embodiments of the present invention;

[0055] FIG. 2 depicts a 3D printing system configured to produce an electric field in accordance with exemplary' embodiments of the present invention;

[0056] FIG. 2A is a schematic illustration of alignment of BTO seeds during printing using the resin formulation in accordance with exemplary embodiments of the present inventions;

[0057] FIG. 3A is a SEM image of high-aspect ratio BTO seeds in accordance with exemplary embodiments of the present invention;

[0058] FIGs. 3B and 3C are SEM images of printed polymer-PMN-PT composite with aligned BTO seeds in accordance with exemplary embodiments of the present invention;

[0059] FIG. 3D is a chart showing seed orientation of BTO seeds in accordance with exemplary embodiments of the present invention;

[0060] FIG. 4 is a flowchart depicting steps for fabricating a piezoelectric textured ceramic in accordance with embodiments of the present invention;

[0061] FIG. 5 A depicts a schematic illustration of the template growth of PMN-PT grains during high-temperature sintering of BTO seeds and PMN-PT particles generated in accordance with exemplary embodiments of the present invention;

[0062] FIG. 5B shows XRD patterns of the textured PMN-PT ceramic generated in accordance with exemplary embodiments of the present invention and the original particles;

[0063] FIG. 5C shows a grain orientation image of a random PMN-PT;

[0064] FIG. 5D shows an inverse pole figure of a random PMN-PT;

[0065] FIG. 5E shows a grain orientation image of a textured PMN-PT generated in accordance with exemplary embodiments of the present invention;

[0066] FIG. 5F show's an inverse pole figure of the textured PMN-PT obtained with EBSD generated in accordance with exemplar}' embodiments of the present invention;

[0067] FIG. 5G shows a comparison of the electric field-induced strains between the textured PMN-PT generated in accordance with exemplary embodiments of the present invention and non-textured PZT ceramic;

[0068] FIG. 5H shows a comparison of dielectric constant of the present invention with other works;

[0069] FIG. 6 depicts optic images of miniature ultrasound transduce probes fabricated using 3D-printed textured PMN-PT ceramics in accordance with embodiments of the present invention;

[0070] FIG. 6A shows acoustic field measurement results, showing the lateral resolution of the as-fabricated transducer of FIG. 6; and

[0071] FIG. 6B shows a comparison of the acoustic pressure generated by the PMN-PT transducer in FIG. 6 to that of a PZT transducer of the same geometry'.

[0072] In the drawings, exemplary embodiments of the invention are illustrated by way of example, it being expressly understood that the description and drawings are only for the purpose of illustration of exemplary embodiments and are not intended as a definition of the limits of the invention.DETAILED DESCRIPTION

[0073] The following description is presented to enable a person of ordinary' skill in the art to make and use the invention, and is provided in the context of particular applications and their requirements. Various modifications to the embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may7be applied to other embodiments and applications without departing from the spirit and scope of the invention. In the following description, numerous details are set forth for the purpose of explanation. However, one of ordinary skill in the art will realize that the invention may be practiced without the use of these specific details. In other instances, well-known structures and devices are shown in block diagram form in order not to obscure the description of the invention with unnecessary' detail. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.

[0074] A method of fabricating a piezoelectric ceramic includes 3D punting a PZT base layer on a polymer support layer; debonding the PZT base layer from the polymer support layer; sintering the PTZ base layer in a PTZ powder bed with heat to form a PTZ element; submerging the PTZ element into an isolation liquid; polarizing the dipoles within the sintered PTZ element; applying an electric field to the PTZ element; and cooling the PTZ element.

[0075] As an example of this method, the inventors performed fabrication by starting with UV-sensitive piezoelectric preparation. A highly particle-loaded slurry consisted of 15-45 vol% PZT nanoparticles (APC 855), 5-15 vol% liquid phase sintering (LPS) agent, lead nitrate (PbNCh) and a UV-sensitive resin made from a mixture of monomers (polyethylene glycol diacrylate, PEGDA) and a photoinitiator. Compared to other PZT nanoparticles, APC 855features a high piezoelectric strain constant (630 pm / V) and electromechanical coupling factor (0.76), which ensures the high performance of the printed part. Lead nitrate was used as the LPS agent due to its low UV light absorption compared to other LPS agents, including lead oxide, and CdBiB, ensuring the printability of the slurry. A combination of 35 vol% PZT and 15 vol% lead nitrate was chosen, which was experimentally optimized to guarantee the printability and piezoelectrical properties.

[0076] The slurry was then fed to a resin tray of a custom-made PpSL system for 3D printing. A thick printing window (2 mm) made of poly dimethylsiloxane (PDMS) was utilized during the process of separating the printed part and the printing window, which prevented small features from being damaged. The oxygen permeability of the PDMS window leads to an oxygen inhibition layer between the printing window and resin that increases the distance between the printed part and printing window and reduces the suction force. In addition, compared to other printing windows, including fluorinated ethylene propylene (FEP) film, acrylic board and glass window, the high compliance of the PDMS window results in a slower separation process and protected the high precision features of the printed parts.

[0077] The as-printed piezocomposites were then sintered to grow the PZT grain size and form the dense PZT ceramic with designed geometries. First, the printed sample was debonded using atw o-step debonding process to remove the supportive polymer. The two-step debonding process reduced the deformation of the printed elements compared to the currently existing direct debonding process, allowing fabrication of small-scale features. After debonding, extra PZT powders was placed on the bottom of an alumina crucible, and the printed element was placed on top of a powder bed. A smaller crucible was used to cover the element and pushed down into the powder bed. The temperature was then increased to 1100°C in 1.5 hours and held for 3 hours to grow the PZT grains in order to form a dense ceramic. LPS started at an elevated temperature. Lead nitrate within the element was converted into lead oxide and melted at 888°C and contracted the PZT particles via surface tension, densifying the PZT architecture. To reduce the lead loss at high temperatures, the liquid sealing method was implemented by placing lead oxide along the edge of the small crucible. During the sintering process, lead oxide melted, sealed the crucible, and created a lead-rich environment to avoid lead loss during the high-temperature sintering. Then, the samples were cooled dow n to room temperature at a rate of 10 °C / min. The sintered PZT material also kept perovskite structure after high-temperature heat-treatment.

[0078] The sintering was followed by a polarization process to align the dipoles within the sintered PZT element and activate the piezoelectric effect. The polarization was conducted in an isolation liquid (e.g., silicone oil 220 of FIG. 2) to prevent the breakdown in air with a polarization electric field higher than 3V / um. Based on the Curie temperature and breakdown electric field (6.5 V / um) of the sintered PZT elements, the temperature and electric field profile of the polarization process was optimized. After reaching the peak value, the electric field was maintained during the cooling process of the isolation liquid to prevent depolarization of the printed element.

[0079] The sintering procedure ensured the formation of a dense ceramic with low porosity and well-maintained lead content, leading to high piezoelectric strain and coupling constants. The acoustic pressure generated by the fabricated 9.75-MHz transducer can be effectively increased by using the curvature design of the elements. Notably, the acoustic pressure is tunable according to the change in the element curvature degree and can exceed some medical thresholds, enlarging the range of applications of the fabricated device.

[0080] The technique allowed for the fabrication of high-performance piezoelectric transducers with complex 3D geometries that are not achievable by any conventional fabrication methods for piezoceramics, including hot-pressing, molding, sanding, and dicing. These complex shapes allow for potential custom transducer applications. Other examples include hemisphere elements for medical imaging and nondestructive testing, cylindrical transducer elements with multiple concentric annular layers filled with a polymer for reducing the traverse vibration and enhancing the thickness vibration, helical elements for generating acoustic beams with vortex motion for ultrasound manipulation, and architected piezo sensors for underwater sensing.

[0081] Improvements to this method, as well as improvements to contemporary methods related to techniques for manufacturing piezoelectric sensors, are disclosed herein.

[0082] FIGs. 1, 2, and 3A-3D depict schematics and data related to the alignment of BTO seeds in accordance with embodiments of the present invention.

[0083] FIG. 1 depicts a schematic illustration of a resin formulation to be used during 3D printing of textured ceramics in accordance with exemplary embodiments of the present invention. In exemplary embodiments, a photosensitive resin for 3D printing (e.g., resin 100 of FIG. 1) includes a photo monomer (e.g., photo monomer 102 of FIG. 1), a matrix ceramic(e.g., matrix ceramic 104 of FIG. 1), and a plurality of template seeds (e g., BTO seeds 106 of FIG. 1).

[0084] In embodiments, the photo monomer (e.g., photo monomer 102) is composed of an acrylate or combination of acrylates (e.g., polyethylene glycol diacrylate (PEGDA) (represented by structural formula 102a in “FIG. 1))”, trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDD A), tri ethylene glycol dimethacrylate (TEGDMA), bisphenol A-glycidyl methacrylate (Bis-GMA), urethane dimethacrylate (UDMA), bisphenol A ethoxylate diacrylate (Bis-EDA), or any combination thereof, to name a few), and may include a photo initiator (for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irg819). diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6- trimethylbenzoylphosphinate (LAP), 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- methylpropiophenone (Irgl 173), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Li), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086), benzophenone, 2- hydroxy-4'-(2 -hydroxy ethoxy)-2 -methylpropiophenone (Irg2959), or a combination thereof, to name a few). In embodiments, the photo initiator is 2 wt% of the photo monomer. In embodiments, the photo initiator is between .1 wt% and 5.0 wt% of the photo monomer (e.g., .1 wt%, .5 wt%, .9 wt%, 1.0 vrt.% , 1.5 wt%, 2.0 wt%, 2.5 vvt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, and 5.0 wt%, to name a few).

[0085] In embodiments, the matrix ceramic (e.g., matrix ceramic 104) includes lead magnesium niobate-lead titanate (Pb(Mgi / 3Nb2 / ?)-PbTiO3), PMN-PT (represented by ball-and- stick model 104a in FIG. 1). In embodiments, the PMN PT molar ratio is between 80:20 and 60:40. In embodiments, the PMN-PT composite (the matrix ceramic) comprises between 15% and 50% of the volume of the photosensitive resin. To illustrate, as an example, in embodiments, the PMN:PT molar ratio of the PMN-PT composite is 65:35 (between 80:20 and 60:40), and the PMT-PT composite (the matrix ceramic) may comprise 30% (between 15% and 50%) of the volume of the photosensitive resin.

[0086] In embodiments, the plurality of template seeds (e.g., template seeds 106) includes a plurality of microcrystal platelets. In embodiments, the microcry stal platelets include barium titanate (BaTiCty). BTO. In embodiments, one or more of the plurality of template seeds has a lateral dimension of between 1-30 pm and a thickness of between 200 nm and 2 pm. In embodiments, each of the plurality of template seeds has an aspect ratio of lateral dimension to thickness of greater than one. For example, in embodiments, one or more of the plurality oftemplate seeds (such as at least 50% of, 75% of, 99% of, or 100% of, to give a few examples) have a lateral dimension of approximately 7 pm and a thickness of approximately 600 nm (for an aspect ratio of approximately 11.6). In embodiments, one or more of the plurality of template seeds have an orientation of <100>. In embodiments, the plurality of template seeds make up between .1% and 10% of the volume of the matrix ceramic. For example, in embodiments, the plurality of template seeds comprise 1% of the volume of the PMT-PT composite. In embodiments, a different percentage of template seeds may be used, including approximately .1%, .5%, 2%, 3% and 4%. 5%, 6%. 7%, 8%. 9%, and 10% of the volume of the matrix ceramic, to give a few examples.

[0087] In embodiments, the photosensitive resin also includes a liquid phase sintering regent (e.g., liquid phase sintering regent 108) and a sintering aid. In embodiments, the liquid phase sintering regent is between 1% and 15% of the weight percentage of the matrix ceramic. In embodiments, the liquid phase sintering regent is lead nitrite (PbfNOs ), the structural formula for which is shown by structural formula 108a. In embodiments, the sintering aid is between .1% and 1% of the weight percentage of the matrix ceramic. In embodiments, the sintering aid includes boric oxide (also referred to as boric anhydride) and copper oxide. To give one example, by way of illustration only, in embodiments, the photosensitive resin includes a lead nitrite liquid phase sintering regent at 5% of the weight percentage of the matrix ceramic and a sintering aid including copper oxide at .2% of weight percentage of the matrix ceramic and boric oxide at .2% of weight percentage of the matrix ceramic.

[0088] FIG. 2 depicts a 3D printing system 200 configured to produce an electric field 216 in accordance with exemplary embodiments of the present invention. In embodiments, the 3D printing system includes a projection system 202, a vat 210, and a plurality of electrode pairs 212. In embodiments, the projection system includes a light engine 204, one or more mirrors 206, and one or more lenses 208. In embodiments, the light engine 204 is a digital micromirror device. In embodiments, the vat 210 is configured to hold the photosensitive resin 214. In embodiments, the photosensitive resin 214 is substantially the same as resin 100. In embodiments, the plurality electrode pairs 212 include a first electrode pair 212a and a second electrode pair 212b and are configured to apply an electric field 216 to the vat of resin 214 in accordance with exemplary embodiments of the present invention. In embodiments, the plurality of electrode pairs includes more than two electrode pairs. In embodiments, the electric field is applied horizontally in the X-Y plane. It will be appreciated that the 3D printing system200 is provided as a non-limiting example only of a 3D printing system capable of generating an electric field to align BTO seeds in accordance with exemplary' embodiments of the present invention.

[0089] FIG. 2A is a schematic illustration of alignment of BTO seeds during printing using the resin formulation in accordance with exemplary embodiments of the present inventions. As shown in FIG. 2A, BTO Template 106a is aligned in an electric field along long axis 2 and long axis 1. In embodiments, long axis 2 corresponds to the electrode pair 212a and long axis 1 corresponds to electrode pair 212b.

[0090] FIG. 4 is a flowchart depicting steps for fabricating a piezoelectric textured ceramic in accordance with embodiments of the present invention. In embodiments, as depicted by step S400, the process begins by providing, in a vat (e.g., vat 210 of 3D printing system 200), a photosensitive resin. In embodiments, the photosensitive resin (e.g., photosensitive resin 214 or resin 100) includes a photo monomer (e.g., photo monomer 102) and / or a photopolymer, a matrix ceramic (e.g., matrix ceramic 104), and a plurality of template seeds (e.g., template seeds 106) in accordance with exemplary embodiments of the present invention.

[0091] In embodiments, the process continues with step S402, by applying an alternating electric field (e.g., electric field 216 of FIG. 2) to the vat (e.g., vat 210). In embodiments, applying the alternating electric field includes (i) applying, using a first plurality of electrodes (e.g., using electrode pair 212a), a first electric field oriented in a first direction; and (ii) applying, using a second plurality of electrodes (e.g., using electrode pair 212b), a second electric field oriented in a second direction. In embodiments, the first plurality of electrodes includes a first electrode pair (e.g., electrode pair 212a) and the second plurality of electrodes includes a second electric pair (e.g., electrode pair 212b). In embodiments, the vat is between all of the electrodes of the first plurality of electrodes and the second plurality of electrodes. For example, the vat may be between the first pair of electrodes and the second pair of electrodes, as depicted in FIG. 2. In embodiments, the first direction is orthogonal to the second direction. In embodiments, the alternating electric field operates at a constant frequency (e.g., 6 kHz, to give an example). In embodiments, the alternating electric field operates at a vary ing frequency. In embodiments, the alternating electric field operates at a frequency below the resonant frequency of the template seeds.

[0092] In embodiments, the process continues with step S404. which may occur simultaneously with and / or after step S402. At step S404, a digital light projection (e.g., usingprojection system 202) is applied to a predetermined portion of the photosensitive resin in order to generate a cured resin structure. In embodiments, the cured resin structure may consist of one or more layers. In embodiments, the digital light projection is applied using a light source (e.g., light engine 204) such as a digital light projector, and a digital micromirror device (DMD). The cured resin structure may be formed on a build plate.

[0093] In embodiments, another form of additive printing may be used in lieu of, or in addition to, digital light projection. For example, another form of additive printing relying on the interaction between the photosensitive resin and light or other form of radiation may be used, such as stereolithography (SLA) or a liquid crystal display (LCD) printer. As another example, direct ink writing, which relies on extrusion of the resin from a nozzle directly onto a platform to 3D print layer-by layer, may be used. In embodiments, the resin used may be formulated based on the form of additive printing used. For example, in embodiments, the amount of photo monomer used, if any, may depend upon the form of printing and whether light projection or other UV curing is used.

[0094] In embodiments, steps S402 and S404 repeat until a predefined cured resin structure is formed. In embodiments, the predefined cured resin structure may be formed according to 3D printing instructions received. In embodiments, the 3D printing instructions are generated based on a 3D model, which may be selected based upon the ultimate application of the generated piezoelectric textured ceramic. For example, instructions may be given to 3D print a piezoelectric textured ceramic in the shape of a transducer.

[0095] In embodiments, the 3D printing instructions are stored in computer-readable memory accessible by the 3D printing system, and used to generate the predefined cured resin structure. For example, the 3D printing instructions may be stored in memory' and used by a controller to provide commands to the elements of the 3D printing systems controlling the curing of the resin (e.g., projection system 202) and physical location of the vat.

[0096] In embodiments, the process continues with step S406. Step 406 includes removing the cured resin structure from the vat. At step S406, post-curing processes may occur, including cleaning excess resin using a solvent and / or additionally curing the cured resin structure from the vat.

[0097] In embodiments, the process continues with step S408. Step 408 includes sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time.In embodiments, the first temperature is below the melting point of the matrix ceramic, for example, between 1215°C and 1250°C in the case ofPMN-PT. In embodiments, the first period of time is for a period of hours, for example. 12 hours, 15 hours, 18 hours, 21 hours, 24 hours, 30 hours, 36 hours, 42 hours, to give a few examples. In embodiments, after S408, a piezoelectric textured ceramic is generated which contains piezoelectric elements. In embodiments, the piezoelectric textured ceramic generated using the process depicted in FIG. 4 exhibits a cry stal grain with a uniformity' of at least 30%. In embodiments, the piezoelectric textured ceramic generated using the process depicted in FIG. 4 exhibits a crystal grain with a uniformity of at least 60%. In embodiments, the piezoelectric textured ceramic generated using the process depicted in FIG. 4 exhibits a grain uniformity of between 60% and 99%. For example, the grain uniformity may be at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5%, and at least 98%, to give a few examples.

[0098] In embodiments, at least one piezoelectric textured ceramic generated in accordance with exemplary embodiments of the present invention is incorporated into a device or application, applications. In embodiments, a plurality of piezoelectric textured ceramics are incorporated into a device or application. For example, one or more piezoelectric textured ceramics may be incorporated in transducers, hypersonic radomes, sonar systems, seafloor mapping devices, medical imaging devices, and in communications and / or data transfer, to name a few. Additional examples include use in sensors (e.g., motion sensors, hydrophones, and environmental monitoring, to give a few examples), actuators (e.g., in atomic force microscopes, ultrasonic welders, and nanopositioning applications, to give a few examples), energy harvesting applications, ultrasonic applications (e.g., ultrasonic cleaning, ultrasonic scalers, and ultrasonic power transducers, to give a few examples), active vibration dampeners, high-frequency loudspeakers, drug delivery devices and low frequency / high power projectors, to name a few.

[0099] To provide a non-limiting example, and for purposes of illustration only, the inventors formulated a resin system 100 based on polyethylene glycol diacrylate (PEGDA) (photo monomer 102) with 2.5% of photo initiator as shown in FIG. 1. The matrix ceramic 104 was chosen as PMN-PT where the PMN and PT molar ratio was 65:35 of which the single crystal gives the highest piezoelectric response. The PMN-PT volume percent was 30% considering the viscosity and printability. In the printing resin, there were also the templateseed 106, BTO, the liquid phase sintering regent 108 lead nitrite, and sintering aid, mixture of copper oxide and boric oxide, to promote the deposition of matrix particles on the surface of templates through liquid phase mass transfer.

[0100] For the template seeds 106, the inventors used <100>-oriented microcrystal platelets of barium titanate (BaTiCh. BTO) with a lateral dimension of ~7 pm and thickness of ~ 600 nm. FIG. 3A is a SEM image of high-aspect ratio BTO seeds 300 in accordance with exemplary embodiments of the present invention. FIGs. 3B and 3C are SEM images of printed polymer-PMN-PT composite (including photo polymer 302 and PMN-PT 304) with aligned BTO seeds 300 in accordance with exemplary embodiments of the present invention. FIG. 3D is a chart showing seed orientation of BTO seeds 300 in accordance wi th exemplary embodiments of the present invention. The high aspect ratio ensured a controllable and high degree of alignment of the BTO seeds 300 under external stimuli, such as shear force and electrical field.

[0101] The inventors chose 1 vol.% of BTO to PMN-PT to maximize the printability' and the crystal growth. The content of BTO seeds affected not only the template growth of PMN- PT ceramics, but also the printing of the resin. Theoretically, the BTO content should be kept at a low level such that the grown ceramic will have minimal numbers of grains which is close to the crystalline structure of single cry stals. A low BTO content also facilitated the printing as the BTO micro platelets blocked UV from fully curing the resin. On the other hand, practically, a relatively higher content of BTO helps sufficient crystal growth. Accordingly, higher and lower vol.% of BTO to PMN-PT are contemplated by embodiments of the present invention.

[0102] Compared with conventional preparation of bulk textured ceramics which typically involves high-pressure densification, 3D printed ceramic lattices lack effective methods to densify the printed structures. To address this limitation, and reduce the porosity' of the printed ceramics, the inventors introduced a liquid phase sintering regent, lead nitrite at 5 wt% of PMN- PT. Dunng the sintering process, lead nitrite decomposes to lead oxide which is a liquid at the template growth temperature and densify the PMN-PT particles due to the capillary' force.

[0103] For textured grown ceramics, the alignment of template seeds BTO is an important step. A high degree of orientation of the template seeds ensures the orientated grow th of the ceramic’s grains and consequently promises the optimal piezoelectric response, and thus limits the flexibility of designing the orientation of the ceramic materials.

[0104] FIGs. 5A-H depicts schematics and data related to the template growth of PMN-PT grains in accordance with embodiments of the present invention. FIG. 5A depicts a schematic illustration of the template growth of PMN-PT grains 504 during high-temperature sintering of BTO seeds 500 and PMN-PT particles 502 generated in accordance with exemplary embodiments of the present invention. FIG. 5B shows XRD patterns of the textured PMN-PT ceramic (XRD pattern 510) and the original particles (XRD pattern 512) generated in accordance with exemplary embodiments of the present invention and the original particles. FIG. 5C shows a grain orientation image of a random PMN-PT. FIG. 5D shows an inverse pole figure of a random PMN-PT. FIG. 5E shows a grain orientation image of a textured PMN-PT generated in accordance with exemplary embodiments of the present invention. FIG. 5F shows an inverse pole figure of the textured PMN-PT obtained with EBSD generated in accordance with exemplary’ embodiments of the present invention. FIG. 5G shows a comparison of the electric field-induced strains between the textured PMN-PT (strain curve 520, 3D-printed PMN-PT) generated in accordance with exemplary embodiments of the present invention and non-textured PZT ceramic and non-textured PZT ceramic (strain curve 522, 3D-printed PZT). FIG. 5H shows a comparison of dielectric constant of the present invention, d33, with other works.

[0105] In order to align the template seeds, the inventors used an electric field to align the high-aspect-ratio BTO seeds, which is also known as dielectrophoresis (DEP). A force is exerted on a dielectric particle when it is subjected to a non-uniform electric field. The di electrophoretic force can be calculated according to Equation 1 : (Equation 1)where, r, I are the radius and length of the particle;+ — is the complex permittivity’;£mis dielectric constant, o is the electrical conductivity7, a> is the field frequency; m, p are the medium and particle respectively, and E is the electric field.

[0106] The digital light proj ection (DLP) 3D printing the inventors used for fabricating the textured ceramics was conducted by curing the photo-sensitive resin in a layer-by-layer fashion. The printing system was incorporated with the AC electric field to align the template seeds during printing, as shown by printing system 200 of FIG. 2. The AC voltage frequency was established at 6 kHz, significantly below the resonant frequency. This choice ensured a stable vibration of the seed within the electric field, avoiding resonant instabilities.Additionally, at this frequency, the template seeds experience a constrained time window under the influence of the attractive force. This limitation aids in achieving a controllable and precise alignment of the seeds. The inventors applied a 2D electric field with two pairs of electrodes (as shown by electrode pairs 212a and 212b), the BTO seeds were aligned with their plane constrained within the 2D electric plane generated by the two pairs of electrodes. By changing the direction of the 2D electric field in a 3D coordination, the inventors were able to achieve arbitrary7alignment of the BTO seeds for controlled and optimal orientation of the ceramic grain.

[0107] The matrix PMN-PT reconstruct their crystal grains which are template by the surface of BTO in <100> direction. Such a template growth is carried out at a high temperature where the matrix stays in solid state with a high diffusivity but not melting. Given the melting point of PMN-PT being 1280°C, the inventors explored the sintering temperature’s effects on the printed textured ceramic. After sintering for 15 h at 1250°C, the textured PMN-PT generated more pores which tended to be electrically penetrated during the poling process. At 1215°C, the inventors were able to obtain textured ceramic with good dielectric stability. FIG. 5A illustrates the crystal growth process of the textured PMN-PT. The X-ray diffraction (XRD) paterns 510 (FIG. 5B) of the textured PMN-PT shows the peaks from (001) and (002) facets were noticeably enhanced and the degree of orientation in the <001> direction was determined as 71% using the Lotgering method. The template grown ceramics was polished with ultrafine nanoparticles and obtained ultra-smooth surface which allowed characterization of the template grow n ceramics with electron backscatering diffraction (EBSD). Compared to random grown PMN-PT (FIGs. 5C and 5D), preferred orientation of the grains of the textured PMN-PT was observed (FIGs. 5E and 5F). It was evidenced by the uniformity of shading in the grain orientation image (FIG. 5E) and the inverse pole figure with the {001 } family dominantly facing up perpendicularly to the surface of the ceramic.

[0108] The EBSD characterizations indicate the grains of the template grown textured PMN-PT are highly oriented. Compared with the inventor’s 3D printed non-textured PZT ceramics, the textured PMN-PT showed much more prominent strain (918 pm / V) in response to the applied electric field, indicating a significantly improved piezoelectric response (see curves 520 and 522 of FIG. 5G). The textured PMN-PT sample delivered a high piezoelectric constant, d33, of 1191 pC / N, which is the highest reported among 3D printed textured ceramics and comparable with conventional highly densified textured ceramics, as shown in FIG. 5H.

[0109] FIG. 6 depicts optic images of miniature ultrasound transduce probes 600 fabricated using 3D-printed textured PMN-PT ceramics 602 in accordance with embodiments of the present invention. FIG. 6A shows acoustic field measurement results, showing the lateral resolution of the as-fabricated transducer of FIG. 6. FIG. 6B shows a comparison of the acoustic pressure generated by the PMN-PT transducer (see datapoints 620) to that of a PZT transducer of the same geometry (see datapoint 622). This highlights the improved performance of the PMN-PT.

[0110] Referring now to FIG. 6, to demonstrate the capability of fabricating sophisticated structures, the inventors 3D printed hemispherical textured PMN-PT elements 602 for applications in ultrasonic probes 600. The samples show good fidelity, which showcases the capability of the approach described herein to achieve 3D architecture ceramics with piezoelectric properties close to single crystals.

[0111] FIG. 6A demonstrates the lateral resolution 606 (170 - 180 um) of the as-fabricated transducers 602 , which was approximately 1.4 mm wide. The acoustic pressure plots in FIG. 6B shows that the 3D-printed PMN-PT ultrasound transducer has improved acoustic pressure compared to that of the 3D-printed non-textured PZT counterparts (compare datapoints 620 with datapoints 622).

[0112] The 3D-printed transducer w as benchmarked against reported micro transducers, as shown in Table 1 below.Table 1 Transducer energy output capability comparison

[0113] In Table 1, Normalized prmsis defined as the negative acoustic pressure generated by the element per unit voltage input per surface area and is used to describe the energy output capability. For the studies that use acoustic intensity to characterize the performance of the transducers, the inventors converted the spatial-peak-pulse-average intensity Isppa into the root-mean-square acoustic pressure prmsusing Equation 2:(Equation 2) where p0is the density of sound propagation medium, and c is the sound velocity in the medium.

[0114] As demonstrated by Table 1, the transducer fabricated in accordance with the embodiments of the present invention has the highest values for the normalized / ?rms compared with other miniatured transducers.

[0115] While this invention has been described in conjunction with the exemplary embodiments outlined above, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, the exemplary embodiments of the invention, as set forth above, are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the invention.

[0116] Now that embodiments of the present invention have been shown and described in detail, various modifications and improvements thereon can become readily apparent to those skilled in the art. Accordingly, the exemplary embodiments of the present invention, as set forth above, are intended to be illustrative, not limiting. The spirit and scope of the present invention is to be construed broadly.

Claims

CLAIMS:What is claimed is:

1. A photosensitive resin for 3D printing comprising a photo monomer, a matrix ceramic, and a plurality of template seeds.

2. The photosensitive resin of claim 1, wherein the photo monomer comprises one or more acrylates selected from the group consisting of: polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDD A), triethylene glycol dimethacrylate (TEGDMA), bisphenol A-glycidyl methacrylate (Bis-GMA), urethane dimethacrylate (UDMA), and bisphenol A ethoxylate diacrylate (Bis-EDA).

3. The photosensitive resin of claim 2, wherein the photo monomer comprises a photo initiator.

4. The photosensitive resin of claim 3, wherein the photo initiator comprises a photo initiator selected from the group consisting of: bis(2,4,6-trimethylbenzoyl)- phenylphosphineoxide (Irg819), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), 2,2-dimethoxy-2- phenyl acetophenone. 2-hydroxy -2 -methylpropiophenone (Irgl 173), lithium phenyl-2, 4,6- trimethylbenzoylphosphinate (TPO-Li), 2.2'-azobis[2-methyl-N-(2- hydroxyethyl)propionamide] (VA-086), benzophenone, or 2-hydroxy-4'-(2- hydroxy ethoxy )-2 -methylpropiophenone (Irg2959).

5. The photosensitive resin of claim 1, wherein the matrix ceramic comprises a PMN-PT (lead magnesium niobate-lead titanate. Pb(Mgi / 3Nb2 / 3)-PbTiO3) composite.

6. The photosensitive resin of claim 5, wherein the PMN-PT composite comprises a PMN:PT molar ratio of 65:35.

7. The photosensitive resin of claim 5, wherein the PMN-PT composite comprises 30% of the volume of the photosensitive resin.

8. The photosensitive resin of claim 1, wherein the plurality of template seeds comprise a plurality of microcrystal platelets comprising barium titanate (BaTiCL).

9. The photosensitive resin of claim 1, wherein each of the plurality of template seeds have a lateral dimension of approximately 7 pm and a thickness of approximately 600 nm.

10. The photosensitive resin of claim 1, wherein each of the plurality of template seeds have an orientation of <100>.

11. The photosensitive resin of claim 1, wherein the plurality of template seeds comprise 1% of the volume of the matrix ceramic.

12. The photosensitive resin of claim 1, wherein the photosensitive resin further comprises a liquid phase sintering regent.

13. The photosensitive resin of claim 12, wherein the liquid phase sintering regent comprises lead nitrite.

14. The photosensitive resin of claim 13, wherein the liquid phase sintering regent comprises lead nitrite at 5% of the weight percentage of the matrix ceramic.

15. The photosensitive resin of claim 1, wherein the photosensitive resin further comprises a sintering aid.

16. The photosensitive resin of claim 15, wherein the sintering aid comprises copper oxide at .2% of the weight percentage of the matrix ceramic and boric oxide at .2% of the weight percentage of the matrix ceramic.

17. A method of fabricating a piezoelectric textured ceramic containing piezoelectric elements by the steps comprising: a. providing, in a vat, a photosensitive resin comprising a photo monomer, a matrix ceramic, and a plurality of template seeds; b. applying an alternating electric field to the vat, wherein applying the alternating electric field comprises: i. applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and ii. applying, using a second plurality of electrodes, a second electric field oriented in a second direction; c. applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; d. removing the cured resin structure from the vat; and e. sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the piezoelectric textured ceramic containing piezoelectric elements, wherein the piezoelectric textured ceramic containing piezoelectric elements exhibits a cry stal grain with a uniformity of at least 60%.

18. The method of claim 17, wherein the first plurality of electrodes comprises a first electrode pair.

19. The method of claim 17, wherein the second plurality of electrodes comprises a second electrode pair.

20. The method of claim 17, wherein the first temperature is between 1215°C and 1250°C.

21. The method of claim 17, wherein the first period of time is 15 hours.

22. The method of claim 17, wherein the first direction is orthogonal to the second direction.

23. The method of claim 17, wherein the photo monomer comprises one or more acrylates selected from the group consisting of: polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDD A), triethylene glycol dimethacrylate (TEGDMA), bisphenol A-glycidyl methacrylate (Bis-GMA), urethane dimethacrylate (UDMA), and bisphenol A ethoxylate diacrylate (Bis-EDA).

24. The method of claim 17. wherein the photo monomer comprises a photo initiator.

25. The method of claim 24, wherein the photo initiator comprises a photo initiator selected from the group consisting of: bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irg819), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6- trimethylbenzoylphosphinate (LAP), 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- methylpropiophenone (Irgl 173), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Li), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086), benzophenone, or 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (Irg2959).

26. The method of claim 24, wherein the matrix ceramic comprises a PMN-PT (lead magnesium niobate-lead titanate, Pb(Mgi / 3Nb2 / ?)-PbTiO3) composite.

27. The method of claim 26, wherein the PMN-PT composite comprises a PMN:PT molar ratio of 65:35.

28. The method of claim 26, wherein the PMN-PT composite comprises 30% of the volume of the photosensitive resin.

29. The method of claim 17, wherein the plurality of template seeds comprise a plurality of microcrystal platelets comprising barium titanate (BaTiOs).

30. The method of claim 17, wherein each of the plurality of template seeds have a lateral dimension of approximately 7 pm and a thickness of approximately 600 nm.

31. The method of claim 17, wherein each of the plurality of template seeds have an orientation of <100>.

32. The method of claim 17, wherein the plurality' of template seeds comprise 1% of the volume of the matrix ceramic.

33. The method of claim 17. wherein the photosensitive resin further comprises a liquid phase sintering regent.

34. The method of claim 33, wherein the liquid phase sintering regent comprises lead nitrite.

35. The method of claim 33, wherein the liquid phase sintering regent comprises lead nitrite at 5% of the weight percentage of the matrix ceramic.

36. The method of claim 17, wherein the photosensitive resin further comprises a sintering aid.

37. The method of claim 36, wherein the sintering aid comprises copper oxide at .2% of the weight percentage of the matrix ceramic and boric oxide at .2% of the weight percentage of the matrix ceramic.

38. A transducer comprising at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps comprising: a. providing, in a vat, a photosensitive resin comprising a photo monomer, a matrix ceramic, and a plurality of template seeds; b. applying an alternating electric field to the vat, wherein applying the alternating electric field comprises: i. applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and ii. applying, using a second plurality of electrodes, a second electric field oriented in a second direction; c. applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; d. removing the cured resin structure from the vat; and e. sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

39. A hypersonic radome comprising at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps comprising: a. providing, in a vat, a photosensitive resin comprising a photo monomer, a matrix ceramic, and a plurality7of template seeds; b. applying an alternating electric field to the vat, wherein applying the alternating electric field comprises: i. applying, using a first plurality of electrodes, a first electric field oriented in a first direction; andii. applying, using a second plurality of electrodes, a second electric field oriented in a second direction; c. applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure: d. removing the cured resin structure from the vat; and e. sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

40. A sonar system comprising at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps comprising: a. providing, in a vat, a photosensitive resin comprising a photo monomer, a matrix ceramic, and a plurality of template seeds; b. applying an alternating electric field to the vat, wherein applying the alternating electric field comprises: i. applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and ii. applying, using a second plurality of electrodes, a second electric field oriented in a second direction; c. applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure: d. removing the cured resin structure from the vat; and e. sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity of at least 60%.

41. A seafloor mapping device comprising at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic is fabricated by the steps comprising: a. providing, in a vat, a photosensitive resin comprising a photo monomer, a matrix ceramic, and a plurality of template seeds; b. applying an alternating electric field to the vat, wherein applying the alternating electric field comprises:i. applying, using a first plurality of electrodes, a first electric field oriented in a first direction; and ii. applying, using a second plurality of electrodes, a second electric field oriented in a second direction; c. applying a digital light projection to a predetermined portion of the photosensitive resin in the vat in order to generate a cured resin structure; d. removing the cured resin structure from the vat; and e. sintering, at a first temperature, the cured resin structure in a sintering furnace for a first period of time to generate the at least one piezoelectric textured ceramic, wherein the at least one piezoelectric textured ceramic exhibits a crystal grain with a uniformity7of at least 60%.