Fabrication of polydimethylsiloxane optical material

Abstract

A lithography-free, mold-free method of fabricating high quality optical material by curing polydimethylsiloxane (PDMS) droplets in or on pre-heated substrates allows lenses with different focal lengths to be made by varying the volume and surface temperature, as well as the substrate.

Claims

1. A method for fabricating an optical lens having a concave shape, comprising: heating a substrate to a pre-selected temperature to produce a heated substrate; depositing a volume of polydimethylsiloxane (PDMS) in liquid form onto a surface of the heated liquid substrate; injecting a volume of injection liquid into the volume of polydimethylsiloxane (PDMS); and allowing the volume of polydimethylsiloxane (PDMS) to cure to solid form around the injection liquid to create an optical lens having a concave shape, a diameter and a focal length, wherein the volume of polydimethylsiloxane (PDMS), the volume of liquid, and the pre-selected temperature are selected to optimize the diameter and the focal length of the optical lens.

2. The method of claim 1, wherein the volume of polydimethylsiloxane (PDMS) is between 0.1 μL and 10 mL.

3. The method of claim 1, wherein the pre-selected temperature is between 60° C. and 300° C.

4. The method of claim 1, wherein the injection liquid is water.

5. The method of claim 1, wherein the volume of polydimethylsiloxane (PDMS) in liquid form further comprises particles incorporated into the PDMS.

6. The method of claim 1, wherein the particles are dyes, nanoparticles, quantum dots, infrared transparent materials, or mixtures thereof.

7. An optical lens having a concave shape prepared by the method of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows (a) an image of droplets of polydimethylsiloxane (PDMS) deposited on a coverslip with a syringe and (b) a representation of how changing the temperature of the pre-heated surface modifies the geometry of a cured PDMS droplet.

(2) FIG. 2 shows an image of optical material formed to have an extended cylindrical lens shape in accordance with preferred embodiments described herein.

(3) FIG. 3 shows an image of optical material having an irregular or free-form extended cylindrical lens shape in accordance with preferred embodiments described herein.

(4) FIG. 4 shows an image of an optical lens having a generally spherical ball-shape or rounded shape in accordance with preferred embodiments described herein.

(5) FIG. 5 shows a diagram of an exemplary arrangement in which PDMS is injected into a fluid substrate onto a heated surface.

(6) FIG. 6 shows an image of convex lenses of increased diameter in accordance with preferred embodiments described herein.

(7) FIG. 7 shows images of 50 μL PDMS droplets dropped on a surface at temperatures of (a) 60° C., (b) 80° C., (c) 100° C., (d) 120° C., (e) 140° C., (f) 160° C., (g) 180° C., (h), 200° C., demonstrating the effect of speed-curing of PDMS to form lenses.

(8) FIG. 8 shows (a) the setup for imaging an LCD with a smartphone camera with a PDMS lens positioned in between to demonstrate changes in lens magnification for PDMS lenses dropped on a surface at varying temperatures and the resulting magnification with (b) no lens and at temperatures of (c) 60° C., (d) 80° C., (e) 100° C., (f) 120° C., (g) 140° C., (h) 160° C., (i) 180° C., and (j) 200° C.

(9) FIG. 9 shows images of uncured PDMS dropped onto a surface of 200° C. with a volume of (a) 50, (b) 75, (c) 100, (d) 125, (e) 150, (f) 175, and (g) 200 μL.

(10) FIG. 10 shows change in focal length for PDMS lenses in response to variations in (a) surface temperature, and (b) droplet volume.

(11) FIG. 11 shows (a) an image of a PDMS lens directly and non-permanently bonded onto the lens element of a smartphone camera, (b) an image of a fingerprint with inset showing magnified image with and without lens, (c) an image of a spider with inset showing magnified portion of trichobotria, and (d) an image of a PenTile Matrix OLED screen with insets showing actual structure design, and the same structure taken without the lens.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(12) The present disclosure relates to a mold-free method of manufacturing optical material by curing polydimethylsiloxane (PDMS) in or on a heated substrate. This method allows optical material with different sizes, shapes, and focal lengths to be made by varying the PDMS volume, the substrate composition and temperature, the distance or positioning between the PDMS and the surface, and other factors. In an initial step, a volume of polydimethylsiloxane (PDMS) in liquid droplet form is ejected from a deposition mechanism such as a nozzle onto a substrate having a pre-selected temperature or into a fluid (gaseous or liquid) substrate having a pre-selected temperature. In a subsequent step, the PDMS is allowed to cure to solid form. The cured lens material may itself form a lens having a diameter and a focal length, wherein the pre-selected volume and the pre-selected temperature are selected to optimize the diameter and the focal length of the lens. In alternate embodiments, the cured lens material may have a cross-section that can be utilized as a lens, or it may form an optical fiber.

(13) In certain embodiments, the preferred PDMS volume is between 0.1 μL and 10 mL. Preferred surface temperature is between 60° C. and 300° C., preferably about 200° C. The diameter of the resulting lens is preferably 2 cm or less in some embodiments and can be greater than 2 cm in other embodiments. The focal length of the resulting lens is between 0.5 mm and 10 cm, and preferably about 6 mm. An imaging resolution of 10 μm, and an optical magnification of ×12 has been demonstrated. The method can also be modified for parallel fabrication that may allow higher throughput. The material cost of the PDMS was calculated to be <$0.01 USD for a 50 μL lens, and can be conveniently attached to a mobile camera or any vision-enhancing lenses via the strong but non-permanent adhesion between PDMS and glass or plastic. The cured PDMS lenses can effectively act in certain embodiments as a supplemental lens that improves the magnification and performance of other lenses. Preferred embodiments include lenses for attachment to the mobile camera modules of any smartphones, tablets, smartwatches, or laptops, as well as lenses for attachment to any wearable products such as eyeglasses or enhanced “smart” glasses. For eyeglasses and wearable products, lenses that are larger work better. When the lenses are attached onto eye spectacles, they can provide the viewer a magnified view of a portion on the spectacle when the object is held at the focal length of the lens, 0.5 mm to 10 cm. No external accessories or attachments are required to obtain the increased magnification for any of the preferred applications, other than the lens itself.

(14) Certain preferred embodiments relate to a method for manufacturing cylindrical lenses using the same general methods described herein. In this embodiment, the volume of dispensed PDMS is continuous and not limited. In addition, one axis of the heated surface is moved relative to the ejection point or the nozzle, for example, the x-axis. The heat-assisted in-situ curing causes the liquid PDMS deposited on surface to cure similarly as described above. However, as the PDMS dispensing is continuous, a long cylindrical shape is formed in the cured lens material. The cross-section of the cured lens material has a controllable lens shape, as shown in FIG. 2. In this embodiment, the heated smooth surface may be moved in a straight line along a single axis relative to the ejection point of the PDMS, and the lens material is formed to have an extended cylindrical lens shape.

(15) Certain additional preferred embodiments relate to a method for manufacturing free-form lenses that do not have a regular convex or cylindrical shape. In this embodiment, similar to the method of manufacturing cylindrical lenses, the volume of dispensed PDMS is continuous and not limited. In this embodiment, the heated surface is moved in any direction. The movement of surface motion relative to the ejection point is not limited to a single axis and direction. The motion can occur in both axes and in different directions to create a printed pattern whereby the cross-section of the material consists of a controllable lens shape, as shown in FIG. 3. In this embodiment, the heated smooth surface is moved in an irregular fashion along more than one axis relative to the ejection point, and the lens material is formed to have an irregular extended cylindrical lens shape. For example, if the surface is moved in an x-y direction, a perpendicular cross-section will have the same perpendicular cross-section as a droplet lens.

(16) In further preferred embodiments, the liquid PDMS is ejected into or onto a heated fluid substrate, which may be a heated liquid substrate or a heated gaseous substrate.

(17) Additional preferred embodiments relate to a method for manufacturing ball shaped lenses. In this embodiment, PDMS is deposited into a heated liquid substrate such as water so that it is submerged. In this embodiment, any water-based (as opposed to oil-based) liquid can be used as the heated liquid substrate. The ejection point or nozzle for ejecting the PDMS can be submerged inside the liquid and near the bottom of the liquid container. In this embodiment, the liquid must be heated without bubbling to enable the PDMS to cure without any bubble defect formation. It is preferable to keep the heated liquid substrate at a temperature below the liquid's nucleation temperature, which would lead to bubbling, so as not to agitate the mixture. Preferably the temperature should be as high as possible, such as about 60° C. Any volume of heated fluid substrate can be used, so long as the volume is large enough to produce the desired lens. The volume of heated fluid substrate may be up to about 10 mL. This method creates spherical or aspherical ball-shaped or rounded lenses similar to that shown in FIG. 4.

(18) Additional preferred embodiments relate to a method for manufacturing convex lenses having increased diameters. In these methods, a PDMS droplet is ejected from an ejection point above a heated liquid substrate and allowed to fall into the liquid substrate, or a PDMS droplet is ejected from an ejection point within a heated liquid substrate and allowed to fall onto a heated surface at the bottom of the liquid. In these embodiments, the same types of liquid substrate can be used as discussed above, namely any suitable water-based liquid heated to a temperature that is as high as possible without reaching the liquid's nucleation temperature. In certain preferred embodiments, the liquid substrate may be in a vessel above a heated surface and a controlled volume of PDMS ejected within the liquid may pass through the liquid substrate over a constant drop height onto the heated surface, as shown in FIG. 5. The resulting curvature of the lens is controlled by the liquid substrate temperature, the volume of the PDMS, the temperature of the surface underneath the liquid substrate, and the additional force of the surface tension of the liquid substrate. In this embodiment, the volume of liquid substrate can be as large as necessary to obtain a significant curvature in the lens, or up to about 2 mL. This method creates convex lenses of increased diameter similar to that shown in FIG. 6. In these embodiments, the lenses may have a diameter of 2 cm or greater.

(19) Additional preferred embodiments relate to a method for manufacturing an optical fiber by PDMS “trail pulling” and instantaneous heating in a gaseous plane. In this embodiment, the PDMS is continuously ejected, and instead of being deposited on a heated substrate, the material instead passes through a heated gaseous plane. Any non-flammable gas can be used, such as air or purified nitrogen. There is no preference on the gas, as it is only providing heating from a heat source that creates the heated gaseous plane. The temperature must be high enough to enable instantaneous PDMS curing (less than about 100 ms curing time). Thus, in preferred embodiment, the gaseous plane should be at a temperature of about 200° C. or higher. The volume of PDMS ejected is continuous. However, the PDMS trail should be as thin as desired to be used in an optical fiber configuration. Accordingly, in preferred embodiments the diameter of the PDMS trail should be no larger than 1 mm. The heated gaseous plane cures the PDMS in a fiber shape and the fiber can be collected beneath the plane directly or by rolling into a reel.

(20) Additional preferred embodiments relate to a method for manufacturing a concave lens in accordance with the general methods described herein. In this method, a portion of PDMS is ejected onto a heated substrate. Subsequently, a liquid such as water is injected into at least one position in the PDMS to adjust the final shape taken by the lens material after curing. Liquid injected that is in contact with the substrate surface within the PDMS will cause the PDMS to take on a concave shape as it cures around the injected liquid. The curvature and optical power of the lens that is formed will depend on the different surface tensions between the PDMS and the liquid and gravity, and will also depend on the volume of the PDMS relative to the volume of injected liquid.

(21) In certain additional embodiments, prior to depositing and curing the PDMS droplet, selected particles, such as dyes or nanoparticles, can be incorporated into the liquid PDMS. The particles could include food coloring, such as Blue #1, Yellow #5, Red #40, and various mixture of two or more of these. All colors of food coloring can be incorporated into PDMS because the other colors are simply a mixture of these colors. These food colorings can either be water- or oil-based. In certain embodiments, the PDMS can be embedded with colored apolar dyes for wavelength filtration, such as Nile Red, Sudan Red, and the like. The PDMS can also be embedded with colored polar dyes for wavelength filtration. In addition, titanium dioxide could be added to the PDMS. This will create a white opaque lens. Other exemplary particles are: Rhodamine 6G, which creates a fluorescent orange/green colored lens; Crystal Violet, which creates a purple colored lens; Methylene Blue, which creates a blue colored lens; Acridine Orange, which creates an orange colored lens; Gold nanoparticles, which create various colors depending on the diameter of the gold nanoparticles; and Iron powder, which creates a grey opaque lens. Additional examples include Cy3, Cy5, Cy7, Cy9, Alexa fluor dyes, silver nanoparticles, CdSe and ZnSe quantum dots, photochromic materials, and infrared transparent materials such as silicon particles, germanium particles, and chalcogenide compounds. All powdered or liquid dyes, as well as colored or opaque nanoparticles, quantum dots or other colored materials, could be added to the liquid PDMS prior to curing. Magnetic nanoparticles can also be embedded in the PDMS.

(22) Generally speaking, in order to incorporate powdered particles into the liquid PDMS, the first step is to dissolve the particles in water, or ethanol, or another solvent that does not interfere with the particles. If the particles are already liquid-based, such as either water or oil-based, this step is not necessary. The particle-liquid mixture is then mixed into uncured liquid PDMS and degassing of the mixture is performed. Then, the same procedure is followed as with un-modified liquid PDMS. The formation of colored lenses facilitates the use of these lenses in not only magnification, but also measuring colorimetric changes in samples of objects. The lenses allow for wavelength selective electromagnetic wave filtering. For example, differently colored lenses can be used to observe the same microscopic samples and obtain relative enhancement or inhibition of different wavelengths.

Example 1. Temperature Characterization

(23) PDMS solution (SYLGARD® 184, Dow Corning) was prepared by mixing manufacture recommended proportions of PDMS base and curing agent by a weight ratio of 10:1. After mixing and vacuum bubble removal, a syringe was used to deposit PDMS on the surface.

(24) To prepare a pre-heated surface, a coverslip was cleaned and placed on top of a hotplate set to 60° C., and an infrared camera was used to verify that the coverslip glass reaches equilibrium temperature. 50 μL of PDMS was dropped on the coverslip from a 2 cm height with the syringe. PDMS cures at room temperature, but exhibits accelerated curing with increasing temperatures. The procedure was repeated with the hotplate temperature set to 80° C., 100° C., 120° C., 140° C., 160° C., 180° C., and 200° C. respectively, with the resulting figures and properties of the droplet shown in FIG. 7. In each case, an infrared camera was employed to verify the coverslip has reached equilibrium temperature.

(25) At 60° C., the PDMS droplet requires >5 minutes to cure, the longer curing time allows the PDMS to spread across the surface to form a very thin, flat lens with negligible magnification. With increasing temperature, the curing time decreases, thus limiting the flow of the droplet and creates a smaller diameter lens. The focal length decreases due to the increase in surface curvature, which increases the magnification of the lens. At a higher temperature of 200° C., the PDMS droplet requires <5 seconds to cure, the droplet cures shortly on contact and exhibits a very high radius of curvature and enhanced magnification. It is significant to note that at this high temperature, no burning or charring was observed.

(26) The optical power of a convex lens is the degree to which it converges light, and can be expressed by the equation P=1/f, where P is the power of the lens, and f is the focal length. FIG. 8 demonstrates the relationship between the optical power of the lens and the curing temperature, the lens is placed on a coverslip glass and positioned between a computer LCD monitor displaying a white screen, and a smartphone camera capturing the image. It is seen that with increasing temperature of curing, the optical power increases as the focal length decreases.

Example 2. Volume Characterization

(27) To investigate the effect on the focal length and magnification on the drop volume, the hotplate was set to a constant temperature of 200° C. and different volumes of PDMS were dropped onto the surface, with all other conditions remaining identical to those described in Example 1 above. Volumes of 50, 75, 100, 125, 150, 175, and 200 μL were used respectively, with the resulting figures and properties shown in FIG. 9.

(28) As the droplet volume increases, the lens diameter increases, however the contact angle only varies within ±4.4%. The center region of the lens is found to exhibit decreasing curvature, and the focal length is found to increase slightly between 50 μL and 100 μL, from 6 mm to 8 mm respectively, and increases significantly between 100 μL and 200 μL, from 12 mm to 60 mm respectively. This can be shown that as the size of the droplet increases, the radius of curvature near the center of the lens no longer increases, and with an increasing volume of the PDMS droplet, the center portion will eventually become flat. This limitation makes it difficult using this method to create practical lenses larger than 2 cm in diameter.

(29) The properties of the lens are determined by its geometric parameters. Since the curing temperature of PDMS determines the speed of curing, and thus the contact angle and diameter of the lens droplet, the focal length of the lens can be accurately tuned in a single-step. As with fluidic lenses, mechanical defects on the curved surface are eliminated with this mold-free process, as the droplet experiences uniform surface forces from all sides during curing. FIG. 10 shows the change in focal length with response to (a) surface temperature, and (b) droplet volume.

Example 3. Numerical Aperture

(30) From the preceding examples, it is shown that the lens created with a 50 μL volume droplet size, cured at 200° C. is most suitable for short-ranged imaging due to its short focal length. This example attempts to characterize the numerical aperture of this particular lens. The focal length of the lens is found to be 6 mm by focusing a white light onto a white plastic board. A 1-watt white LED flashlight source was positioned 1 m away from the lens, and a white plastic board on the other side of the lens was moved slowly towards the lens until a focused image was observed. The maximum usable curvature of the 6.0 mm diameter lens was found by superimposing a curve-fitted ellipse and taking the length where the lens outline is within ±1% of the ellipse, which yields a maximum usable curvature of roughly 3.8 mm. The numerical aperture of a lens is expressed as NA=n sin θ, where n is the index of refraction of the medium in which the lens is working (n.sub.air=1), and θ is the half-angle of the maximum cone of light that can enter or exit the lens. For a focal length of 6 mm, and an effective radius of 1.9 mm, the half-angle is found to be 17.571°, and the numerical aperture is found to be 0.422.

Example 4. Use of Lenses with Smartphones

(31) Add-on accessories to turn a smartphone into a magnifying device are widely available; however, most of these attachments significantly increase the bulk of the device. To demonstrate a practical application, the PDMS lens (50 μL cured at 200° C.) was attached to a Nokia Lumia 520 budget smartphone camera (Microsoft, Redmond, Wash., USA) with a 5-megapixel camera as shown in FIG. 11(a). The adhesive property of PDMS on glass and plastic surfaces allows the PDMS lens to bind non-permanently onto the camera lens without supporting structures, and is not prone to falling off.

(32) Images taken from the smartphone with no further image processing are shown in FIG. 11(b)-(d). FIG. 11(b) shows an image of a finger taken with the camera without PDMS lens, and the inset taken with the PDMS lens attached clearly showing sub-millimeter fingerprint structures including sweat pores. FIG. 11(c) shows an image of a spider taken with the PDMS lens attached, and the inset shows a digitally magnified portion of the image. The thinnest thrichobotria structures on the legs of the spider, measure roughly 15 μm in width. FIG. 11(d) shows an image of an organic light emitting diode (OLED) display with a PenTile matrix pixel geometry on a Nokia Lumia 800 smartphone displaying a white screen. The inset shows the actual geometry of the pixel matrix, the larger pixel measuring 20 μm in width, the smaller pixel and gaps measure 10 μm in width. A minimum discernible resolution of roughly 10 μm was achieved.

(33) The magnification of the lens was found to be 12× by comparing the observed size of an arbitrary structure in a clearly focused image taken with the smartphone, and with a commercial microscope (Olympus IX-70, Olympus Corp) with 200× total magnification. The magnification of the smartphone with PDMS lens can be further enhanced by combining software based digital magnification.

Example 5. Use of Lenses with Eyeglasses

(34) A 300 microliter lens was prepared at 200° C. as described above in Example 1, with a resulting magnification of 3×. The lens was attached to a pair of eye spectacles via the natural adhesion of PDMS to the spectacle lens. The spectacle wearer was able to view items clearly in focus with a 3× magnification when looking through the spectacle with the attached PDMS lens at any object when held at roughly 5 cm away from the spectacle.

Example 6. Focal Length

(35) A 1 microliter lens was prepared at 200° C. as described above in Example 1, with a resulting focal length of 0.5 mm. A 1 mL (1000 μL) volume lens as also prepared at 200° C. as described above in Example 1. In this case, the resulting lens was completely flat in the middle with an infinite focal length. This lens did not distort or change the direction of light and is actually useless as a lens. Although it is possible to construct any range of focal length, up to an infinite focal length, the maximum usable range is approximately 10 cm. 10 cm is the maximum effective usable range for viewing microscopic samples.

Example 7. Color Effects

(36) A red lens and a green lens were prepared according to Example 1 above, except that red and green dyes were incorporated into the liquid PDMS for each lens prior to curing. The xylem/phloem of a plant histological cross section was observed with both lenses. With the red lens, the green objects (xylem) appeared enhanced, while the red objects (phloem) appeared suppressed. With the green lens, the opposite occurred. Thus these lenses are useful as an image filter for enhancing/suppressing desired wavelengths of light for easier identification of features and measuring of colorimetric changes.