The present invention relates in general to nanocomposite optic devices and elements. The invention relates in particular to methods of manufacturing nanocomposite optical devices with integrated conductive electrodes using ink-jet printable nanocomposite materials.
Electro-optic devices are utilized to modulate light for a variety of applications. Macro sized electro-optic devices, such as a kerr cell, are typically manufactured from large crystals and bulk conductive electrodes. Micro sized electro-optic devices, such as waveguide electro-optic modulators, are manufactured on wafers with materials deposited via combinations of chemical, thermal and vapor deposition techniques. This application relates to another approach.
The present invention is directed to nanocomposite refractive-gradient optical-devices. In one aspect, a nanocomposite optical device comprises of a cured optically transparent nanocomposite ink and a treated conductive nanocomposite-ink. The treated conductive nanocomposite-ink integrated within the nanocomposite structure. The treated nanocomposite-ink having electrical, thermal or both electric and thermal communication to the exterior of the optical device and the same communication with at least a portion of the optically transparent nanocomposite within the optical-device.
The accompanying drawings, which are incorporated in and constitute a part of the specification, schematically illustrate preferred embodiments of the present invention, and together with the general description given above and the detailed description of preferred methods and embodiments, given below, serve to explain principles of the present invention.
Referring now to the drawings, wherein like components are designated by like reference numerals. Drawings are characterized by Cartesian (mutually perpendicular) axes x, y, and z. Although anyone skilled in the art can transform the axis to other coordinates or topologies. When referring to an optical-device, the z-axis refers generally to the direction of light propagation, and x and y being transverse axes. Methods of manufacture and preferred embodiments of the present invention are described further herein below.
Here conductive-inks 104A and 104B are exemplary of electrodes within the optical-device. Conductive-inks 104A and 104B are characterized by respective pads 105A and 105B on the exterior of optical-device 11 and respective members 106A and 106B. Pads 104A and 104B can be sized to allow for probe contact, soldering, or heat transfer to a heat sink. Members 106A and 106B, each independently can have electrical, thermal, or both electrical and thermal communication from the pad to the member. The treated conductive-ink can be sized and arranged within the optical-device in proximity to one another for electric communication, generating electric fields between the members, or positioned to transfer heat from the surrounding nanocomposite to exterior pads 105A and 105B.
A preferred method of manufacture for the optical-device is by ink-jet printing technology.
Printing apparatus 20 has reservoirs 212A and 212B that hold nanocomposite-ink 222A and 222B, respectively. Reservoirs 222A and 222B provide printing-heads 216A and 216B with nanocomposite-ink 222A and 222B via feed-lines 214A and 214B, respectively. Printing-heads 216A and 216B deposit nanocomposite-ink 222A and 222B, on substrate 218 at particular voxels, thereby forming a nanocomposite structure, such as the optical-devices of the present invention. Voxels refer to positions in three-dimensional space. Stage 217 positions substrate 218, with respect to the printing-heads, for deposition of the nanocomposite-inks at particular voxels.
Substrate 218 can be, or be made, from the group comprising plastics, glasses, metals, ceramics, organic resins, optics, molds, electronic circuits, light sources, wafers, and wafers with integrated electronics. Substrate 218 can become part of the optical element or alternatively the optical-device may be removed from the substrate. For applications in which the substrate becomes part of the optical-device, the substrate may be chosen for specific properties. For example, in applications where the optical-device will become integrated with a light source, the substrate material may be the light source. The optical-device could correct an some aspect of an optical system the substrate could be one of the components in the optical system. Alternatively, the substrate may be a mold material with anti-sticking properties, allowing removal of the optical-device from the mold.
After deposition of nanocomposite-ink from one of the printing-heads, substrate 218 can be positioned with respect to radiation source 219A for selective-curing of the nanocomposite-ink, at voxels. Selective-curing refers to localized radiation about voxels, activating the organic-matrix. Activation of the organic-matrix solidifies the nanocomposite-ink thereby forming the nanocomposite. Selective-curing means zero-curing, partial-curing, or fully-curing, which respectively means not solidifying, partially solidifying, or fully solidifying the nanocomposite-ink. Another radiation source 219B flood cures the nanocomposite-ink on the substrate. Flood curing is desirable when the all the nanocomposite-ink needs to be partially or fully cured.
The nanocomposite-inks can be different by the nanofiller type, the organic-host matrix type, or concentration of the nanofillers and combinations thereof. Non-limiting examples of nanofillers include beryllium oxide (BeO), aluminum nitride (AlO), silicon carbide (SiC), zinc oxide (ZnO), zinc sulfide (ZnS), zirconium oxide (ZrO), yttrium orthovanadate (YVO4), titanium oxide (TiO2), copper sulfide (CuS2), cadmium selenide (CdSe), lead sulfide (PbS), molybdenum disulfide (MoS2) and silicon dioxide (SiO2) including those with core, core-shell, and core-shell-ligand architectures. The refractive-index within the optical-device can be modified by the nanocomposite-ink used. The nanocomposite-ink can be tuned by the organic-matrix type, the nanofiller type, and the concentration of the nanofillers in the organic-matrix. The refractive-index of a nanocomposite-ink will be the summation by percent volume of the optical properties of the organic-matrix, or organic-host, and the nanofillers. Concentration by volume of the nanoparticles to the organic-host can be about 0.25% to about 70% volume, depending on desired properties. Various examples of nanoparticle and organic-matrix combinations and chemistries is described in U.S. patent application Ser. No. 14/036,660, assigned to the assignee of the present invention and the complete disclosure of which is hereby incorporated by reference in its entirety. Additionally, the nanocomposite-ink can be chosen and the optical-device structured to compensate chromatic aberration or increase chromatic dispersion, see U.S. patent application Ser. No. 14/278,164, assigned to the assignee of the present invention and the complete disclosure of which is hereby incorporated by reference in its entirety. Further, electro-optic nanofillers can be utilized in the optical-device and implemented to manufacture electro-optic modulators, see U.S. patent application Ser. No. 14/278,164, assigned to the assignee of the present invention and the complete disclosure of which is hereby incorporated by reference in its entirety. Similarly, optically nonlinear (NLO) nanofillers can be utilized in the optical-device and implemented to achieve optically nonlinear effects for applications which require optical limiting, see U.S. patent application Ser. No. 14/293,574, assigned to the assignee of the present invention and the complete disclosure of which is hereby incorporated by reference in its entirety.
The conductive nanocomposite-ink are preferably an ink-jet printable conductive-ink. The conductive-inks can be deposited concurrently or after deposition of the optical nanocomposite-ink. Concurrent deposition allows for complex 3-dimensional configurations of the conductive-inks. The deposition of the optical nanocomposite-ink can be directly onto smooth surfaces of the optical-device or in structured surfaces. For instance the optical nanocomposite-ink can be deposited forming a structure or channel, then partially cured to allow for guided deposition of the conductive-ink without mixture of the two inks. Alternatively, UV lithography techniques, nanoimprinting, single point CNC, or fluid jet polishing can be used to form channels.
Two suitable types of electrically conductive-inks are metal-based and graphene-based. The metal-based conductive-inks include metalorganic decomposition ink (MOD-ink) and more generally, aqueous based conductive nanocomposite-ink. Of the metal-based conductive-inks, the aqueous based conductive-inks are the preferred. MOD-inks are solvent based inks with metallic salts such as silver salt. However, the preferred aqueous based nanocomposite-inks endows a variety of advantages over conventional MOD-ink based on organic solvents in printing narrow conductive patterns without irregular morphologies and without residual contaminants. The aqueous based metal nanocomposite-inks are suspensions of metal nanoparticles such as silver and copper. The aqueous-based nanocomposite-inks are commercially available at a variety of manufacturers, for example, silver based nanocomposite-inks are available at Novacentrix in Austin, Tex. in The United States, Cabot Corporation in Boston, Mass. in The United States, and Samsung ElectroMechanics in Suwon, Gyeongg-do in South Korea.
The metal-based conductive-ink requires treatment, usually a sintering process, in order to create continuous connectivity of the conductive nanoparticles. The sintering process can include implementation of a furnace to increase the temperature of the conductive-ink, but temperatures of the optical-device should be kept below the glass transition of the polymers. Preferably the temperature of the EO-modulator is kept below 150° Celsius (C.). A number of techniques can be implemented to avoid high temperatures while allowing continuous connectivity of the conductive nanoparticles. Hydrochlorides solutions can be used to dissolve chemical coating on the nanoparticles. Direct localized heating of the conductive-inks can be achieved through direct resistive heating. Pulsed light can sinter the material via pulsed ultraviolet xenon arc lamps, near infrared, or other radiation sources.
The graphene-based nanocomposite-ink are suspensions of graphene, graphene-oxide, or other graphite-based particles. A typical procedure for preparing non-oxidized graphene-based conductive-ink is to grind natural graphite flakes into smaller particles, approximately 5 microns of less, then disperse in deionized water with or without a dispersing agent and with or without sonication. One example of a deionized water with a dispersing agent is Deionized water with 0.1% by weight of dispersing agent, Zonyl® FSO surfactant can be used to obtain a suspension of graphene flakes. Zonyl® FSO is available from DuPont, headquartered in Wilmington, Del. of the United States. Sonication aids in dispersing the graphite in the solution and reducing aggregation.
Another graphene-based (or graphite-oxide) nanocomposite-ink are suspensions of graphene-oxide flakes. Graphene-oxide can be obtained by oxidation of graphite using strong oxidizing agents. For example graphite flakes can be oxidized with sulfuric acid, nitrate, and potassium permanganate or with potassium chlorate and nitric acid, known as the Hummers and Brodie methods respectively. Oxygenated functionalization causes the graphene-oxide to have increased layer separation and make the material hydrophilic. Using sonication the graphene-oxide can be dispersed in water. Treatment of the graphene-oxide dispersion results in the conductive layers of graphene. Methods of treating the graphene-oxide solution includes treatment with hydrazine hydrate at 100 degrees Celsius for 24 hours, exposing the dispersion to hydrogen plasma for a few second, Joule heating by applying current to the conductive-inks, or by irradiating the dispersion with a strong pulse of light. Light of wavelengths in the ultraviolet, near-infrared, infrared, and microwave can be used. For treatment within the optical-device, light radiation from a laser can irradiate the conductive-inks either collectively with a large beam or selectively with a focused beam.
During treatment of the graphene-oxide, most carboxyl, hydroxyl and epoxide groups are removed from the graphene-oxide, resulting in conductive graphene. During this process gases, for example CO and CO2 are formed. For those conductive-inks that are encapsulated in the nanocomposite, voids can be made into the optical-device allowing escape of gases during treatment.
Yet another of the conductive-inks are carbon nanotube (CNT) based inks. CNT-based ink are prepared with a conductive polymer such as poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and carboxyl functionalized single-walled carbon nanotubes (SWCNT-COOHs).
Graphene, graphene-oxide, and other graphene based products are commercially available at a variety of manufacturers. For example, graphene products are available from; Graphene Supermarket in Calverton, N.Y. of the United States, ACS Material of Medford, Mass. of the United States, and Grafen Chemical Industries Co. of Ankara, Turkey.
For those configurations of the optical-device in which a conductive path is required for external communication, like that shown in
High loading of thermally conductive nanoparticles, such as aluminum nitride, or other ceramics and metal-oxides nanoparticles allow for thermally conductive, yet electrically insulated conductive-inks. Such inks can be used as heat sinks and thermal connection to components within the optical-device.
The optical-device and various embodiments described have a variety of useful utilities and applications. In general, the optical-device described herein allows manufacture of any optic which requires thermal or electrical communication-within the device. For example, the conductive-ink can be deposited in the shape of a aperture and absorb or reflect light while allowing heat to dissipate to the external surface of the optical-device. The conductive-ink can act as electrical circuitry within the optical-device allowing for modulation of electro-optic or optically nonlinear nanocomposite materials. Additionally the conductive-ink can be deposited to form an antenna or inductive loop antenna, to communicate with or charge other components within the optical-device.
From the description of the present invention provided herein one skilled in the art can design the optical-device and implement them in the described applications in accordance with the present invention. Those skilled in the art to which the present invention pertains will recognize that while above-described embodiments of the inventive optical-device and method of manufacture are exemplified using particular configurations, others may be used without departing from the spirit and scope of the present invention. Further, combinations of the various described embodiments and the combinations of refractive-gradients described in those embodiments can be implemented.
In summary, the present invention is described above in terms of particular embodiments. The invention, however, is not limited to the embodiments described and depicted herein. Rather, the invention is limited only by the claims appended hereto.
Number | Date | Country | |
---|---|---|---|
Parent | 14307071 | Jun 2014 | US |
Child | 16224512 | US |