NOVEL TRANSPARENCY AND COLOR TUNABLE ELECTRO-OPTICAL DEVICE USING COLLOIDAL CORE/SHELL NANOPARTICLES
20190004390 ยท 2019-01-03
Inventors
Cpc classification
G02F1/172
PHYSICS
C09K11/025
CHEMISTRY; METALLURGY
International classification
G02F1/17
PHYSICS
C09K11/02
CHEMISTRY; METALLURGY
Abstract
According to one embodiment, a product is a mixture including a solvent and generally spherical colloidal nanoparticles, the colloidal nanoparticles each having a core and a shell surrounding the core, and an electrode. In addition, the mixture is characterized as having a transparency to light in a predetermined wavelength range, where the transparency increases as a voltage of the electrode increases.
Claims
1. A product, comprising: a mixture comprising a solvent and generally spherical colloidal nanoparticles, the colloidal nanoparticles each having a core and a shell surrounding the core; and an electrode, wherein the mixture is characterized as having a transparency to light in a predetermined wavelength range, wherein the transparency increases as a voltage of the electrode increases.
2. The product of claim 1, wherein the colloidal nanoparticles migrate toward one side of the mixture upon application of the voltage to the electrode.
3. The product of claim 1, wherein at least one electrode is transparent.
4. The product of claim 1, wherein at least some of the cores are light emitting.
5. The product of claim 1, wherein at least some of the cores include a colorant applied to a base material of the cores.
6. The product of claim 1, wherein a color hue of the mixture changes as the transparency changes.
7. The product of claim 1, wherein the mixture is characterized as having a transparency of at least 90% light transmission upon application of a predetermined voltage to the electrode.
8. The product of claim 1, wherein the predetermined wavelength range is only a portion of the wavelengths in the ultraviolet to infrared range, wherein the transparency of the mixture does not significantly change for a second wavelength range in the ultraviolet to infrared range as the voltage of the electrode increases.
9. The product of claim 1, wherein the shell is silicon-based.
10. The product of claim 1, wherein the shell has a positive charge.
11. The product of claim 1, wherein the shell has a negative charge.
12. The product of claim 1, wherein the solvent is a polar solvent, wherein a boiling point of the solvent is greater than about 150 degrees Celsius.
13. The product of claim 1, further comprising at least one spacer forming a chamber having sides defining an interior, wherein the mixture is in the interior of the chamber.
14. The product of claim 1, the mixture having a specific color, the mixture being characterized as changing color across the visible spectrum in direct correlation to a concentration of the nanoparticles wherein a concentration of the nanoparticles is selected to provide the specific color of the mixture.
15. The product of claim 14, wherein changing the concentration of the nanoparticles changes the color of the mixture across a visible spectrum.
16. A product, comprising: a plurality of generally spherical colloidal nanoparticles each having a core and a shell surrounding the core.
17. The product of claim 16, wherein the nanoparticles have an average diameter in a range of about 50 to about 200 nanometers.
18. The product of claim 16, wherein at least some of the cores are light emitting.
19. The product of claim 16, wherein the core is light absorbing in selected regions of the electromagnetic spectrum.
20. The product of claim 16, wherein the core is light reflecting in selected regions of the electromagnetic spectrum.
21. The product of claim 16, wherein at least some of the cores include a colorant applied to a base material of the cores.
22. The product of claim 16, wherein the core is silicon-based.
23. The product of claim 16, wherein the shell has a positive charge.
24. The product of claim 16, wherein the shell has a negative charge.
25. A method, comprising, applying a voltage to an electrode of a cell containing a mixture comprising a solvent and generally spherical colloidal nanoparticles for increasing a transparency of the mixture, the colloidal nanoparticles each having a core and a shell surrounding the core.
26. A method of claim 25, wherein the colloidal nanoparticles migrate toward one side of the mixture upon application of the voltage to the electrode.
27. (canceled)
28. (canceled)
29. The product of claim 1, wherein a concentration of the generally spherical colloidal nanoparticles in the mixture is in a range of about 5 to about 30 weight % in the mixture.
30. The product of claim 2, wherein the mixture is physically characterized as having a greater relative transparency when the colloidal nanoparticles are migrated toward the one side of the mixture upon application of the voltage to the electrode.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0030] The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations.
[0031] Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc.
[0032] It must also be noted that, as used in the specification and the appended claims, the singular forms a, an and the include plural referents unless otherwise specified.
[0033] The following description discloses several preferred embodiments of an electro-optical device using colloidal core/shell nanoparticles and/or related systems and methods.
[0034] In one general embodiment, a product is a mixture including a solvent and generally spherical colloidal nanoparticles, the colloidal nanoparticles each having a core and a shell surrounding the core, and an electrode. In addition, the mixture is characterized as having a transparency to light in a predetermined wavelength range, where the transparency increases as a voltage of the electrode increases.
[0035] In another general embodiment, a product includes a plurality of generally spherical colloidal nanoparticles each having a core and a shell surrounding the core.
[0036] In yet another general embodiment, a method includes applying a voltage to an electrode of a cell containing a mixture comprising a solvent and generally spherical colloidal nanoparticles, each having a core and a shell surrounding the core, for increasing a transparency of the mixture.
[0037] A list of acronyms used in the description is provided below. [0038] EPD Electrophoretic deposition [0039] EtOH Ethanol [0040] Fe.sub.2O.sub.3 Ferric oxide [0041] FWHM Full width half maximum [0042] ITO Indium tin oxide [0043] IR Infrared [0044] PVP Polyvinylpyrrolidone [0045] SEM Scanning Electron Microscopy [0046] SiO.sub.2 Silicon dioxide, silica [0047] SPD Suspended particle device [0048] TEM Transmission Electron Microscopy [0049] TEOS Tetraethyl orthosilicate [0050] USAXS Ultrasmall-angle X-ray scattering [0051] UV Ultraviolet [0052] ZnS Zinc sulfide
[0053] According to Mie scattering theory and Beer-Lambert law, the light scattering by particles and resulting transmittance is significantly affected by the particle size, concentration of particles, and the thickness of a device. Therefore, the ability of particles to absorb and transmit different kinds of light may depend on interparticle distance. Various embodiments described herein include an electric responsive mixture of colloidal core/shell nanoparticles dispersed in a liquid suspension medium and the properties associated with this mixture in the presence of an applied electric field.
[0054] In one embodiment, the ordered structure of particle arrangement relative to scattering light may affect the transparency of the mixture containing the particles. In some approaches, the ordered structure of the particle arrangement may resemble crystallinity of the ordered structure thereby resulting in transparency. In the absence of applied electric field, particles in suspension may have not only interparticle distances that are far apart, possibly farther than a visible wavelength, but also less ordered particle arrangement and therefore scatter more light. By applying an electric field, responsive particles move toward an electrode, become closer together and the interparticle distance becomes shorter relative to the amount of potential applied to the electrode. The particle arrangement may become more ordered, approaching crystallinity. Counterintuitive to conventional EPD methods in which an electric field results in formation of visible structure at the deposition electrode, various embodiments described herein demonstrate that in response to an applied electric field, nanoparticles organize in a particle arrangement at the deposition electrode and become transparent.
[0055] Furthermore, various embodiments take advantage of unique combinations of characteristics such as optimal particle size, size distribution, the spacing between the electrodes, and particle concentration. Each of these characteristics may play important roles in achieving efficient structural color as well as transparency tunable SPD. Thus, various embodiments described herein demonstrate tunable transparency in response to an electrical field by adjusting the particle arrangement (such as the crystallinity of structure) in fabricated SPD using inorganic colloidal nanoparticle with optimal size, optimal size distribution and optimal particle concentration. According to Bragg-Snell Law in Photonic Crystals, the optimal particle size to reflect or transmit the light in the visible range is highly affected by the refractive index of embodiments. Typically, the optimal particle size may be in the range from tens of nanometers to up to 300 nm. Furthermore, the crystallinity of structure may be significantly affected by particle size distribution and particle concentration. For example, particle concentration of 5-30 wt % in solution with 5-10% of size distribution can be optimal to demonstrate tunable transparency. One skilled in the art, once armed with the teachings presented herein, would be able to determine optimal parameters for a given application of this technology without the need for undue experimentation.
[0056]
[0057] In one embodiment, a product may include a plurality of generally spherical colloidal nanoparticles 102 each having a core 110 and a shell 112 surrounding the core 110, as illustrated in a cross-sectional view in
[0058] In some embodiments, the core particles may be light absorbing or reflecting in selected regions of the electromagnetic spectrum. Core particles with band gap (E.sub.g) range from 1.8 eV to 3.1 eV can absorb and reflect the visible light. These materials can be CdS, CdSe, Fe.sub.2O.sub.3, WO.sub.3, and GaP. When the core particles absorb in one region of the light, they appear with complimentary color by the light reflection. For example, violet light absorbing core particles such as CdS can reflect the yellow light. When core particles with larger band gap (E.sub.g>3.2 eV) such as ZnO, ZnS, TiO.sub.2, and SiO.sub.2, all the light in the visible range can be not absorbed but reflected. Furthermore, core particles composed of Cr.sup.3+, Cu.sup.2+, and Co.sup.2+ compounds such as Cr.sub.2O.sub.3 (green), CuO (green) and Al.sub.2CoO.sub.4 (blue) can also reflect the light in the visible range by inter-atomic excitation.
[0059] In an exemplary embodiment, the core of the nanoparticle may include a pigmentary material, for example, a highly faceted single crystal -Fe.sub.2O.sub.3, that may enhance the color contrast with pigment-induced absorption.
[0060] In one embodiment, at least some of the cores 110 of the colloidal nanoparticles 102 may be light emitting, e.g., may have a known light emitting material therein. For example, but not limited to, at least some of the cores 110 of the colloidal nanoparticles 102 may exhibit photoluminescence. In some approaches, the core of the core/shell colloidal nanoparticle may include rare earth activated phosphor.
[0061] In various embodiments, at least some of the cores 110 may include a colorant, for example, but not limited to, a dye, a pigment, etc., may be applied to a base material of the cores 110. In other approaches, the base material of the core 110 may be selected to provide a color.
[0062] In some embodiments, the shell 112 that surrounds the core 110 of the nanoparticle 102 may be silicon-based. In some approaches, the shell 112 may have a negative charge, and include materials such as silica, titanium, etc. For example, according to Stber method, which is an example of sol-gel process, negatively charged SiO.sub.2 shells can be fabricated by the hydrolysis and condensation process of tetraethyl orthosilicate (TEOS) (i.e. silica precursors) in the presence of water and ammonia. In other approaches, the shell 112 may have a positive charge by the surface modification using silane coupling agents.
[0063] In some embodiments, the shell may improve the suspension properties of the colloidal nanoparticles in the solvent. According to various embodiments, the shell thickness sh.sub.th may affect the interparticle distance that may be defined by the core-to-core distance d.sub.ctc between adjacent nanoparticles. In some approaches, the interparticle distance may be referred to as the intercore distance. In one embodiment, the shell 112 may control the distance d.sub.ctc between the cores of neighboring colloidal nanoparticles, as indicated on
[0064] In an exemplary embodiment, nanoparticles with a shell 112 having a thin shell thickness sh.sub.th may have a shorter interparticle distance d.sub.ctc than nanoparticles 102 with a shell 112 having a thicker shell thickness sh.sub.th. Thus, the shell thickness sh.sub.th of the nanoparticles 102 may define the interparticle distance d.sub.ctc between the nanoparticles 102 of a concentration of nanoparticles 102 in a mixture 106 and, thereby determine the reflectance and structural color of the mixture 106 during assembly of the nanoparticles 102 with an applied electric field V.
[0065] In various embodiments, the shell properties of the colloidal nanoparticles may be tuned for different applications. In some approaches, the shell may have hydrophobic properties. In other approaches, the shell may have hydrophilic properties.
[0066] In an exemplary embodiment, the shell of the nanoparticle may include a SiO.sub.2 coating that may improve the suspension properties and control the intercore distances, as indicated by d.sub.ctc in
[0067] According to an exemplary embodiment, the assembly and tuning of Fe.sub.2O.sub.3/SiO.sub.2 core/shell nanoparticle arrays allow the generation of tunable structural colors with distinct reflected and transmitted color behaviors. The use of Fe.sub.2O.sub.3/SiO.sub.2 core/shell nanoparticles with a moderate polydispersity (for example, 7%, as may be confirmed by synchrotron-based ultrasmall-angle X-ray scattering (USAXS)), along with a variation in the shell thickness and/or particle concentration may provide multiple pathways to tune the color spectrum of the assembly of nanoparticles. In some approaches, the color tunability observed by varying the concentrations may also be emulated by modulating the electric field applied to a diluted suspension of particles inside an electrophoretic deposition (EPD) cell.
[0068] In various embodiments, the nanoparticles 102 may have an average diameter d, as shown in
[0069]
[0070] In one embodiment as shown in
[0071] The solvent 104 in the mixture 106 may be a polar solvent. In various embodiments, the solvent (i.e. suspending medium) may be chosen as to maintain the suspended colloidal nanoparticles in gravitational equilibrium. In some embodiments, the solvent may provide electrochemical stability with a dielectric constant greater than about 30 and may have a boiling point greater than about 150 degrees Celsius. For example, but not limited to, the solvent 104 may include propylene carbonate, dimethylformamide, dimethyl sulfoxide, etc. In some approaches, the suspension of colloidal nanoparticles may be enhanced by a liquid suspending medium includes one or more non-aqueous, electrically resistive liquids with high dielectric constants.
[0072] The product 100, according to one embodiment, also includes an electrode 108. According to one embodiment, as shown in
[0073] In some embodiments, the electrodes 108 may be transparent of at least 90% light transmission (for example, but not limited to, not opaque, translucent, etc).
[0074] In various embodiments, the thickness of the cell that contains the mixture 106 may be defined by the thickness sp.sub.th of the spacers 114 that are positioned between the electrodes 108. The path of light through the electrodes 108 (the electrodes may be transparent) may determine not only the reflected color of the cell by controlling the relative intensity of structural and pigmentary colors of the mixture of colloidal nanoparticles in dielectric solvent but also the light transmissivity. In one embodiment, the reflected color and the light transmissivity may be tuned by the spacer thickness sp.sub.th that defines the cell thickness between the electrodes 108. As an example but not limiting to the embodiments described herein, the reflected colors as well as the light transmittance observed in the absence and presence of applied voltage under same electric field with a spacer thickness sp.sub.th of 500 m spacing may be significantly different from the reflected colors and the light transmittance observed with a spacer thickness sp.sub.th of 25 m spacing under the same conditions of electric field. The difference in reflected colors between the two thicknesses may be due to enhanced relative intensity of pigmentary color and possibly different response of the mixtures in each cell to electric stimuli. Furthermore, the difference in transmissivity between the two thicknesses may be due to higher scattering events in thicker cell thereby reducing the transmission of the incident light.
[0075] According to an exemplary embodiment, the photonic color of a mixture with a 500 m spacing between the electrodes may change from yellow to pink and then to deep red as the applied voltage increases. Some embodiments demonstrate the versatility of the EPD cell device which may be used to generate the full visible color spectrum via changing the spacer thickness, particle concentration, silica shell thickness (sh.sub.th of SiO.sub.2), and applied voltage.
[0076] According to one embodiment, the product 100 may include least one spacer 114 (for example, barrier, gasket, etc) for forming a chamber having sides defining an interior. Moreover, the mixture 106 may be in the interior of the chamber.
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[0079] In some embodiments, the mixture 106 may create a different between transmitted and reflected colors in the cell 120 with applied electric field. In an exemplary embodiment, the behavior of the mixture of colloidal Fe.sub.2O.sub.3/SiO.sub.2 nanoparticles in dielectric solvent may give rise to behavior comparable with the Lycurgus cup effect, in which the transmitted and reflected colors in the cell is attributed to the difference between the pigmentary color (intrinsic color) of Fe.sub.2O.sub.3/SiO.sub.2 and the structural color from Fe.sub.2O.sub.3/SiO.sub.2 nanoparticle arrangement.
[0080] Without wishing to be bound by any theory, the inventors believe the transparency change may be obtained more clearly in a device with mono-dispersed particles with a spherical shape because there is a reduction of the scattering centers such as pores and grain boundaries when these particles are concentrated in the presence of an electrical field. Furthermore, it appears the increased transparency may be attributed to an enhanced crystallinity of nanoparticle arrangement. In the presence of an electric field, the nanoparticle structure may have enhanced crystallinity and periodic arrangement, thereby increasing the transparency as compared with the random or less ordered particle structure in the absence of an electric field. Furthermore, the defects (e.g., scattering centers) such as pores and grain boundary in the structure appear to be reduced by densification of colloidal nanoparticles at a larger electric field.
[0081] In various embodiments, the core/shell colloidal nanoparticles may be suspended in highly dielectric liquid media with optimal concentration for electrical responded color and transparency tunable device. In the presence of an applied electrical field, the colloidal nanoparticles may assemble and generate a transparency in the suspension thereby creating an optical stop and pass band.
[0082] In one embodiment, light-emitting core/shell colloidal nanoparticles have enhanced light-emitting properties as the core/shell colloidal nanoparticles may undergo light transparency structural behavior in a SPD device in the presence of applied electrical field. In some approaches, application of the electric field causes the light-emitting nanoparticles to assemble, and thereby may enhance the light-emitting properties of the nanoparticles (such as the light emitting from the device becomes brighter).
[0083] In some embodiments, the mixture 106 may be characterized as having a transparency that increases as a voltage V of the electrode 108 increases. The transparency to light may occur in a predetermined wavelength range. In some approaches, the predetermined wavelength range may be in the visible region. In other approaches, the predetermined wavelength range may be in the UV range. In yet other approaches, the predetermined wavelength range may be in the infrared (IR) range.
[0084] In some embodiments, the core/shell colloidal nanoparticle may be tuned to a predetermined wavelength region in the presence of applied electric field. In some approaches, the size of the nanoparticle core may be tuned to a predetermined wavelength. In other approaches, the thickness of the shell may be tuned to a predetermined wavelength. In yet other approaches, one or more of the characteristics of the core/shell colloidal nanoparticle may be tuned to a predetermined wavelength.
[0085] In some embodiments, the predetermined wavelength range may be only a portion of the wavelengths in the ultraviolet to infrared range. In some approaches, the transparency of the mixture may not significantly change for a second wavelength range in the ultraviolet to infrared range as the voltage of the electrode increases. The second wavelength range may not overlap the wavelength range for which a bandgap effect is desired. In some approaches, the second wavelength range may be within the predetermined wavelength range. In other approaches, the second wavelength range may be overlapping the predetermined wavelength range. In yet other approaches, the second wavelength range may be outside the predetermined wavelength range.
[0086] In an exemplary approach, there may be a less than 10% change in transparency of the mixture for a second wavelength range in the ultraviolet to infrared range as the voltage of the electrode increases. For example, but not limited to, a smart window may include a mixture of nanoparticles comprised of material that absorbs in the IR region that continually blocks thermal, radioactive heat (blocking incoming IR via absorbance) while changing to transparency as the voltage of the electrode increases (providing clarity of the window via transmittance of visible light). As another example, the smart window may include a mixture of nanoparticles comprised of material that absorbs in the UV region that continually blocks UV radiation (blocking incoming UV via absorbance, e.g. ZnS) while changing to transparency as the voltage of the electrode increases (providing clarity of the window via transmittance of visible light).
[0087] As an example, a smart window may have core/shell colloidal particles that includes energy absorbing material that absorbs in the IR range but allows visible light through, so the smart window has transparency while blocking IR light, and thereby reducing heat typically generated by IR light. In another example of a smart window, core/shell colloidal particles may include material that absorbs UV light (for example, ZnS/SiO.sub.2), thereby allowing sunlight through a window while blocking harmful UV light. Thus, depending on the type of material, optical band gaps ranging from UV, visual to IR may be created.
[0088] In other embodiments, the mixture 106 may be characterized as having a transparency of at least 90% light transmission upon application of a predetermined voltage V to the electrode 108. In some approaches, the application of a predetermined voltage may increase the interparticle distance between the core/shell nanoparticles of the mixture. In other approaches, the application of a predetermined voltage may decrease the interparticle distance between the core/shell nanoparticles of the mixture.
[0089] In some embodiments, a color hue of the mixture 106 may change as the transparency changes as a voltage V of the electrode 108 changes.
[0090] In various embodiments, the colloidal nanoparticles 102 may migrate toward one side of the mixture 106 upon application of the voltage V to the electrode 108. In one embodiment of product 100 as shown in
[0091] In various embodiments, turning the voltage off and thereby removing the applied electric field may reverse the change in transparency of the mixture 106 in the cell 120 that occurs in the presence of an applied electric field. In some approaches, turning the voltage off and thereby removing the applied electric field may reverse the color change of the mixture 106 in the cell 120 that occurs in the presence of an applied electric field. The color change and/or transparency change may be fully reversible. In some embodiments, the response time corresponding to applied voltage may be almost instantaneous.
[0092]
[0093] According to one embodiment as shown in
[0094] In one embodiment of the method 200, the colloidal nanoparticles may migrate toward one side of the mixture upon application of the voltage to the electrode. In one approach, at least one electrode is transparent.
[0095] In one embodiment of the method 200, the mixture may be characterized as having a transparency of at least 90% light transmission upon application of a predetermined voltage to the electrode.
[0096] In one embodiment, the method 200 includes the mixture having a specific color, where a concentration of the nanoparticles is selected to provide the specific color of the mixture. The mixture, in various embodiments, may be characterized as changing color across the visible spectrum in direct correlation to a concentration of the nanoparticles, rather than simply changing to a shade of the same color. Thus, the particular color of the mixture, e.g., in the absence of a voltage, can be selected by selecting a concentration of nanoparticles that provides the desired color.
Experimental Methods
[0097] Synthesis of -Fe.sub.2O.sub.3 Nanocubes and Nanoparticle Clusters and ZnS Nanoparticle Clusters:
[0098] -Fe.sub.2O.sub.3 nanocubes and nanoparticle clusters were prepared adopting a microwave assisted hydrothermal approach. Briefly, 1.8 g of PVP (Sigma-Aldrich, Mw=55 000) was added to 40 mL of N,N-dimethylformamide (Sigma-Aldrich, 99.8%) and stirred for 30 min to completely dissolve the reagents. Thereafter, 0.1 mmol of Fe(NO.sub.3).sub.3.9H.sub.2O (Sigma-Aldrich, >99.95%) was added in the solution, vigorously stirred for 15 min. Note that for the nanoparticle cluster synthesis, 0.1 ml nitric acid (Sigma-Aldrich, ACS reagent 70%) was further added in the solution and stirred for 10 min. Thereafter, the solution mixture was transferred into in a microwave oven (SPX-80 from CEM Corp., using single mode and continuous power at 2.45 GHz), and heated to 180 C. for 2 h.
[0099] In terms of ZnS nanoparticle synthesis, 1 g PVP was dissolved in 200 ml deionized water and the solution was heated to 80 C. Subsequently, 0.01 mol thioacetamide (Sigma-Aldrich, ACS reagent >99%) was added, followed by an addition of nitric acid (0.2 mL). Thereafter, 0.2 mol zinc nitrate hexahydrate (J. T. Baker, 99.0%) was added into the solution and stirred for 2 h and then removed to convectively cool to room temperature. As-prepared samples were later isolated from the mother liquor by centrifugation at 10,000 rpm for 20 min and washed with the mixture of water and ethanol (EtOH) (water:vEtOH=1:1) for three times and stored in EtOH for future use.
[0100] Synthesis of -Fe.sub.2O.sub.3/SiO.sub.2 and ZnS/SiO.sub.2 Core/Shell Nanoparticles:
[0101] -Fe.sub.2O.sub.3/SiO.sub.2 and ZnS/SiO.sub.2 core/shell colloids were prepared through a modified Stber method. Typically, 20 mg of -Fe.sub.2O.sub.3 nanocubes or -Fe.sub.2O.sub.3 nanoparticles or ZnS nanoparticle clusters was added to 20 mL EtOH with 1 mL ammonium hydroxide (J. T. Baker, 28%) and 3 mL Mill-Q water and stirred vigorously for 10 min. 0.04 mL TEOS (Sigma-Aldrich, 99.999%) was added to the solution every 20 min for the desired time (e.g., 1-2 h) so the total volume of TEOS was 0.08-0.32 mL and stirred for another 0-22 h at room temperature. The obtained core-shell particles were washed with EtOH through repetitive centrifugation and redispersion. The nanoparticles were finally dispersed in propylene carbonate at greater than 5 wt % of Fe.sub.2O.sub.3/SiO.sub.2 or ZnS/SiO.sub.2, which was the critical concentration for exhibiting reflective structural color.
[0102] Fabrication of an EPD Cell and Patterned TiPt Deposited Electrode: The Fe.sub.2O.sub.3/SiO.sub.2 colloids were then injected between two indium tin oxide (ITO) electrodes (1 in.1 in.) separated by a 25 m spacer of kapton tape to investigate the electrophoretic response of structural color from Fe.sub.2O.sub.3/SiO.sub.2 colloids in propylene carbonate.
[0103] Characterization:
[0104] SEM images were obtained at 3 kV on a JEOL JSM-7401F instrument (JEOL USA, Inc, 11 Dearborn Road, Peabody, Mass. 01960). Specimens for all microscopy experiments were prepared by dispersing the as-prepared product in EtOH, sonicating for 2 min to ensure an adequate dispersion of the nanostructures, and dipping one drop of the solution onto a Si wafer for SEM.
[0105] The zeta potential of the suspended particles was measured with a ZetaSizer Nano ZS90 (Malvern Instruments, Inc, Enigma Business Park, Grovewood Road, Malvern, Worcestershire, US WR14 1XZ).
[0106] The optical properties of Fe.sub.2O.sub.3/SiO.sub.2 colloids in propylene carbonate were measured using a Perkin-Elmer Lambda 950 spectrophotometer (PerkinElmer, 520 South Main Street, Suite 2423, Akron, Ohio 44311, USA) equipped with an integrating sphere in the static state to examine the effect of concentration and silica shell thickness on the structural coloration. An Ocean Optics HR2000+ (Ocean Optics, Inc, 830 Douglas Avenue, Dunedin, Fla. 34698, USA) with a balanced tungsten source (400-900 nm) was used to investigate the effect of applied voltage on the coloration in an EPD cell and angle dependency of the structural color.
Experimental Results
[0107] Fe.sub.2O.sub.3/SiO.sub.2 and ZnS/SiO.sub.2 Core/Shell Nanoparticles
[0108] Scanning electron microscopy (SEM) images of synthesized -Fe.sub.2O.sub.3 and ZnS/SiO.sub.2 core/shell nanoparticles as responsive materials are shown in
[0109]
[0110]
[0111] Tunability of Color of Fe.sub.2O.sub.3/SiO.sub.2 Suspensions
[0112] The as-prepared suspensions of Fe.sub.2O.sub.3/SiO.sub.2 colloids are solvent exchanged to propylene carbonate, upon which they self-assemble and generate structural ordering due to electrostatic repulsion between particles. Propylene carbonate was chosen as a solvent because it exhibits excellent electrochemical stability and low vapor pressure.
[0113] The characteristics of suspensions of nanoparticles with a core diameter of about 40 nm and a shell thickness of about 40 nm are shown in
[0114] As shown in
[0115] The structural photonic color produced by the self-assembled nanoparticle arrays blue-shifts as the particle concentration increases (18 wt %, 21 wt %, 25 wt %, 35 wt %), as shown in
[0116] Structural Ordering and Interparticle Distance of Fe.sub.2O.sub.3/SiO.sub.2Suspensions
[0117] High fidelity examination of the structural ordering and interparticle distances of Fe.sub.2O.sub.3/SiO.sub.2 suspensions with different particle concentrations was performed with USAXS measurements. USAXS provided a measurement of the structural correlation in nanostructured ensembles, which then could be used to understand the interactions of visible light with the nanostructural assembly.
[0118] In order to examine the interparticle interactions in the Fe.sub.2O.sub.3/SiO.sub.2 nanoparticle system with different particle concentration in more detail, the structure factor S(q) was calculated by dividing I(q) with the form factor representing the specific size and shape of the scatters.
[0119]
where s=182.65 nm (q.sub.pk=0.00344 A.sup.1) for 14 wt % (
[0120] It was somewhat surprising that a relatively small difference of interparticle distance between 14 and 21 wt % (30 nm) gave rise to a significant blue-shift of color from green to purple (color not shown, but wavelength curves shown in
[0121] In order to further demonstrate the crystallinity of the structures, the full width half maximum (FWHM) of the widths of the primary USAXS peak of each structure in
was 539.4 nm for 14 wt % and 636.6 nm for 21 wt %, which was consistent with the decreased bandwidth of the optical reflectance spectrum at 21 wt % (FWHM57 nm) as compared with the spectrum at 14 wt % (FWHM82 nm) in suspension (data not shown). For both cases, was only a few times the dominant length scale of spatial correlations (s) (i.e., =2.95 s for 14 wt % and =4.15 s for 21 wt %). As shown in
[0122] Schematic drawings of the nanoparticle arrangement for 14 and 21 wt % Fe.sub.2O.sub.3/SiO.sub.2, based upon the structural information derived from the USAXS, are shown in
[0123] Transparency of the Device Using Fe.sub.2O.sub.3/SiO.sub.2Nanoparticles in Suspension
[0124] As shown in
[0125]
[0126] Light Transmission Spectra of Colloidal Nanoparticle Suspensions with Increased Voltage
[0127]
[0128]
[0129]
[0130] In Use
[0131] The various embodiments described herein present a product that is capable of tuning the transparency in response to electric field for versatile and multifunctional smart windows and display technologies. Moreover, some embodiments describe an ideal particle size and size distribution for the generation of electrical tunable structural color and transparency for smart windows and refractive display, electronic ink (E-ink), E films, and electrophoretic display devices.
[0132] Furthermore, color generation resulting from combination of colloidal particle arrangements may give rise to structural colors, along with inherent pigmentary colored nanoparticles, for useful and refractive displays,
[0133] The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure.
[0134] While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.