WO2023229853A1 - Résine photosensible à indice de réfraction élevé pour impression 3d - Google Patents
Résine photosensible à indice de réfraction élevé pour impression 3d Download PDFInfo
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- WO2023229853A1 WO2023229853A1 PCT/US2023/021863 US2023021863W WO2023229853A1 WO 2023229853 A1 WO2023229853 A1 WO 2023229853A1 US 2023021863 W US2023021863 W US 2023021863W WO 2023229853 A1 WO2023229853 A1 WO 2023229853A1
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- mixture
- dimensional object
- metal oxide
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- optical
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/264—Arrangements for irradiation
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B33Y80/00—Products made by additive manufacturing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0037—Production of three-dimensional images
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Definitions
- Embodiments of the present invention provide a new methodology of production of a photoresin possessing tunable refractive index that can be used in a 3D printing that employs the two-photon lithographic processing of optical components or elements.
- Embodiments of the invention additionally provide a composite photoresin material produced according to an implementation of the method of the invention and/or an optically-transparent film or a three- dimensional object that comprises a material of a mixture (which includes a photoresin doped with a portion of a metal oxide organic compound such that a distribution of metal oxide particles of said compound in said mixture is substantially spatially uniform, which mixture is substantially optically transparent to light at a first wavelength and substantially photopolymerizable when exposed to light at a second wavelength that is half of the first wavelength, and which mixture is substantially devoid of agglomeration of the metal oxide particles)
- a mixture which includes a photoresin doped with a portion of a metal oxide organic compound such that a distribution of metal oxide particles of said compound in said mixture is substantially spatially uniform, which mixture is substantially optically transparent to light at a first wavelength and substantially photopolymerizable when exposed to light at a second wavelength that is half of the first wavelength, and which mixture is substantially devoid of agglomer
- FIG. 3 Focal length of micro-lenses, fabricated from the photoresin material configured according to an embodiment of the invention, was measured using collimated light from a helium-neon laser with a camera mounted on a translation stage.
- FIGs. 5A, 5B, 5C, 5D illustrate results of TPL 3D printing from a CAD model (FIG. 5A), and optical images (procured with the use of a microscope) of a structure printed with the use of an embodiment of a photoresin mixture configured according to an embodiment of the invention: image with focusing on the bottom of the structure (FIG. 5B), in the middle of the structure (FIG. 5C), and at the top of the structure (FIG. 5D).
- FIG. 6A shows plots of refractive indices for undoped IP-Dip, a GLYME/PO/TiCE nanocomposite, and a GLYME/PO/TiO2/IP-Dip composite.
- FIG. 6B additionally illustrates dispersion of refractive indices for IP-Dip with various concentrations of the dopant represented by the GLYME/PO/TiCE nanocomposite and identifies the focal lengths of lenslets (such as that discussed in reference to FIG. 2) fabricated from a corresponding version of the doped IP-Dip.
- FIG. 6C illustrates the dependence of the refractive index of the doped IP-Dip on the volume fraction (doping concentration) of the GLYME/PO/TiO2 nanocomposite.
- FIGs. 7A, 7B Measured focal length for a micro-lens (FIG. 7A) and ray tracing tolerance of refractive index at design wavelength (FIG. 7B).
- FIGs. 8A, 8B, and 8C illustrate three-dimensional structures printed with the use of a composite resin (photoresin mixure, formed according to the idea of the invention).
- FIG. 5D illustrates, on a larger scale, a portion of the upper surface of the micro-lens of FIG. 8C showing the relief structure on the lens surface, thereby demonstrating the spatial resolution capabilities of TPL 3D printing process when an embodiment of the photoresin mixture configured according to the idea of the invention is used.
- sol-gel methodology is employed to simultaneously synthesize and functionalize metal oxide nanoparticles that are intended to be further used as dopants for commercially available TPL resins (host materials) to produce mixtures with spatially-uniformly distributed dopants.
- TPL resins host materials
- the refractive index of the resulting material is then varied or modulated, as discussed with the use of practical examples below.
- Agglomeration of particles and related terms describe the presence of particle matter, dispersed in the host material, the size of which exceeds a predetermined value (in one non-limiting example - 10 am) as determined with the use of dynamic light scattering (DLS) methodology (described, for example, in en.wikipedia.org/wiki/Dynamic_light_scattering, the disclosure of which is incorporated herein by reference).
- DLS dynamic light scattering
- GLYME Glycidyl Methacrylate
- PO Propylene Oxide
- the total molarity of epoxide in the solvent was preferably kept as 1 ,3M in order to maintain concentration as high as possible before precipitation or aggregation.
- the solution was aged at room temperature for 5-7 days before processing.
- the contents of solvent, excess water, and reaction byproducts were reduced (and optionally, removed) by evaporation.
- the epoxide was not fully removed before combining the nanocomposite with the commercial TPL resin of choice. Some of the epoxides reacted and attached to the surface of the metal oxide nanoparticles and the unreacted epoxides were left in the solution. Most of the reaction byproducts had boiling points below 150 deg C and were removed during evaporation of the solvent.
- viscosity of the resulting resin-based composite material is important at least for the following reasons: when printing in the dip in laser lithography (DiLL) configuration, the microscope objective needs to be able to move freely through tire resin-based material without damaging tire already- printed portion of the structure; if viscosity is too low, the maximum height of the printed structure is likely to be limited (i.e. the resin-based material used for printing will effectively spread over the substrate, reducing the vertical extent thereof above the substrate); the viscosity' is a factor for the amount of oxygen diffusion during the printing process, which can affect the polymerization of the resin-based material and therefore the resolution of the printing process.
- DiLL dip in laser lithography
- the refractive index of the configured resin-based material was measured using a Meticon 2010 prism coupler with light at five wavelengths.
- the sample was prepared by printing a 5mm x 5mm x lOum thin film with the Nanoscribe printer. Due to the limited field of view of the Nanoscribe system, the film was printed by stitching multiple sections sized about 300 um x 300 um. While this way of printing could result in somewhat excessive exposure where the stitching windows overlapped and the boundaries could arguably cause scattering and losses during prism coupling, clear modes were nonetheless easily discernable with tire used instrument.
- OPP photon polymerization
- a second thin film was fabricated using a spin coater and UV flood exposure. The resin was diluted with ethanol to achieve thin films for spin coating.
- the synthesized photoresin material (interchangeably referred to herein as a resin-based material or a composite resin material or denoted with a similar term) lends itself to fabrication of three-dimensional objects that are different from a thin film.
- an optical thin film is defined as a thin film layer of material ranging in thickness from nanometers to a few micrometers in thickness and generating interference of visible light upon reflection and/or transmission of such light through such film.
- a micro-lens - specifically, a convcx-plano lens - was designed and printed with its planar side on a coverslip, as shown in FIG. 2. Freedom of variation of a shape of a surface, allowed by a 3D-printing process, was used to define the convex surface of the lens to be a rotationally symmetric aspheric surface defined as
- the camera was initially focused on a surface of the coverslip; images were taken of the focusing beam as the camera was translated away from the coverslip.
- the relative beam width was determined by taking cross sections of the beam in the images at each z distance and finding the Full-Width- Half-Maximum (FWHM) value.
- the beam waist and the spot size were determined by fitting the FWHM values to the well-known expression for a Gaussian beam width.
- the synthesized nanoparticle solution 404 (the image of which in a bottle is presented on the left side of FIG. 4A) had a reddish-amber hue after evaporation of the solvent (ethanol, in one case) .
- the loading of about 0.5 volume fraction of nanoparticles in the solution was demonstrated, as shown in FIG. 4B.
- the diameters of the suspended in this solution nanoparticles of the metal oxide were measured using Dynamic Light Scattering (DLS) to be smaller than 10 nm.
- DLS Dynamic Light Scattering
- GLYME itself is known to be able to be photopolymerized with the addition of a photoinitiator
- the GLYME- functionalized metal oxide (in one case - l i O2 ) nanocomposite was proven to possess the same ability.
- the GLYME- functionalized TiO 2 nanocomposite has limited practical usefulness in that it allows to only to create very thin films (with thicknesses smaller than about 200 nm) for traditional 2D photolithography using one-photon polymerization (see Optical Materials Express, 1 June 2011, vol. 1, No. 2, pp 252-258), but such material was never even been applied to TPL for 3D printing.
- IP -Dip, IP-S, and IP-nl62 which are all produced by Nanoscribe, to name just a few; these specific resins are all either acrylate or methacrylate functional groups, and are transparent at 780 nm and photoactive polymerizable at 390 nm, which were the operational wavelengths used in discussed experiments).
- Adding the IP resin does dilute tire original nanocomposite and lowers tire maximum achievable refractive index.
- FIGs. 6A, 6B illustrates measured RI for doped and undoped IP-Dip resin.
- plots of FIG. 6B additionally indicate doping concentrations of the same GLYME/PO/T1O2 nanocomposite.
- the focal length of the micro-lens from FIG. 2 had an expected back focal distance (BFD) of
- Hie measured back focal distance (BFD) at the beam waist was 800.1 microns. Uris corresponds to a deviation of 1.2% from the value predicted by the ray tracing.
- the refractive index of the lens can be determined by relating the BFD and the refractive index using the ray tracing model as illustrated in FIG. 7B. This method predicts the refractive index of this resin to be 1.668 at 633 nm. From the prism coupler measurements, this value was measured to be 1.6602. The difference between the refractive index as determined by the two methods is 0.0078, corresponding to 0.47% of either refractive index.
- the initial value of the refractive index of the IP-Dip resin was increased by 0.13 from 1.53 to 1.66 at 633 nm by doping such resin, as described, with 52 vol% of the nanocomposite consisting of TiO2, glycidyl methacrylate, and propylene glycol. Even higher indices were achievable by starting with a higher index base resin.
- the scope of the invention includes additional increase of the index of the nanocomposite by reducing the volume of the epoxides used, provided the molarity of the epoxides remains high enough (in one non-limiting case - of about 1.3 M) to mediate nanoparticle growth.
- Tuning tire proportions of tire PO and GLYME while maintaining the overall epoxide molarity can also be used to raise the index of the nanocomposite but may affect the miscibility of the nanoparticles with the TPL resin. This non-miscibility could increase scattering of the material, and lead to poor performance during 3D printing.
- the resulting resins are promising for several applications in optics and photonics.
- references throughout this specification to "one embodiment,” “an embodiment,” “a related embodiment,” or similar language mean that a particular feature, structure, or characteristic described in connection with the referred to “embodiment” is included in at least one embodiment of the present invention.
- appearances of the phrases “in one embodiment ⁇ "in an embodiment ⁇ and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment. It is to be understood that no portion of disclosure, taken on its own and in possible connection with a figure, is intended to provide a complete description of all features of the invention.
- two values being "substantially equal" to one another implies that the difference between the two values may be within the range of +/- 20% of the value itself, preferably within the +/- 10% range of the value itself, more preferably within the range of +/- 5% of the value itself, and even more preferably within the range of +/- 2% or less of the value itself.
- ROM read-only memory devices within a computer
- ROM read-only memory devices
- a computer I/O attachment such as CD-ROM or DVD disks
- writable storage media e.g. floppy disks, removable flash memory and hard drives
- information conveyed to a computer through communication media including wired or wireless computer networks.
- firmware and/or hardware components such as combinatorial logic, Application Specific Integrated Circuits (ASICs), Field-Programmable Gate Arrays (FPGAs) or other hardware or some combination of hardware, software and/or firmware components.
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Abstract
Des technologies de lithographie à deux photons (TPL) de Modem fournissent des procédés pratiques pour l'impression 3D de caractéristiques de taille submicronique dans des photopolymères. La capacité d'accorder les propriétés optiques du matériau de résine utilisé pour le TPL est hautement souhaitée car elle étend les capacités d'impression 3D. Des procédés de synthèse et de fonctionnalisation simultanées de nanoparticules d'oxyde métallique sont présentés pour être utilisés pour modifier la conception de résines commerciales hors du commerce pour produire un produit à base de résine dérivée avec un indice de réfraction accordable dépassant celui de n'importe quelle résine non modifiée disponible dans le commerce classique.
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US20190317255A1 (en) * | 2016-12-12 | 2019-10-17 | Lg Chem, Ltd. | Optical film and image display device including same |
US20210394437A1 (en) * | 2018-07-31 | 2021-12-23 | Prellis Biologics, Inc. | Methods and systems for three-dimensional printing |
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US20190317255A1 (en) * | 2016-12-12 | 2019-10-17 | Lg Chem, Ltd. | Optical film and image display device including same |
US20210394437A1 (en) * | 2018-07-31 | 2021-12-23 | Prellis Biologics, Inc. | Methods and systems for three-dimensional printing |
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Title |
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GUO QINGCHUAN, GHADIRI REZA, WEIGEL THOMAS, AUMANN ANDREAS, GUREVICH EVGENY, ESEN CEMAL, MEDENBACH OLAF, CHENG WEI, CHICHKOV BORIS: "Comparison of in Situ and ex Situ Methods for Synthesis of Two-Photon Polymerization Polymer Nanocomposites", POLYMERS, MOLECULAR DIVERSITY PRESERVATION INTERNATIONAL (M DP I) AG., CH, vol. 6, no. 7, CH , pages 2037 - 2050, XP093115480, ISSN: 2073-4360, DOI: 10.3390/polym6072037 * |
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