US20080254210A1

US20080254210A1 - Optical elements and methods for making thereof

Info

Publication number: US20080254210A1
Application number: US12/144,525
Authority: US
Inventors: Shui T. Lai; Lawrence Sverdrup
Original assignee: Lai Shui T; Lawrence Sverdrup
Current assignee: Ophthonix Inc
Priority date: 2002-07-11
Filing date: 2008-06-23
Publication date: 2008-10-16
Also published as: US20050046957A1; WO2006029268A2; US7420743B2; WO2006029268A3

Abstract

Optical elements are made using micro-jet printing methods to precisely control the type, position and amount of polymer deposited onto a substrate. In preferred embodiments, the proportions of two or more different polymer compositions are varied over the course of the deposition process to deposit adjoining polymer pixels in the form of a film on the substrate surface. The optical properties of each adjoining polymer pixel can be selected to provide a predetermined optical property, including a specific value of index of refraction. Preferably, the film has a radially non-monotonic refractive index profile and/or an angularly non-monotonic refractive index profile.

Description

RELATED APPLICATION INFORMATION

This application is a continuation-in-part of U.S. patent application Ser. No. 10/253,956, filed Sep. 24, 2002, which claims priority to U.S. Provisional Patent Application No. 60/395,878, filed Jul. 11, 2002, both of which are hereby incorporated by reference in their entireties. Disclosure Document No. 514428, deposited with the U.S. Patent and Trademark Office on Jun. 28, 2002, is also incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention
This invention relates to optical elements and methods of making them by using micro-jet printing methods to precisely control the type, position and amount of polymer deposited onto a substrate.
2. Description of the Related Art
Optical elements such as eyeglass lenses are typically made by casting, grinding and/or polishing blanks made from glass or plastics such as polycarbonate and polyethylene glycol diallyl dicarbonate (CR39). However, lenses made by these fabrication techniques are only capable of correcting relatively simple vision problems. Other fabrication techniques have been developed to address more complex vision problems, but these techniques are uneconomical because they are relatively complicated and not well-suited for mass production.
Lens elements with a spatially varying index of refraction are known, see, e.g., U.S. Pat. No. 6,089,711. The material for the fabrication of such lenses can be made by a variety of processes such as sol-gel, infusion, and diffusion. However, these fabrication techniques produce lenses having a radial gradient profile in which the index of refraction increases or decreases monotonically across the radius of the lens because the gradient is obtained by a diffusion process. These fabrication techniques are inapplicable to the manufacture of lenses in which the index of refraction at any particular point can be specified in a controlled manner to produce a radially non-monotonic refractive index profile. Arrays of microlenses have been made by irradiating a photopolymerizable or photocrosslinkable substance with laser light having an uneven distribution of intensity, see U.S. Pat. No. 5,998,096. However, the presence of unreacted photoreactive substances remaining within the irradiated article often presents stability problems.
Micro-jet printing methods have been reported which are said to be capable of printing arrays of microlenses onto a substrate, see U.S. Pat. Nos. 5,498,444; 5,707,684; and W. Royall Cox et al., “Micro-Optics Fabrication by Ink-Jet Printing,” Optics and Photonics News, pp. 32-35, June 2001. Methods have also been reported for modifying the surface of lenses to correct for optical aberrations, see U.S. Pat. No. 6,086,204. However, such methods seek to control optical properties by controlling the thickness of the lens, rather than by controlling the refractive index of the material from which the lens is made. Methods have also been reported for varying the effective index of refraction by using lithographic methods to produce very small bore holes in the lens material, see U.S. Pat. No. 5,585,968.

SUMMARY OF THE INVENTION

The present invention relates to optical elements and methods for making them by depositing controlled amounts of polymers onto a substrate with a high degree of spatial resolution to form polymer pixels. In preferred embodiments, selected amounts of two or more polymer compositions, each having a different individual optical property, are deposited onto the substrate in a manner that averages the individual optical properties at any particular point in the resulting optical element. For example, two polymers, each having a different refractive index, may be deposited onto a surface in controlled proportions that vary as a function of position across the surface of the substrate, resulting in an optical element in which the refractive index varies in a desired fashion as a function of position within the element.
Preferred methods provide exceptionally precise control over optical properties as a function of position within the optical element, and thus provide optical elements having unique optical properties. Preferred optical elements include lenses that can correct relatively complicated or higher order aberrations that may cause vision problems.
These and other embodiments are described in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects of the invention will be readily apparent from the following description and from the appended drawings (not to scale), which are meant to illustrate and not to limit the invention, and wherein:

FIGS. 1A-1C schematically illustrate a plurality of spray heads projecting polymer droplets onto nearly the same location on a substrate in various proportions to form adjoining polymer pixels.

FIGS. 2A-2B schematically illustrate a plurality of spray heads projecting polymer compositions onto a substrate.

FIG. 3 is a schematic drawing showing a preferred pre-mix spray head for projecting polymer compositions onto a substrate in various proportions.

FIG. 4 is a schematic drawing showing a preferred pre-mix spray head having valves for controlling the pre-mix of polymer compositions.

FIG. 5 is a schematic drawing showing a preferred pre-mix spray head having valves for controlling the composition of a polymer/solvent pre-mix.

FIGS. 6A-6B are schematic drawings illustrating methods of controlling refractive index by controlling the relative sizes of the deposited polymer droplets.

FIG. 7 shows diagrams of wavefront profiles for various types of vision or optical instrument aberrations.

FIG. 8 is a flow chart illustrating an embodiment for making a lens that corrects for specific aberrations in the human eye.

FIG. 9 is a schematic drawing illustrating a cross-sectional view of a preferred film that comprises adjoining polymer pixels.

FIG. 10 is a schematic drawing illustrating a preferred airjet spray unit in which separate streams of atomized polymer droplets are intermixed and then projected.

FIG. 11 is a schematic drawing illustrating a cross-sectional view of a preferred airjet spray unit in which separate polymer composition streams are intermixed, then atomized and projected.

FIG. 12 is a schematic drawing illustrating a cross-sectional view of a portion of a preferred airjet spray unit in which two separate streams of atomized polymer droplets are directed at a substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Preferred embodiments are directed to methods and systems for making optical elements. Preferred optical elements comprise a continuous film containing a relatively large number of relatively small polymer “pixels.” The individual polymer pixels are the basic building blocks of the preferred optical element and are loosely analogous to the traditional pixels that are the basic building blocks of an image on a television screen. The polymer pixels are preferably arranged within the optical element is such a way that an eye or observing instrument perceives continuity, similar to the way that an image on a television screen appears to be continuous. For example, the polymer pixels in an optical element such as an eyeglass lens are preferably so small and close together that the unaided human eye does not readily perceive that the focusing effect produced by the lens is due to the individual pixels. Preferably, the polymers pixels are contiguously adjoined to one another at their edges to form a continuous film (see FIG. 9, discussed below). The optical properties of an individual polymer pixel are preferably relatively constant throughout the pixel (except near boundaries where mixing may occur when a pixel adjoins another pixel having a different optical property). The optical properties of the optical element can be varied from point to point throughout the optical element by controlling the optical properties of the individual polymer pixels making up the optical element.
In preferred embodiments, control over the optical properties of the individual polymer pixels is exercised by precisely depositing selected amounts of two or more polymer compositions, each having a different individual optical property, onto a substrate in the form of polymer pixels, such that the desired optical property is produced at any particular pixel in the resulting optical element by averaging the individual optical properties of the materials comprising each polymer pixel. This “averaging” may result when the constituents of the two or more polymer compositions mix together to form a single pixel. Averaging of an optical effect may also be produced when the constituents of the two polymer compositions remain separated after deposition on the substrate surface, but are so small and close together that an eye or observing instrument perceives them to be a single pixel.
Polymer pixels are preferably deposited using a Polymer Projection Deposition System (PPDS) that rapidly projects a large number of very small polymer droplets at precisely controlled pre-selected locations on a substrate. Micro-jet polymer printing methods generally known to those skilled in the art are examples of PPDS's when used as described herein. PPDS's are described in U.S. Pat. Nos. 5,235,352, 5,498,444 and 5,707,684, all of which are hereby incorporated by reference in their entireties and particularly for the purpose of describing PPDS's. PPDS's are commercially available from MicroFab Technologies, Inc., Plano, Tex. An “airjet” is an additional example of a PPDS. The term “airjet” refers to a device that uses a gas (such as air) to create and/or project a collection of small particles or droplets toward a desired location (e.g., a suitable surface), and thus includes various devices that use air to project a polymer through a nozzle, with or without prior atomization of the polymer. The term “airjet” and “micro-jet” are not mutually exclusive, and thus an airjet may be a micro-jet and vice versa. Examples of airjets are described in U.S. Patent Application Publication Nos. 2003/0020768 and 2003/0048314, both of which are hereby incorporated by reference in their entireties and particularly for the purpose of describing airjets. In preferred embodiments, one or more of the various spray heads described in greater detail below are airjets. Thus, for example, the spray heads of the embodiments illustrated in FIGS. 1-5 may be airjets. A preferred PPDS comprises a computerized control unit that controls the projecting of a first polymer composition and a second polymer composition onto pre-selected locations on a substrate, in a plurality of pre-selected ratios of the first polymer composition to the second polymer composition.
Many properties of the resulting optical element can be controlled by depositing polymers onto a substrate as described herein, including mechanical, physical, chemical and optical properties. Preferably, optical properties are controlled, including without limitation index of refraction, polarizability, Verdet constant, Kerr constant, electro-optical constant, birefringence, and absorption. More preferably, an optical property is controlled in a point-to-point manner throughout the film to provide a non-monotonic profile in the property, as measured radially and/or angularly (in circular coordinates). For example, a preferred film has a radially non-monotonic refractive index profile and an angularly non-monotonic refractive index profile. In a preferred embodiment, the optical element is a lens that comprises a continuous polymer film having a radially non-monotonic refractive index profile and/or an angularly non-monotonic refractive index profile.
Preferred methods for making optical elements involve the projection of two or more polymer compositions onto pre-selected locations on a substrate. The term “polymer composition,” as used herein, is a broad term that refers to a composition that comprises a polymer. The term “polymer” includes all forms of polymer and their precursors, including without limitation pre-polymers, polymer solutions, polymer emulsions, polymer microemulsions, solid polymers, polymer melts, and/or mixtures thereof. For example, a polymer composition comprising liquid pre-polymers may be projected by a PPDS onto a substrate, then cured (e.g., by heat or irradiation) to form solid polymer pixels. The wavelength of irradiation used to cure the pre-polymer may vary over a broad range, e.g., x-ray, ultraviolet (UV) visible, infrared, microwave, millimeter wave, etc. The irradiation may comprise particle radiation, e.g., particle beam, electron beam and/or ion beam. Preferred pre-polymers are UV-curable. A polymer composition comprising a solvent may likewise be projected onto a substrate, and the solvent evaporated to form solid polymer pixels. A polymer composition comprising solid particulate polymers may be projected onto a substrate, then heated to form solid polymer pixels. A polymer composition comprising a molten polymer can be projected onto a substrate, then cooled to form solid polymer pixels. Polymer emulsions or microemulsions are polymer compositions that may be projected onto a substrate, and the carrier liquid evaporated to form solid polymer pixels. For embodiments in which two or more high molecular weight polymers are projected, the individual polymers preferably form mutually miscible blends in all proportions. Preferably, there are relatively large differences in the indices of refraction between each of the individual polymers.
Optical elements and the polymer compositions used to form them can include a wide variety of polymer types. Non-limiting examples of polymer types include poly(acrylate), poly(methylmethacrylate), poly(vinylidene chloride), polycarbonate, poly(vinyl butyral), poly(ethylene), ethylene/1-alkene copolymer, poly(ethylene terephthalate), poly(acrylonitrile), poly(butadiene), polystyrene, acrylonitrile-butadiene-styrene (ABS) terpolymers, allyl diglycol carbonate polymer, poly(methyl pentene), polyamide (e.g., nylon), poly(2,6-dimethyl-1,4-phenyleneoxide), poly(vinyl methyl ether), epoxy polymer, thiol-ene polymer, silicone polymer, and blends, mixtures, copolymers, and pre-polymers thereof. Pre-polymers are preferred. Polymers containing aromatic compounds or nitrogen atoms, and/or atoms of high atomic weight such as sulfur, bromine or metals generally have a higher index of refraction. Non-aromatic polymers devoid of atoms with high atomic weight and fluoropolymers generally have lower indices of refraction. High refractive index polymers can be dissolved in monomers to obtain a high index polymer composition.
Preferred polymer compositions are polymerizable compositions that have been found to be particularly well-suited for use in the methods described herein. Preferred polymerizable compositions comprise a first ene monomer and a first thiol monomer together having a refractive index of 1.55 or greater; and a second ene monomer and a second thiol monomer together having a refractive index of less than 1.55. The monomers may be intermixed in any order to form the polymerizable composition. The polymerizable compositions are preferably made by preparing a high index composition comprising the first ene monomer and a first thiol monomer; preparing a low index composition comprising second ene monomer and a second thiol monomer, and may involve intermixing the high index composition and the low index composition to form the polymerizable composition. The refractive indices of each of the monomer pairs (e.g., the refractive index of the first ene monomer and the first thiol monomer together) are measured apart from the polymerizable composition. To determine the refractive index of the ene monomer and thiol monomer apart from the polymerizable composition, a test sample is prepared which contains the ene monomer and thiol monomer together in the same relative proportions as in the polymerizable composition. The refractive index of the test sample is then determined at 25° C. Those skilled in the art will recognize that various mixtures of the components are themselves polymerizable compositions. For example, the first ene monomer and a first thiol monomer together form a polymerizable composition, and likewise the second ene monomer and the second thiol monomer together form a second polymerizable composition.
The refractive index of the polymerizable composition may be varied over a broad range by varying the relative amounts of the high index composition and the low index composition, and by appropriate selection of the ene and thiol monomers themselves. The ratio of high index composition to low index composition in the polymerizable composition may vary over a broad range of from about 0:100 to about 100:0. Preferably, the ratio is selected by considering the refractive index of the individual components, using routine experimentation to confirm that the resulting mixture provides the desired refractive index after polymerization. Preferably, the relative amounts of ene and thiol monomers are selected such that subsequent polymerization forms a polymer having the desired physical properties, e.g., mechanical and optical properties. More preferably, the relative amounts of ene and thiol monomers in the polymerizable composition are such that the number of ene functional groups is about equal to the number of thiol groups. The high index composition and the low index composition are preferably intermixed by the methods described herein, e.g., as described below with respect to FIG. 1.
A wide variety of ene and thiol monomers are useful for making polymerizable compositions. Preferred ene and thiol monomers and the refractive indices of preferred high and low index compositions are described in the Examples below. The refractive indices of other high and low index compositions may be determined by routine experimentation. In any particular polymerizable composition, the first ene monomer may be the same as the second ene monomer, or the first thiol monomer may be the same as the second thiol monomer, so long as the first ene monomer and the first thiol monomer together have a refractive index of 1.55 or greater, as measured apart from the polymerizable composition, and the second ene monomer and the second thiol monomer together have a refractive index of less than 1.55, also as measured apart from the polymerizable composition. Preferably, the first ene monomer is selected from the group consisting of styrene, divinylbenzene,
Preferably, the first thiol monomer in the polymerizable composition is selected from the group consisting of thiobisbenezenethiol,
Preferably, the second ene monomer is:
Polymer compositions may comprise one or more additives incorporated for various reasons, e.g., to affect the properties of the resulting polymer pixels and/or to facilitate the fabrication process. Non-limiting examples of such materials include solvents, surfactants, crosslinking agents, polymerization inhibitors, polymerization initiators, viscosity modifiers, stabilizers, colorants, pH adjusters, fillers, low-index particles, high-index particles, and metals. Polymer compositions comprising a high index composition and a low index composition preferably comprise one or more additives selected from the group consisting of polymerization initiator (e.g., photoinitiator, thermal initiator), polymerization inhibitor, antioxidant, photochromic dye, and UV-absorber. Preferred polymer compositions have a solution viscosity in the range of about 1 centipoise (cP) to about 2000 cP, preferably about 1 cP to about 80 cP, as measured at the temperature and shear rate used to project the composition onto the substrate. High-index particles and metals are preferred additives for optical applications. High-index particles, including metals, metal oxides and metal fluorides, are preferably incorporated into the polymer composition in an amount that increases the refractive index of the resulting polymer pixel by about 0.001 or more. Preferred high index particles are nanoparticles having a size that does not scatter the wavelength of interest when incorporated into the optical element. Preferred nanoparticles have a refractive index that is higher than the polymer contained in the polymer pixel into which the nanoparticles are incorporated, more preferably a refractive index of about 1.6 or higher. Preferred nanoparticles comprise a polymer, a metal, and/or metal oxide, more preferably titanium dioxide (TiO₂) and/or lanthanum oxide (La₂O₃). Nanoparticles can be incorporated into polymer compositions in a variety of ways, preferably by dispersing them in the polymer composition using a surface active agent. Metals can be incorporated into polymer compositions in the form of nanoparticles or in other ways. For example, organometallic compounds containing the metal of interest can be dissolved or dispersed in a polymer composition. An example of a stable organo-metallic compound for such use is titanium tetraisopropoxide, see U.S. Pat. No. 6,394,613. Other organometallic compounds include triphenyl bismuth and various organotin compounds.
Preferably, at least a portion of the solid polymer pixels in the continuous polymer film each comprise a first material and a second material, the first material being different from the second material in an optical property. For example, the first material in a particular polymer pixel may be a polymer and the second material in that pixel may be a different polymer, a metal, and/or a nanoparticle, the different polymer, metal, and/or nanoparticle having refractive index that is different from the refractive index of the first polymer. Preferably, the first and second materials in the polymer pixel form a polymer/polymer, polymer/metal or polymer/nanoparticle mixture. The term “polymer/polymer” refers to a mixture containing two or more polymer types, preferably as described above. The term “polymer/metal” refers to a mixture containing a least one polymer and at least one metal. The metal may be dissolved in the polymer and/or dispersed in the polymer, e.g., dispersed in the form of a nanoparticle, preferably as described above. The term “polymer/nanoparticle” refers to a mixture containing a least one polymer and at least one type of nanoparticle, preferably a dispersed nanoparticle as described above.
Polymer compositions may be deposited onto a broad variety of substrates. Preferred substrates include glass, polymer, metal, ceramic, crystal, paper, and semiconductor surfaces. In one embodiment, the optical element is a continuous free-standing film that is removed from the substrate after fabrication. For this embodiment, the substrate preferably has non-stick surface to minimize adhesion to the film, permitting the film to be easily peeled from the substrate after it is made. In another embodiment, the substrate is substantially transparent. Those skilled in the art will understand that the term “substantially transparent” means that the substrate is sufficiently transparent for its intended use. For example, lens blanks used for making eyeglasses are preferred examples of substantially transparent substrates. Such substrates are considered substantially transparent even if their optical transparency is reduced by tinting or coating to produce, e.g., sunglasses, because after such tinting or coating the substrate remains sufficiently transparent for its intended use. Lens blanks include plano blanks (having no corrective power) as well as lenses having various degrees of corrective power. A preferred lens blank is selected from the group consisting of a plano blank, an optical blank with positive focusing power, an optical blank with negative focusing power, an optical blank with focusing power and cylindrical power, and an optical blank with progressive addition lens (PAL) power. In a preferred embodiment, the substantially transparent substrate and the continuous film together comprise a lens. Other preferred substrates include the optics of viewing instruments such as telescopes, microscopes, cameras, binoculars, and ophthalmic diagnostic instruments such as confocal scanning ophthalmoscopes, as well as other instruments that contain precision optical elements such as refractive elements (e.g., lenses), reflective elements (e.g., mirrors and beam splitters), and/or diffractive elements (e.g., gratings and acousto- and electro-optical crystals).
The polymer pixels in the optical element are preferably “solid,” meaning that they are substantially free of uncured or partially cured polymer. Wavefront aberrators having a variable index of refraction have been prepared by selective curing of a polymer, see U.S. Patent Application Publication No. 2002/0080464 A1, but contain non-solid areas in which the polymer is not completely cured. It has been found that the presence of significant amounts of uncured or partially cured polymer in the polymer pixels can result in stability problems if the extent of cure changes over time and affects the optical properties of the optical element. Solid polymer pixels may be flexible or rigid, and thus the continuous film comprising the polymer pixels may also be flexible or rigid, depending on factors such as the thickness of the film and the type of polymer. The solid polymer pixels may be deposited on the continuous film or the continuous film may consist essentially of contiguous adjoining polymer pixels. The continuous film may comprise a plurality of layers, preferably with each layer comprising solid polymer pixels, or may be a layer within another structure. Continuous films may contain gaps, holes or apertures as desired, e.g., to form an optical element having a particular configuration. Continuous films comprise a plurality of polymer pixels, preferably at least about 50 adjoining polymer pixels, more preferably at least about 1000 adjoining polymer pixels. The average size of the polymer pixels is preferably about 200 microns or less, more preferably in the range of about 0.1 micron to about 200 microns, even more preferably in the range of about 0.1 micron to about 10 microns, most preferably in the range of about 0.1 micron to about 1 micron. For non-symmetrical polymer pixels, size is measured along the longest dimension. In a preferred embodiment, the average size of the pixels is below the size at which the pixels scatter the radiation of interest. For visible light, the average size of the pixels is preferably about 0.4 micron or less, more preferably about 0.3 micron or less.
Preferably, the properties of any particular solid polymer pixel are controlled by mixing two or more polymer compositions to thereby average the corresponding properties of the constituents of each polymer composition. The proportions of each individual polymer composition deposited at any given location on the substrate may be varied from 0% to 100%, by weight based on total weight. Various methods may be used to control the proportions of the individual polymer compositions deposited. A preferred method for making an optical element comprises forming a first polymer pixel on a substrate, the first polymer pixel comprising a first polymer composition and a second polymer composition in a first ratio; (b) forming a second polymer pixel adjoining the first polymer pixel, the second polymer pixel comprising the first polymer composition and the second polymer composition in a ratio that is different from the first ratio; and (c) repeating steps (a) and (b) to thereby form a continuous film comprising a plurality of adjoining polymer pixels.
For example, FIG. 1A illustrates a preferred embodiment in which two polymer compositions are projected onto a substrate using a spray unit 100 that is controlled by a computerized controller 105, the spray unit 100 comprising a first spray head 110 and a second spray head 115. In this embodiment, the first spray head 110 contains or is charged with a first polymer composition comprising a high refractive index polymer, and the second spray head 115 contains or is charged with a second polymer composition containing a low refractive index polymer. For example, the first polymer composition may be a high index composition comprising the first ene monomer and a first thiol monomer and the second polymer composition may be a low index composition comprising a second ene monomer and a second thiol monomer. The spray heads 110 and 115 are positioned an operative distance from a substrate 120. Deposition is conducted by projecting a first polymer droplet from the first spray head 110 onto a pre-selected location on the substrate 120 to form a first deposited polymer droplet 125, the first polymer droplet containing a first amount of the first polymer composition. Deposition is further conducted by projecting a second polymer droplet 130 from the second spray head 115 in close proximity to the first deposited polymer droplet 125, the second polymer droplet containing a second amount of the second polymer composition.
The deposition process continues as illustrated in FIG. 1B by forming a first polymer pixel 135 by mixing the first deposited polymer droplet 125 and the second polymer droplet 130. The first polymer pixel 135 comprises the first polymer composition and the second polymer composition in a first ratio. At least one of the first and second spray heads 110 and 115 is then adjusted to allow an additional droplet to be projected, the additional droplet being different from at least one of the first and second droplets 125 and 130. In the illustrated embodiment, first and second spray heads 110 and 115 are each adjusted to alter the relative amounts of the first and second polymer compositions, respectively, to be projected. This may be accomplished in various ways, e.g., by adjusting the compositions and/or the sizes of the droplets, see FIG. 6 (discussed below), and/or the number of droplets (also discussed below). In FIG. 1B, the positioning of the first and second spray head heads 110 and 115 with respect to the substrate 120 is also adjusted, e.g., by moving the substrate laterally as indicated by the first arrow 140, and/or by moving the spray unit laterally as indicated by the second arrow 145, and/or by pivoting the spray heads 110 and 115 (not shown), etc. These adjustments to the spray heads and their positions relative to the substrate can by conducted in any order, for example, the first spray head 110 may be adjusted before the second spray head 115, or vice versa, or the spray heads may be adjusted simultaneously, and are preferably controlled by the computerized controller 105. The deposition process is then repeated as illustrated in FIG. 1B by projecting new first and second polymer droplets 150 and 155 from spray heads 110 and 115 to thereby form a second polymer pixel 160 adjoining the first polymer pixel 135 as shown in FIG. 1C, the second polymer pixel comprises the first polymer composition and the second polymer composition in a second ratio, different from the first ratio. A continuous film comprising a plurality of adjoining polymer pixels may then be formed by repeating the deposition process in a like manner, preferably by adjusting the spray heads and their positions to the extent and in the manner needed to form a continuous film having the desired properties. The polymer compositions may be heated or cooled by, e.g. heating or cooling the first and second spray heads 110 and 115 as desired, e.g., to adjust the viscosities of the polymer compositions. It is understood that the ratio of first polymer to second polymer in one polymer pixel can be the same as in an adjoining polymer pixel, and thus the first and second spray heads 110 and 115 do not always need to be adjusted to alter the relative amounts of the first and second polymer compositions, respectively, to be projected.
For the embodiment illustrated in FIG. 1, the forming of the polymer pixels preferably takes place by at least partially intermixing the contents of projected droplets on the surface of the substrate. Preferably, at least about 50%, more preferably at least about 75%, of the adjoining solid polymer pixels in a continuous film comprise a mixture of a first polymer and a second polymer, as determined at the center of the polymer pixel. Those skilled in the art will appreciate that such mixing need not take place prior to the deposition of the next droplet, and thus may take place after a number of droplets have been deposited on the substrate, e.g., as illustrated in FIG. 6 (discussed below). It will also be appreciated that a pixel may contain only one polymer composition (excluding boundary effects with other pixels, where edge mixing may occur), e.g., a pixel formed from only one polymer droplet, or that a pixel may be formed from many polymer droplets, depending on the size desired for the pixel. Thus, in a preferred embodiment, the composition of a pixel formed from many polymer droplets is controlled by adjusting the first and second spray heads 110 and 115 to control the relative number of droplets projected from each spray head onto the substrate location at which the polymer pixel is formed.
Those skilled in the art will appreciate that the composition of a pixel may also be controlled by subsequent processing, e.g., by polymerization or crosslinking of any reactive constituents (e.g., monomers, prepolymers, crosslinking agents) in the pixel. For example, as discussed above, polymer compositions that are polymerizable compositions have been found to be particularly well-suited for use in the methods described herein. Polymerization and/or crosslinking may be conducted using methods appropriate for the reactive constituents of the pixel as known to those skilled in the art. Preferably, polymerization and/or crosslinking are accomplished by heating the deposited pixels and/or by exposure to radiation, e.g., UV-irradiation.
In the embodiment illustrated in FIG. 1, both of the spray heads 110 and 115 project the polymer droplets to nearly the same point on the substrate. The first and second polymer droplets may be projected sequentially (with or without a lapse of time between projection) or simultaneously. For example, in the embodiment illustrated in FIG. 2 (not to scale), spray unit 200 is controlled by computerized controller 201 and comprises spray heads 205 and 210. A first deposited polymer droplet 215 is projected by spray head 205 onto a location 220 on the substrate 225 as shown in FIG. 2A. The spray unit 200 and/or the substrate 225 moves laterally so that a second polymer droplet 230 projected from spray head 210 onto the substrate 225 is deposited in close proximity to the first polymer droplet 215 as shown in FIG. 2B. After deposition, the first and second polymer droplets 215 and 230 are free to intermix to form a polymer pixel, preferably a solid polymer pixel having a refractive index that is a weighted average of the refractive indices of the polymer compositions contained in each of the first and second polymer droplets 215 and 230. As indicated in FIG. 2B, the deposition process continues in a similar manner by projecting new first and second polymer droplets 235 and 240 from the first and second spray heads 205 and 210, respectively. In the illustrated embodiment, the polymer droplets projected by the first spray head 205 comprise a high refractive index polymer, and the polymer droplets projected by the second spray head 210 comprise a low refractive index polymer. The properties of adjoining polymer pixels can be made to differ by, e.g., adjusting the first and second spray heads 205 and 210 to vary the size of the projected droplets and/or the relative amounts of the high refractive index polymer and low refractive index polymer, respectively, contained within the projected polymer droplets. The properties of adjoining polymer pixels can also be made to differ by controlling the relative number of droplets deposited by each spray head. The polymer compositions may be heated or cooled prior to projection by, e.g., heating or cooling the first and second spray heads 205 and 210 as desired, e.g., to adjust the viscosities of the polymer compositions. The embodiments illustrated in FIGS. 1 and 2 may comprise additional spray heads for projecting additional polymer compositions in a similar manner.
It is apparent from the foregoing that the spray heads may be adjusted to alter the droplet size and/or relative amounts of constituents in the polymer compositions contained in the droplets. Thus, those skilled in the art will appreciate from the foregoing that deposition may also be conducted using a single spray head by repeatedly adjusting the spray head to alter the relative proportions of the polymer compositions charged to the spray head. Such a method may be conducted, for example, as generally described above by using only one of the spray heads illustrated in FIG. 1 or 2. A preferred method comprises positioning a spray head an operative distance from a substrate; charging the spray head with a first polymer composition; projecting a first polymer droplet from the spray head onto the substrate to form a first polymer pixel on the substrate; charging the spray head with a second polymer composition different from the first polymer composition; adjusting the positioning of the spray head with respect to the substrate; and projecting a second polymer droplet from the spray head onto the substrate to form a second polymer pixel adjoining the first polymer pixel. A continuous film comprising a plurality of adjoining polymer pixels may be formed by repeating these steps. Each polymer droplet may result in a separate polymer pixel, or a polymer pixel may be formed from a plurality of droplets deposited in close proximity on the substrate.
Those skilled in the art will appreciate that multiple spray heads or spray units may be used in the PPDS's described herein, and that any or all of the various functions of the PPDS are preferably controlled by a computerized controller. Preferably, the controller is programmed by inputting a desired optical property profile, and controls the amount and type of each polymer deposited at each location on the substrate to produce, e.g., an optical element having a desired refractive index profile. A preferred spray unit comprises one or more airjets. Examples of preferred spray units comprising airjets are described in U.S. Patent Application Publication Nos. 2003/0020768 and 2003/0048314. Additional examples of preferred spray units comprising airjets are illustrated in FIGS. 10-12.
Additional steps may be carried out to facilitate the forming of the solid polymer pixels. Preferably, polymer pixels are formed by localized mutual diffusion between deposited polymer droplets containing different constituents. Such diffusion is preferably facilitated by heating, e.g., by heating the substrate. Heating and/or reduced pressure may also be used to evaporate any solvent present in the deposited polymer pixels to form solid polymer pixels. Heating may also be used to cure a pre-polymer to form solid polymer pixels. Pre-polymers may also be cured by other methods known to those of skill in the art, depending on the specific pre-polymer, e.g., by irradiation, preferably by ultraviolet light or electron beam.
Intermixing of the polymer compositions may also take place prior to projecting. For example, FIG. 3 illustrates a preferred embodiment in which two polymer compositions are pre-mixed in a spray head 300, then projected onto a substrate 305. Deposition may continue in the general manner discussed above to form adjoining solid polymer pixels. The proportions of the constituents in each of the resulting polymer pixels can be controlled in various ways. For example, in the embodiment shown in FIG. 3, a spray head 300 comprises a mixing chamber 310 to contain a polymer droplet 315, the chamber having an orifice 320 sized to permit the polymer droplet 315 to be expelled from the chamber. Preferably, the volume of the polymer droplet 315 is in the range of about 10 picoliters to about 10 microliters. The spray head 300 also has a first inlet 325 connecting the mixing chamber 310 to a first reservoir 330, the first inlet 325 being sized to permit passage of a first solvent or first polymer composition into the mixing chamber 310 from the first reservoir 330. The spray head 300 also has a first actuator 335 operatively disposed to expel a pre-selected quantity of the first solvent or first polymer composition from the first reservoir 330 into the mixing chamber 310 and, optionally, out of the orifice 320 as a first constituent of the polymer droplet 315. The spray head 300 also has a second inlet 340 connecting the mixing chamber 310 to a second reservoir 345, the second inlet 340 being sized to permit passage of a second solvent or second polymer composition into the mixing chamber 310 from the second reservoir 345. The spray head 300 also has a second actuator 350 operatively disposed to expel a pre-selected quantity of the second solvent or second polymer composition from the second reservoir 345 into the mixing chamber 310 and, optionally, out of the orifice 320 as a second constituent of the polymer droplet 315.
Each of the first and second actuators 330 and 345 is capable of generating a full polymer droplet or a fraction of a polymer droplet and controls the flow of each polymer composition from each of the respective reservoirs 330 and 345 into the mixing chamber 310. In the illustrated embodiment, the first polymer composition in the first reservoir 330 contains a high refractive index polymer and the second polymer composition in the second reservoir 345 contains a low refractive index polymer. The composition of the polymer droplet 315 can be varied from droplet to droplet, as the first and second actuators 335 and 350 controlling the flow of the polymer compositions into the mixing chamber each provide fractions of a droplet through the first and second inlets 325 and 340, respectively, the fractions preferably adding to one. Preferably, the first and/or the second actuators 335 and 350 are controlled by a computerized controller 355, thereby enabling the computer to control the quantity of first solvent or first polymer and/or second solvent or second polymer entering the mixing chamber 310. The first and second actuators 335 and 350 may be operated to project the polymer droplet from the mixing chamber 310, or the mixing chamber may be equipped with a third actuator (not shown) for this purpose. Those skilled in the art will appreciate that additional reservoirs containing additional polymer compositions may be attached to the mixing chamber 310 by additional inlets. All or part of the spray head 300 may be heated or cooled as desired, e.g., to adjust the viscosities of the polymer compositions.
Another method for intermixing two or more polymer compositions prior to projecting is illustrated in FIG. 4 (not to scale). A spray head 400 comprises a chamber 405 to contain a polymer droplet 410, the chamber 405 comprising an orifice 415 sized to permit the polymer droplet 410 to be expelled from the chamber. Preferably, the volume of the polymer droplet 410 is in the range of about 10 picoliters to about 10 microliters. The spray head 400 further comprises a first inlet 420 attached to the chamber 405 and sized to permit passage of a first solvent or a first polymer composition into the chamber 405 from a suitable reservoir (not shown). The first inlet 420 is equipped with a first valve 425, preferably computer controlled by controller 428, the first valve 425 being adjustable to allow a pre-selected quantity of the first solvent or the first polymer composition to enter the chamber 405 from the inlet 420. The spray head 400 also comprises a second inlet 430 attached to the chamber 405 and sized to permit passage of a second solvent or a second polymer composition into the chamber 405. The second inlet 430 is equipped with a second valve 435, preferably computer controlled (either by a controller 428 or by a different controller 438 as shown), the second valve 435 being adjustable to allow a pre-selected quantity of the second solvent or the second polymer composition to enter the chamber 405 from the inlet 430. The spray head 400 also comprises an actuator 440 operatively disposed to expel the polymer droplet 410 from the chamber 405 through the orifice 415. Preferably, the actuator also draws the first and second polymer compositions into the chamber 405. Preferably, the spray head 400 also comprises means for pressurizing the fluid first polymer composition and/or the second polymer composition such as a pump or pumps (not shown) attached to the inlets 420, 430 and/or respective polymer reservoirs. The spray head 400 also preferably comprises means for drawing the fluid first polymer composition and/or the second polymer composition into the chamber such as the actuator 440 or a pump attached to the chamber 405.
In the embodiment illustrated in FIG. 4, the first polymer composition comprises a high refractive index polymer and the second polymer composition comprises a low refractive index polymer. In operation, the flow of the polymer compositions into the chamber 405 is controlled by the first and second valves 425 and 435, which are preferably electro-mechanically activated and controlled by a computer. Liquid volume and/or flow monitoring devices can also be included (not shown). The chamber 405 preferably has a small volume, so that the composition of the projected polymer droplets can be rapidly altered. All or part of the spray head 400 may be heated or cooled as desired, e.g., to adjust the viscosities of the polymer compositions. The spray heads illustrated in FIGS. 3 and 4 are examples of the spray heads that can be used in the methods illustrated in FIGS. 1 and 2. Preferably, a computerized controller is used to control the PPDS's, including the spray units and spray heads described herein. Although the difference in refractive index in the first and second polymer compositions in the illustrated embodiment is controlled by using polymers having different refractive indices, those skilled in the art will understand that the difference in refractive index can be achieved in other ways. For example, the first and second polymer compositions may contain the same polymer, but different amounts or types of a metal or a high-index nanoparticle.
As discussed above, the polymer compositions may comprise a solvent. Preferred solvents reduce the viscosity of the polymer composition into a range that is suitable for projecting by the methods described herein. Solvents for various polymers are know to those skilled in the art, and are preferably selected on the basis of factors such as performance, cost, toxicity, and/or environmental acceptance. A spray head may be adjusted to introduce varying quantities of solvent into a polymer composition, thus varying the amount of polymer contained in the resulting projected polymer droplet. For example, FIG. 5 illustrates a spray head 500 generally similar to the spray head 400 illustrated in FIG. 4, except that a solvent is introduced into chamber 505 by way of a second inlet 530 and a second valve 535. The spray head 500 illustrated in FIG. 5 comprises a chamber 505 to contain a polymer droplet 510, the chamber 505 comprising an orifice 515 sized to permit the polymer droplet 510 to be expelled from the chamber. Preferably, the volume of the polymer droplet 510 is in the range of about 10 picoliters to about 10 microliters. The spray head 500 further comprises a first inlet 520 attached to the chamber 505 and sized to permit passage of a first polymer composition into the chamber 505 from a suitable reservoir (not shown). The first inlet 520 is equipped with a first valve 525, preferably computer controlled by a controller 528, the first valve 525 being adjustable to allow a pre-selected quantity of the first polymer composition to enter the chamber 505 from the inlet 520. The spray head 500 also comprises a second inlet 530 attached to the chamber 505 and sized to permit passage of a solvent into the chamber 505. The second inlet 530 is equipped with a second valve 535, preferably computer controlled (either by the controller 528 or by a different controller 538 as shown), the second valve 535 being adjustable to allow a pre-selected quantity of the solvent to enter the chamber 505 from the inlet 530. The spray head 500 also comprises an actuator 540 operatively disposed to expel the polymer droplet 510 from the chamber 505 through the orifice 515. Preferably, the actuator also draws the first polymer composition and solvent into the chamber 505. Preferably, the spray head 500 also comprises means for pressurizing the fluid first polymer composition and/or the solvent such as a pump or pumps (not shown) attached to the inlets 520, 530 or the respective reservoirs. The spray head 500 also preferably comprises means for drawing the fluid first polymer composition or the solvent into the chamber such as the actuator 540 or a pump attached to the chamber 505.
The amount of polymer composition in each projected droplet 510 may thus be controlled on a droplet-by-droplet basis by varying the relative ratio of the polymer composition and the solvent. The amount of polymer composition in the droplet can vary from 0 to 100% by volume. Preferably, the solvent is present in an amount effective to adjust at least one property selected from the group consisting of first polymer composition viscosity, second polymer composition viscosity, and volume ratio of the first polymer composition to the second polymer composition. Practice of this embodiment allows the composition and viscosity of the droplet to be modified by the solvent, preferably while maintaining a relatively constant droplet size. The viscosity of the droplet may also be modified by adjusting the temperature of the polymer composition. The temperature may be adjusted by controlling the temperature of the polymer prior to and/or after projection of the droplet. For example, the polymer may be stored in a temperature-controlled container prior to deposition, and/or the temperature of the air surrounding the droplet during projection may be controlled. Those skilled in the art will appreciate that any of the spray heads described herein may be adjusted in a like manner to vary the composition, viscosity and/or size of the resulting projected polymer droplet.
The properties of the continuous film can be controlled on a pixel-by-pixel basis in three dimensions by depositing one or more layers of polymer droplets. For example, FIG. 6 schematically illustrates layers comprising deposited polymer droplets. In the illustrated embodiments, a high refractive index polymer is represented by the filled semi-circles and a low index polymer is represented by the open semi-circles. For simplicity of illustration, only two types of deposited polymer droplets are shown, without any mixing or interdiffusion, but it will be appreciated that other types of polymer droplets may be deposited and that localized mixing may occur. In FIG. 6A, all of the deposited polymer droplet are approximately the same size and there are an equal number of high and low index droplets. After mixing (not shown), the illustrated droplets will form a polymer pixel having a refractive index about midway between the refractive indices of the individual polymer pixels. In FIG. 6B, there are an equal number of high and low index droplets, but the high index droplets are about ⅓ the size of the low index droplets. After mixing (not shown), the resulting polymer pixel will have an index of refraction that is lower than in FIG. 6A because of the higher proportion of low index polymer contained in the deposited polymer droplets. Deposition of the droplets shown in FIG. 6B on a substrate in close proximity to the droplets shown in FIG. 6A will, after localized mixing, result in adjoining polymer pixels in which the refractive index varies from one pixel to the other.
The methods described above provide exceptional control over the refractive index of the resulting optical element as a function of position. By controlling the proportions of the various constituents (and thus the refractive index) in each pixel, the number of pixels deposited on the substrate, and the position of each pixel, a continuous film having a non-monotonic profile in an optical property can be formed. Optical elements having a radially monotonic profile in an optical property, typically refractive index, have been disclosed, see U.S. Pat. No. 6,089,711 and H. J. Trost, “Using prop-On Demand Technology for Manufacturing GRIN Lenses,” Proc. 2001 Ann. Mtg. ASPE, 10-15 Nov. 2001 (ASPE Raleigh N.C. 2001), pp. 533-536. The refractive index profile in such optical elements rises or falls steadily along a radius from a central point, without reversals or oscillations. In this context, those skilled in the art will understand that an optical element having a “radially non-monotonic” profile has a varying optical property that does not simply stay the same, rise steadily, or decrease steadily along a radius from a central point. Preferably, the continuous films described herein have a radially non-monotonic refractive index profile, more preferably a radial refractive index profile that has at least two inflection points (points at which the increasing or decreasing refractive index reverses direction), even more preferably at least three inflection points, most preferably at least four inflection points. Each of these inflection points can be selectively controlled to be at any location within the optical element. The refractive index profile is determined parallel to the surface of the continuous film or, if the film surface is curved, parallel to a plane tangent to the curved surface.
The methods described herein also enable the manufacture of optical elements having an angularly non-monotonic profile in an optical property. An “angular” profile is measured along an arc defined by a radius from a central point and is also determined parallel to the surface of the continuous film or, if the film surface is curved, parallel to a plane tangent to the curved surface. The length of arc along which the angular profile is measured is 45° (or less, if the configuration does not permit a 45° measurement). Thus, an “angularly non-monotonic” profile has a varying optical property that does not simply stay the same, rise steadily, or decrease steadily along a 45° arc at a particular radius from a central point. Preferably, the continuous films described herein have an angularly non-monotonic refractive index profile, more preferably an angular refractive index profile that has at least two inflection points (points at which the increasing or decreasing refractive index reverses direction), even more preferably at least three inflection points, most preferably at least four inflection points. Each of these inflection points can be selectively controlled to be at any location within the optical element.
Preferably, micro-jet and/or airjet methods generally known to those skilled in the art are used to deposit the polymer compositions onto the substrate. These micro-jet and airjet methods provide excellent control over the position and amount of polymer deposited. The polymer compositions are preferably projected by a PPDS in the form of polymer droplets onto adjacent locations on the substrate so that the resulting solid polymer pixels are adjoining. Such adjacent deposition preferably results in a continuous polymer film, and also tends to facilitate blending. Various droplet sizes and size distributions can be used. Droplet size is preferably selected to provide the desired gradation of properties in the resulting optical element. For example, smaller droplets tend to produce smaller pixels and thereby provide finer spatial resolution and finer control of refractive index. The volume of the polymer droplet (and the corresponding deposited droplet) may vary, depending on the size desired for the pixel, and is preferably about 20 microliters or less, more preferably about 2 microliters or less, most preferably about 0.2 microliter or less.
Polymers that do not form compatible blends are preferably deposited onto the substrate in the form of very small deposited polymer droplets that do not intermix and that are adjacent to one another. The size of these deposited polymer droplets is preferably small enough so that the resulting scattering in not significant. Scattering depends on the size of the deposited polymer droplets relative to the wavelength of the impinging radiation. When the deposited polymer droplets are small relative to the wavelength, the eye or observing instrument cannot resolve the separation between the individual deposited polymer droplets and thus pixels are formed optically by averaging the optical properties of the individual deposited polymer droplets. For visible light, the average size of the deposited polymer droplets is preferably about 0.4 micron or less, more preferably about 0.2 micron or less.
Polymer compositions are preferably prepared by considering the desired optical properties of the resulting continuous film. For example, for continuous films in which the adjoining polymer pixels comprise a mixture of a first polymer and a second polymer, the first polymer preferably has a refractive index that is different from the second polymer, so that polymer pixels having a range of refractive indices can be prepared. Preferably, the first polymer has a refractive index of about 1.5 or less, more preferably about 1.45 or less. Preferably, the second polymer has a refractive index greater than 1.5, more preferably about 1.6 or greater. For polymer pixels that contain metals or nanoparticles, e.g., high refractive index nanoparticles, the adjoining solid polymer pixels may each comprise the same type of polymer. The amount and/or type of metals and/or nanoparticles present are preferably adjusted to provide the desired refractive index profile. The amounts of the constituents in the polymer compositions and mixtures thereof that produce the desired optical property in the resulting solid polymer pixels can be estimated using the well known rule of mixtures, then refined by routine experimentation. Alternatively, the index profile can also be controlled by incorporating low index nanoparticles thereby producing lower index of refraction pixels. For example, to maximize the dynamic range of the index of refraction using a device as depicted in FIGS. 1A and 1B, the first spray head 110 may contain a first polymer composition which comprises a high index polymer and high index nanoparticles (and/or a metal), and the second spray head 115 may contain a second polymer composition which comprises a low index polymer and low index nanoparticles. Thus, the index of refraction difference between the first and second polymer compositions may be further enhanced by the addition of the nanoparticles.
Computers and controllers are referred to herein are broad terms that refer to devices such as microprocessors, microcontrollers and similar programmable electronic devices. These devices preferably comprise hardware, firmware and/or software configured to control the operations of the systems described herein in accordance with the steps and methods set forth. Preferably, a computer is used to control the projection of the polymer compositions so that the correct amount of each is deposited at the various locations across the substrate to obtain the locally desired optical property. As used herein, the term “computer” is a broad term that refers to any device that computes, especially a programmable electronic machine that performs high-speed mathematical or logical operations or that assembles, stores, correlates, or otherwise processes information. Thus, a preferred embodiment provides a computer programmed to direct the operations of a PPDS to prepare an optical element as described herein.
Greater thickness of the deposited polymer film generally produces greater dynamic range in optical path difference. By controlling the net amount of polymer material deposited at all locations, an optical film of any desired thickness may be formed. This can be accomplished in a single pass of the spray head, or with multiple passes. If desired, the viscosity of a deposited film can be increased by, e.g., partial curing of any pre-polymers after each pass of the spray head. In preferred embodiments, differences in the materials from which the solid polymer pixels are made produce at least part of the desired radially non-monotonic profile in the optical property. The desired radially non-monotonic profile can also be achieved by combining both effects, i.e., by utilizing differences in the materials from which the solid polymer pixels are made and by varying the thickness of the film at various points. Thus, these embodiments are distinguished from optical elements in which only the shape or thickness of the optical element is used to vary the optical properties.
Preferably, the substrate surface is adjusted so that the deposited polymer droplets do not spread excessively or bead up excessively and fail to wet the substrate. Surface wetting can be affected by coatings or treatments applied to the substrate. Preferred surface treatments are selected from the group consisting of applying a surfactant, increasing surface energy, decreasing surface energy, increasing hydrophobicity, and decreasing hydrophobicity. Methods for carrying out these treatments are known to those skilled in the art. For example, surface energy can be increased by plasma treatment of the surface. Increased surface energy typically results in more spreading and better wetting of the substrate. Suitable equipment for carrying out various surface treatments is commercially available, e.g., from Tri-Star Technologies of El Segundo, Calif. In addition to, or instead of, such surface treatments, a thin coating may be applied to the substrate surface prior to deposition of the polymers as is typically done in the case of inkjet overhead transparencies. This coating may consist of an absorbing layer, or it may be a non-absorbing layer with suitable wetting characteristics.
Prior to the curing of deposited polymer droplets that contain pre-polymers or monomers, the deposited polymer droplets are preferably allowed to mix and/or diffuse into one another sufficiently that the resulting index variation is smooth, thus minimizing any scattering or spatial frequency noise associated with abrupt index variations from pixel to neighboring pixel. The time required for this diffusion is preferably controlled so that adequate diffusion occurs, but also to prevent excessive diffusion that could affect lower spatial frequencies of the index profile that it may be desirable to maintain. Projecting a larger quantity of smaller polymer droplets, and/or overlapping the pixels as they are deposited on the substrate, tends to decrease the diffusion time. The diffusion time also depends upon the polymer viscosities and the temperature, and is preferably determined by routine experimentation. Inadequate diffusion may be observed as index variations on the scale of the solid polymer pixels using a microscope equipped with differential interference contrast (DIC). A phase-shifting interferometer, commercially available from Zygo Corporation, in Middlefield, Conn. may be used to ensure that the correct overall optic is obtained and that excessive diffusion has not taken place.
There are a variety of modes in which the optical element can be formed, including a free-standing film mode, a coating mode, and a sandwich mode. For example, a continuous film may be formed on the surface of a non-stick substrate, then peeled from the substrate to form a free-standing film. Alternatively, a continuous film may be applied to the free surface of an optical substrate, or sandwiched between two substrates.
The sandwich mode has the advantage that thickness is controlled, and the surfaces of the continuous film are forced to be optically flat. Preferably, the surface of the film has a flatness of about λ/10, where λ is the wavelength of the radiation for which the optical element is designed. For a curved surface, the surface of the film is preferably such that the deviation from the desired curvature is less than about 0.02 diopter. There is essentially no free surface of the polymer film, so that any environmental requirements on the polymer may be relaxed. For example, an environmental requirement might be for the exposed polymer surfaces to resist scratches or absorption of moisture. The surface of the continuous film need not satisfy these requirements if it is protected between two substrates. In the sandwich mode, the continuous film may also act as an adhesive. For example, such a sandwich mode may be formed by first projecting polymer droplets upon one substrate as described elsewhere herein to form a continuous film comprising adjoining polymer pixels, and then subsequently applying a second substrate or cover to the free surface of the continuous film. Preferably, the thickness of the continuous film is not substantially changed, in order to minimize distortion of the optical property profile formed by the solid polymer pixels. If the deposited polymer droplets comprise a prepolymer, curing may take place before or after the second substrate is applied. If the viscosity of the deposited prepolymer-containing droplets is sufficiently high, curing may be obtained with no outside support of the two substrates. If the volume change of the prepolymer-containing droplets during curing is negligible, then the separation of the substrates can be controlled with solid shims located at the edges of the substrate. If the shrinkage of the prepolymer-containing droplets is not negligible, then compressible shims may be utilized. The compressible shims may provide a stop position for the cover, and/or may provide a flexible thickness adjustment to facilitate removal of any voids between the cover and the film. Alternatively, beads with diameter equal to the desired substrate separation and with refractive index matched to the average index can be added to the prepolymer-containing droplets. Preferably, the index matched shim beads are deposited only in those regions of the optic that are intended to have constant index, and not in the areas of rapidly varying index.
A preferred way of practicing the coating and/or sandwich modes is by projecting polymer droplets onto a substrate as described elsewhere herein to form a continuous film comprising adjoining polymer pixels, and then placing a polymer composition onto the film. The polymer composition is preferably a liquid at the time of placement and may be placed onto the film by a variety of coating techniques such as by spin coating, film coating, dip coating, and/or by projecting drops of the polymer composition onto the film. In the coating mode, the polymer composition preferably solidifies by, e.g., cooling from the melt, evaporation of a solvent, crosslinking, and/or polymerizing, depending on the nature of the polymer composition.
In the sandwich mode, a second substrate or cover is placed over the continuous film to thereby sandwich the polymer composition between the substrate and the cover. The polymer composition may be placed onto the film and/or onto the cover prior to placing the cover over the film; and/or the polymer composition may be injected between the cover and film after the cover is placed over the film, as desired. The polymer composition is preferably in a liquid form at the time that it is sandwiched between the cover and substrate. The cover may be a lens, lens blank, plano lens, protective film, etc., and may be flat or curved, depending on the desired application. The viscosity of the polymer composition is preferably such that it fills any gaps or spaces that might otherwise form between the cover and the film. The refractive index of the polymer composition, upon solidification, is preferably about the same as the cover. Preferably, the polymer composition is a polymerizable composition as described above, more preferably a UV-curable polymerizable composition. The polymerizable composition may be polymerized before or after being sandwiched between the cover and film, or may be polymerized in stages both before and after sandwiching.
Another way of practicing the sandwich mode is by first projecting polymer droplets upon one substrate as described elsewhere herein to form a continuous film comprising adjoining polymer pixels, and then subsequently depositing a coating onto the continuous film. In this manner, for example, a scratch-resistant coating may be applied to protect the underlying continuous film. The coating may be applied by traditional coating techniques or by PPDS methods known to those skilled in the art, or by the deposition methods described herein (preferably without varying the composition of the projected droplets, so that an optically uniform coating results).
Another mode is to apply the pre-polymer film to the free surface of an optical substrate and cure it or otherwise solidify it in that position, as an external coating. Preferably, such a polymer film has adequate environmental properties such as hardness and moisture resistance. One advantage of this mode is that only one substrate is required. Preferably, the free surface of the cured polymer film is optically smooth. To cause this to occur, the viscosities of the polymer compositions are preferably such that the deposited polymer droplets are self-leveling. A final polishing or machining including diamond turning may be utilized.
The optical elements described herein are useful in a variety of applications. In one embodiment they are used in the form of a correcting optic for microscopes, telescopes, binoculars, cameras and other optical instruments. In another, they are used in the form of a thin film correcting optic incorporated into eyeglasses to remove low and high order aberrations of the human eye to improve vision beyond the current state of the art, which currently only corrects for cylinder and focus errors.
Conventional glasses correct only for cylinder and focus errors of the human eye. Examples of these aberrations are shown in the wavefront profile plots illustrated in FIGS. 7A and 7B. The vertical axis (height) of the plots represents the extent of distortion of the wave front. Human eyes may include, in addition, higher-order wave front aberrations that are not describable in terms of cylinder and focus. These aberrations, however, may be described in terms of Zernike polynomials. Plots illustrating some representative examples of high-order Zernike polynomials are shown in FIGS. 7C-7D. FIG. 7E depicts a measurement of the combined low and high order wave front aberrations in the eye of a human subject. FIG. 7F depicts an index of refraction profile correcting the aberration of the human eye in FIG. 7E.
The methods described herein can be applied to correcting both low and high order aberrations. In FIG. 8, a flowchart is shown illustrating a method of manufacturing a vision correction device. A measurement is first made 810 to determine the wavefront aberrations of the patient eye. The aberrations can be generally divided into two categories, the low order aberrations 820, consisting of sphere, cylinder and axis, and the high order aberrations 830 including various orders of coma, trefoil, and spherical aberration. Methods for measuring such wavefront aberrations are well known and can be conducted with commercially available instruments, as demonstrated in FIG. 7F. Next, an ophthalmic lens blank is selected 840 which corrects at least a portion of the low order aberration in a manner similar to what is currently provided by an optometrist. Then, a PPDS 850 as described herein is used to deposit a continuous film on the ophthalmic lens blank to produce a lens that corrects the high order aberrations when positioned in front of the patient's eye. This layer can be applied to the front or the back surface of the ophthalmic lens blank. A protective cover may then be applied. Alternatively, the film layer can be covered with a protective coating for enhancement of scratch resistance. The flowchart in FIG. 8 also shows an alternate route of selecting a plano blank 860, and the PPDS in this case is used to create a continuous film 870 that corrects both the low and high order aberrations. Thus, the optical element may correct one or more low order aberrations and/or high order aberrations, and/or any portion thereof.
Preferred optical elements comprise a continuous film, the continuous film comprising a plurality of solid polymer pixels. FIG. 9 is a cross-sectional perspective view illustrating such a continuous film 900. In the illustrated embodiment, a first solid polymer pixel 905 has a refractive index that is different from an adjoining second solid polymer pixel 910. In one embodiment, the first pixel 905 contains a first epoxy polymer and a second epoxy polymer in a first ratio. The first epoxy polymer has a refractive index that is different from the second epoxy polymer, so that the refractive index of the first pixel 905 is the weighted average of the individual refractive indices of the first and second epoxy polymers. The second pixel 910 contains the first epoxy polymer and the second epoxy polymer in a second ratio that is different from the first ratio. Since the ratio is different, the refractive index of the second pixel 910 is different from the refractive index of the first pixel 905. In another embodiment, the first pixel 905 and the second pixel 910 both contain the same polymer, but the second pixel 910 contains an amount of high index nanoparticles or an amount of metal additive that causes the second pixel 910 to have a higher refractive index than the first pixel 905. In the illustrated embodiment, first and second pixels 905, 910 form part of a layer that overlies an underlying layer that comprises third and fourth pixels 915, 920. The bottom side of the film 900 is shown in contact with a substantially transparent substrate 925. The top side of the film 900 may be in contact with a second substrate 930, so that the continuous film 900 forms a layer between the first substrate 925 and the second substrate 930. The film 900 has a uniform thickness in the illustrated embodiment, but may have a non-uniform thickness if desired.
Preferred spray units comprising airjets are illustrated in FIGS. 10 and 11. The spray unit 600 illustrated in FIG. 10 comprises an enclosure 625. A low index polymer enters the enclosure 625 by passing through an inlet 610 and intermixing with air supplied to the inlet 610 by another inlet 620. Likewise, a high index polymer enters the enclosure 625 by passing through an inlet 605 and intermixing with air supplied to the inlet 605 by another inlet 615. Upon exiting the inlets 610, 605, the low index and high index polymers (respectively) form a mixture of airborne particles 630. The respective amounts of low index polymer and high index polymer in the mixture of airborne particles 630 may be controlled by the valves 621, 616, respectively. The force of the air and polymers entering the enclosure 625 may be sufficient to cause the mixture of airborne particles 630 to exit the enclosure through outlet 640, or additional air may be supplied to the enclosure 625 through another inlet 635. The mixture of airborne particles 630 exiting the enclosure 625 by outlet 640 may be directed towards a substrate (not shown) to thereby deposit a polymer pixel containing a mixture of high and low index polymers onto the substrate in the manner generally described above for other embodiments. The composition of any particular pixel may be controlled by using the valves 621, 616 to control the amounts of low index and high index polymer in the mixture of airborne particles 630 exiting the enclosure 625 through the outlet 640. Those skilled in the art will recognize that gases other than air (e.g., nitrogen) may be used as desired, and that alternative valve arrangements may be used to control the respective amounts of low and high index polymers in the mixture of airborne particles 630.
The spray unit 700 illustrated in FIG. 11 comprises an enclosure 725. A low index polymer passes through an inlet 714 and intermixes with air supplied to the inlet 714 by another inlet 715. Likewise, a high index polymer passes through an inlet 713 and intermixes with the air supplied by the inlet 714 and with the low index polymer supplied by the inlet 714. The resulting mixture of air, low index polymer and high index polymer passes through outlet 716 and forms a mixture of airborne particles 730 in the enclosure 725. The respective amounts of low index polymer and high index polymer in the mixture of airborne particles 730 may be controlled by the valves 721, 720, respectively. The force of the air and polymers entering the enclosure 725 may be sufficient to cause the mixture of airborne particles 730 to exit the enclosure through outlet 740, or additional air may be supplied to the enclosure 725 through another inlet 735. The mixture of airborne particles 730 exiting the enclosure 725 by outlet 740 may be directed towards a substrate (not shown) to thereby deposit a polymer pixel containing a mixture of high and low index polymers onto the substrate in the manner generally described above for other embodiments. The composition of any particular pixel may be controlled by using the valves 721, 720 to control the amounts of low index and high index polymer in the mixture of airborne particles 730 exiting the enclosure 725 through the outlet 740. Those skilled in the art will recognize that gases other than air (e.g., nitrogen) may be used as desired, and that alternative valve arrangements may be used to control the respective amounts of low and high index polymers in the mixture of airborne particles 730.
FIG. 12 illustrates the manner in which two streams of airborne polymer particles 755, 765 may be directed at a substrate 770 by using two airjet nozzles 750, 760, respectively. In the illustrated embodiment, an airborne stream of low index polymer particles 742 is supplied to nozzle 750 and an airborne stream of high index polymer particles 745 is supplied to nozzle 760. Mixing of the high index and low index polymers occurs on or near the substrate 770 upon exiting the airjet nozzles 750, 760, thereby depositing polymer droplets on the substrate 770 in a manner similar to that depicted in FIG. 1.
In another embodiment, the methods described herein may be used to improve the resolution of viewing instruments such as telescopes, microscopes, cameras, binoculars, and ophthalmic diagnostic instruments such as confocal scanning ophthalmoscopes, as well as other instruments that contain precision optical elements such as refractive elements (e.g., lenses, prisms), reflective elements (e.g., mirrors and beam splitters), and/or diffractive elements (e.g., gratings, diffractive lenses, lens arrays, and binary optics). The methods described herein may also be used to produce lenses, prisms, reflective and diffractive elements of any dimensions. Preferably, the optical element is a lens selected from the group consisting of a lens with positive focusing power, a lens with negative focusing power, and a lens with cylindrical focusing power. In many cases the cost of manufacturing highly precise optical elements adds significantly to the cost of the resulting instrument. This cost may be reduced by providing optical elements that are initially less precise (and therefore less costly), and applying the relatively low cost methods described herein to improve their precision.
Optical elements may be used to refract electromagnetic radiation over a broad spectral range from radio waves to X-rays, including visible and non-visible wavelengths. Preferred optical elements refract electromagnetic radiation selected from the group consisting of microwave, millimeter wave, infrared, visible, ultraviolet, and X-ray. In preferred embodiments, optical elements are employed in microwave and millimeter wave systems. For example, microwave and millimeter wave antennas are often manufactured with significant aberrations that can be corrected by an optical element as described herein.
The methods and systems described herein may be combined in various ways to provide a system for making an optical element. A preferred system comprises a substrate; a spray unit charged with at least a first polymer composition and a second polymer composition, the spray unit being capable of projecting the first composition and the second composition onto a plurality of pre-selected locations on the substrate, in a plurality of pre-selected ratios of the first polymer composition to the second polymer composition; and a control unit operatively connected to the spray unit, the control unit controlling the projecting of the first polymer composition and the second polymer composition onto the pre-selected locations on the substrate, in the plurality of pre-selected ratios of the first polymer composition to the second polymer composition. Preferred polymer compositions, substrates and spray units for use in the system are described above. Preferably, the control unit comprises a computer.
Preferably, the projecting of the first polymer composition and the second polymer composition onto the pre-selected locations is controlled according to a pre-selected refractive index profile. For example, in a preferred embodiment, a measurement of the low and/or high order wave front aberrations in the eye of a human subject is obtained and used to generate a refractive index profile that corrects the aberrations. Commercially available instrumentation, e.g., the COAS™ system from WaveFront Sciences, Inc., Albuquerque, N. Mex., may be used to measure the low and/or high order wave front aberrations as shown in FIG. 7E. Aberrations may also be measured as described in U.S. patent application Ser. No. 10/014,037, filed Dec. 10, 2001, and U.S. patent application Ser. No. 10/076,218, filed Feb. 13, 2002, both of which are hereby incorporated by reference in their entireties, and particularly for the purpose of describing methods of measuring the eye and other optical systems. A refractive index profile that corrects the aberrations may then be generated as shown in FIG. 7F, in a manner known to those skilled in the art. The refractive index profile may then be input into a computerized controller operatively connected to a PPDS system as described herein and configured to produce a lens that corrects the wave front aberrations when placed in front of the eye. The measurement of the eye, generation of the refractive index profile, manufacture of the lens, and fitting of the lens to the patient may be carried out in a single location or at two or more locations remote from one another. For example, the eye may be measured by a local optometrist, who then transmits the resulting aberration information (or the corresponding refractive index profile) to a manufacturing site where the lens is produced. After production, the finished lens may then be sent to the optometrist for fitting to the patient. The manufacturer may use a lens blank as a substrate. The lens blank may itself be a lens that corrects at least a portion of the low order distortion, or may be a plano blank. The methods described herein may be used to produce lenses that correct all or part of the aberrations, including low order aberrations, high order aberrations, and/or any combination thereof. For example, in a preferred embodiment, the finished lens is a progressive addition lens (PAL).

Example 1

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (high index): 23.0 g of reactive Bisphenol A glycerolate (1 glycerol/phenol) diacrylate (BPGDA, n_D=1.557), 46.0 g of ethanol, 0.23 g of photoinitiator (Irgacure 184).
Part II (low index): 25.0 g of reactive 2-hydroxy ethyl methacrylate (HEMA, n_D=1.453), 25.0 g of ethanol, 0.25 g of photoinitiator (Irgacure 184).

Examples 2-7

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 1 as shown in Table 1. Table 1 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE1

	Composition

No.	Part II (%)	Part I (%)	n_D(uncured)	n_D(cured)

2	0	100	1.417	1.558
3	20	80	1.413	1.535
4	40	60	1.411	1.516
5	60	40	1.407	1.504
6	80	20	1.405	1.483
7	100	0	1.404	1.474

Example 8

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (low index): 50.0 g of reactive tri(propylene glycol) diacrylate (TPGDA, n_D=1.450), 50.0 g of ethanol, 0.51 g of photoinitiator, Irgacure 184, and 0.52 g of thermal initiator, azoisobutyronitrile (AIBN).
Part II (high index): 162.8 g of reactive Bisphenol A glycerolate (1 glycerol/phenol) diacrylate (BPGDA, n_D=1.557), 162.8 g of ethanol, 1.63 g of photoinitiator, Irgacure 184, and 1.63 g of thermal initiator, azoisobutyronitrile (AIBN).

Examples 9-14

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 8 as shown in Table 2. Table 2 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by thermal/UV curing each of the polymerizable compositions.

	TABLE 2

	Composition

No.	Part I (%)	Part II (%)	n_D(uncured)	n_D(cured)

9	0	100	1.4497	1.5595
10	20	80	1.4365	1.5431
11	40	60	1.4286	1.5302
12	60	40	1.4214	1.5203
13	80	20	1.4120	1.4725
14	100	0	1.4045	1.4560

Example 15

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (high index): An ene and a thiol of the following structures, 1% Irgacure 184 and 1% Irgacure 819:
Part II (low index): An ene and a thiol of the following structures, 1% Irgacure 184 and 1% Irgacure 819:

Examples 16-21

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 15 as shown in Table 3. Table 3 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE 3

	Composition

No.	Part I (%)	Part II (%)	n_D(uncured)	n_D(cured)

16	100	0	1.6150	1.6405
17	80	20	1.5882	1.6152
18	60	40	1.5618	1.5889
19	40	60	1.5370	1.5652
20	20	80	1.5105	1.5403
21	0	100	1.4895	1.5205

Example 22

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (high index): Styrene, divinylbenzene, thiobisbenzenethiol, 1% Irgacure 184 and 1% Irgacure 819.
Part II (low index): An ene and a thiol of the following structures, 1% Irgacure 184 and 1% Irgacure 819:

Examples 23-28

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 22 as shown in Table 4. Table 4 also shows the refractive indices (n_D) of each polymerizable composition and the refractive index of the one of the polymers obtained by UV-curing a polymerizable composition.

	TABLE 4

	Composition

No.	Part I (%)	Part II (%)	n_D(uncured)	n_D(cured)

23	100	0	1.6733	HAZY
24	80	20	1.6396	HAZY
25	60	40	1.6030	HAZY
26	40	60	1.5692	HAZY
27	20	80	1.5332	HAZY
28	0	100	1.4850	1.5125

Example 29

Examples 30-35

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 29 as shown in Table 5. Table 5 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE 5

	Composition

No.	Part I (%)	Part II (%)	n_D(uncured)	n_D(cured)

30	100	0	1.5608	1.5927
31	80	20	1.5421	1.5772
32	60	40	1.5291	1.5637
33	40	60	1.5123	1.5474
34	20	80	1.4980	1.5319
35	0	100	1.4852	1.5170

Example 36

Examples 37-42

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 36 as shown in Table 6. Table 6 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE 6

	Composition

No.	Part I (%)	Part II (%)	n_D(uncured)	n_D(cured)

37	100	0	1.5742	1.6124
38	80	20	1.5542	1.5962
39	60	40	1.5371	1.5763
40	40	60	1.5182	1.5547
41	20	80	1.5009	1.5341
42	0	100	1.4852	1.5170

Example 43

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (high index): Two enes and a thiol of the following structures, and 1% Irgacure 184:
Part II (low index): An ene and a thiol of the following structures, 1% Irgacure 184 and 1% Irgacure 819:

Examples 44-49

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 43 as shown in Table 7. Table 7 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE 7

	Composition

No.	Part II (%)	Part I (%)	n_D(uncured)	n_D(cured)

44	100	0	1.4802	1.5121
45	80	20	1.4990	1.5300
46	60	40	1.5120	1.5423
47	40	60	1.5306	1.5654
48	20	80	1.5502	1.5847
49	0	100	1.5674	1.5905

Example 50

A kit having Parts I and II was made by intermixing the following ingredients:
Part I (high index): An ene (18 g) and a thiol (10.98 g) of the following structures, Brij 52 (surfactant, 0.02 g), Brij 58 (surfactant, 0.02 g), Irgacure 184 (0.161 g) and Irgacure 819 (0.119 g):
Part II (low index): An ene (50 g) and a thiol (32.66 g) of the following structures, Irgacure 184 (0.27 g):

Examples 51-56

A series of polymerizable compositions were prepared by intermixing the relative amounts (weight basis) of Parts I and II of the kit of Example 50 as shown in Table 8. Table 8 also shows the refractive indices (n_D) of each polymerizable composition and the corresponding refractive indices of the polymers obtained by UV-curing each of the polymerizable compositions.

	TABLE 8

	Composition

No.	Part II (%)	Part I (%)	n_D(uncured)	n_D(cured)

51	100	0	1.4820	1.5104
52	80	20	1.5094	1.5380
53	60	40	1.5327	1.5648
54	40	60	1.5571	1.5906
55	20	80	1.5786	1.6150
56	0	100	1.6004	1.6405

It will be appreciated by those skilled in the art that various omissions, additions and modifications may be made to the processes described above without departing from the scope of the invention, and all such modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.

Claims

1. A system for making an optical element, comprising:

a substrate;

a spray unit charged with at least a first polymer composition and a second polymer composition, the spray unit being capable of projecting the first composition and the second composition onto a plurality of pre-selected locations on the substrate, in a plurality of pre-selected ratios of the first polymer composition to the second polymer composition; and

a control unit operatively connected to the spray unit, the control unit controlling the projecting of the first polymer composition and the second polymer composition onto the pre-selected locations on the substrate, in the plurality of pre-selected ratios of the first polymer composition to the second polymer composition.

2. The system of claim 1 in which the spray unit comprises a plurality of spray heads.

3. The system of claim 1 in which the first polymer composition comprises a type of polymer that is different in an optical property from the second polymer composition.

4. The system of claim 1 in which at least one of the first polymer composition and the second polymer composition comprises nanoparticles having an index of refraction of at least about 1.6.

5. The system of claim 4 in which the first polymer composition comprises a polymer that is the same type as the second polymer composition.

6. The system of claim 1 in which at least one of the first polymer composition and the second polymer composition comprises a solvent.

7. The system of claim 1 in which the substrate is substantially transparent.

8. The system of claim 1 in which the control unit comprises a computer.

9. The system of claim 8 in which the controlling is conducted according to a pre-selected refractive index profile.

10. The system of claim 9 in which the substrate is a lens blank selected from the group consisting of a plano blank, an optical blank with positive focusing power, an optical blank with negative focusing power, an optical blank with focusing power and cylindrical power, and an optical blank with progressive addition lens power.

11. The system of claim 1 in which the spray unit comprises an airjet.

12. The system of claim 2 in which each of the spray heads comprises an airjet.

13. A method for making an optical element, comprising:

(a) projecting a first polymer composition and a second polymer composition via an airjet onto a substrate to form a first polymer pixel, the first polymer pixel comprising the first polymer composition and the second polymer composition in a first ratio;

(b) projecting the first polymer composition and the second polymer composition via the airjet onto the substrate to form a second polymer pixel, the second polymer pixel adjoining the first polymer pixel, the second polymer pixel comprising the first polymer composition and the second polymer composition in a second ratio that is different from the first ratio; and

(c) repeating steps (a)-(b) to thereby form a continuous film comprising a plurality of adjoining polymer pixels.

14. The method of claim 13 in which the substrate is a lens blank

15. The method of claim 14 in which the continuous film has a refractive index profile selected from the group consisting of a radially non-monotonic profile and an angularly non-monotonic profile.

16. The method of claim 14 in which the lens blank is selected from the group consisting of a piano lens, a lens with positive focusing power, a lens with negative focusing power, and a lens with cylindrical power.

17. The method of claim 13 in which the optical element is a lens.

18. The method of claim 17 in which the lens is a progressive addition lens.

19. A system for making an optical element, comprising

means for projecting a first polymer composition and a second polymer composition via an airjet onto a substrate to form a first polymer pixel, the first polymer pixel comprising the first polymer composition and the second polymer composition in a first ratio;

means for projecting the first polymer composition and the second polymer composition via the airjet onto the substrate to form a second polymer pixel, the second polymer pixel adjoining the first polymer pixel, the second polymer pixel comprising the first polymer composition and the second polymer composition in a second ratio that is different from the first ratio; and

means for repeating the projecting to form the first polymer pixel and the projecting to form the second polymer pixel, to thereby form a continuous film comprising a plurality of adjoining polymer pixels.

20. The method of claim 19 in which the continuous film has a refractive index profile selected from the group consisting of a radially non-monotonic profile and an angularly non-monotonic profile.

21. The method of claim 20 in which the optical element is a lens.

22. A method for making an optical element, comprising:

(a) forming a first polymer pixel on a substrate, the first polymer pixel comprising a first polymer composition and a second polymer composition in a first ratio;

(b) forming a second polymer pixel adjoining the first polymer pixel, the second polymer pixel comprising the first polymer composition and the second polymer composition in a ratio that is different from the first ratio;

(c) repeating steps (a)-(b) to thereby form a continuous film comprising a plurality of adjoining polymer pixels; and

(d) placing a third polymer composition onto the continuous film.

23. The method of claim 22 in which the third polymer composition forms a coating over the continuous film.

24. The method of claim 22 further comprising placing a cover over the continuous film to thereby sandwich the third polymer composition between the substrate and the cover.

25. The method of claim 24 in which the third polymer composition is placed onto the continuous film by first placing the third polymer composition onto the cover, then placing the cover over the continuous film.

26. The method of claim 24 in which the third polymer composition has a refractive index that is about the same as that of the cover.

27. The method of claim 22 in which the third polymer composition is a polymerizable composition.

28. The method of claim 27 further comprising polymerizing the polymerizable composition.

29. The method of claim 28 in which the polymerizing is conducted by exposing the polymerizable composition to ultraviolet radiation.