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US20190324206A1 - Plasmonic Nanoparticle Layers with Controlled Orientation - Google Patents

Plasmonic Nanoparticle Layers with Controlled Orientation Download PDF

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US20190324206A1
US20190324206A1 US16/473,458 US201816473458A US2019324206A1 US 20190324206 A1 US20190324206 A1 US 20190324206A1 US 201816473458 A US201816473458 A US 201816473458A US 2019324206 A1 US2019324206 A1 US 2019324206A1
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nanoparticles
plasmonic nanoparticles
layer
layers
article
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Guoliang Liu
Assad U. Khan
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Virginia Tech Intellectual Properties Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1226—Basic optical elements, e.g. light-guiding paths involving surface plasmon interaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B26/00—Optical devices or arrangements for the control of light using movable or deformable optical elements
    • G02B26/02—Optical devices or arrangements for the control of light using movable or deformable optical elements for controlling the intensity of light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/132—Integrated optical circuits characterised by the manufacturing method by deposition of thin films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/101—Nanooptics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1221—Basic optical elements, e.g. light-guiding paths made from organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component

Definitions

  • Plasmonic nanoparticles are particles whose electron density may be coupled with electromagnetic radiation of wavelengths that are far larger than the particle due to the nature of the dielectric-metal interface between the medium and the particles.
  • Articles incorporating plasmonic nanoparticles have use in applications ranging from solar cells, sensing, spectroscopy to cancer treatment.
  • the present invention provides methods that provide articles having plasmonic nanoparticles by applying the particles using the layer-by-layer technique.
  • the method results in the formation of composite films of polyelectrolytes and plasmonic nanoparticles.
  • the present invention provides methods that form nanoprisms having plasmonic properties.
  • the present invention provides a layer of plasmonic nanoparticles located between opposing layers of dielectric materials.
  • the plasmonic nanoparticles may be at least two different metals, have different plasmonic resonance wavelengths.
  • the plasmonic nanoparticles may be configured to absorb, reflect, scatter, and transmit light.
  • the layer of plasmonic nanoparticles may be comprised of oriented nanoparticles, randomly oriented nanoparticles, or combinations thereof.
  • the present invention provides an article comprising a plurality of layers of plasmonic nanoparticles located between opposing layers of dielectric materials.
  • at least two layers have plasmonic nanoparticles having different plasmon resonance wavelengths.
  • at least two layers have plasmonic nanoparticles having the same plasmon resonance wavelengths.
  • each layer has plasmonic nanoparticles configured to absorb, reflect, scatter, and transmit light.
  • the layers of plasmonic nanoparticles are oriented parallel to substrate or layers, randomly oriented in all directions or has combinations thereof.
  • the present invention provides an article comprising layers of nanoparticles wherein one of the layers has oriented plasmonic nanoparticles and at least one other layer has randomly oriented nanoparticles.
  • the present invention provides an article comprising a plurality of layers of plasmonic nanoparticles sandwiched between layers of dielectric materials which may have different thicknesses, the same thicknesses or combinations thereof.
  • the present invention provides an article comprising a plurality of layers wherein at least two layers of plasmonic nanoparticles have different surface densities, the same surface densities or combinations thereof.
  • the dielectric material is a polymer.
  • the present invention provides an article comprising a plurality of layers of plasmonic nanoparticles wherein at least two layers of the plasmonic nanoparticles have plasmonic nanoparticles having the same or different metals.
  • the present invention provides an article comprising a plurality of layers of plasmonic nanoparticles wherein at least two layers of the plasmonic nanoparticles having the same or different metal oxides.
  • the present invention provides an article comprising a plurality of layers of plasmonic nanoparticles wherein at least one layer of the plasmonic nanoparticles has metal plasmonic nanoparticles and another layer of the plasmonic nanoparticles has metal oxide plasmonic nanoparticles.
  • FIGS. 1A, 1B, 1C and 1D are schematics that show a layer-by-layer assembly used in one embodiment of the present invention.
  • FIG. 2 is the top view of a detector assembly used to measured optical properties (% T, % R, and % A) for an embodiment of the present invention.
  • FIGS. 3A, 3B and 3C are schemes for randomly distributed nanoplates in polymer matrix, corresponding optical image of the film and film cross-section SEM image showing nanoparticle.
  • FIGS. 3D, 3E and 3F are schemes for oriented nanoplates on substrate prepared by layer-by-layer assembly, corresponding optical image and SEM image showing most particles are lying flat on the substrate for an embodiment of the present invention.
  • FIGS. 3G and 3H show % T, % R, and % A spectrum plotted as a function of wavelength (400-2000 nm) at different angles (6° to 75°) at 1° increment for an embodiment of the present invention.
  • FIG. 4A shows an optical image of colloidal solution of Ag nanoparticles of increasing sizes from a-h in accordance with an embodiment of the present invention.
  • FIG. 4B shows representative TEM images of the colloidal nanoparticles where the size can be seen increasing for an embodiment of the present invention.
  • FIG. 4C shows extinction spectra of the corresponding nanoparticles in FIG. 4A for an embodiment of the present invention.
  • FIG. 4D shows an optical image of one monolayer of Ag nanoparticles on glass slides showing various colors and increasing size from a-h in accordance with an embodiment of the present invention.
  • FIG. 4E shows the corresponding representative scanning electron microscope (SEM) image of the deposited Ag nanoparticles in FIG. 4D for an embodiment of the present invention.
  • FIGS. 4F shows the percentage transmittance, reflectance, and absorptance of the nanoparticles films for an embodiment of the present invention.
  • FIG. 5A shows an incubation time study showing the optical image of glass slides which were placed in nanoparticles solution for various times for embodiments of the present invention.
  • FIG. 5B is a corresponding SEM images of the deposited nanoparticles on glass slides shown in FIG. 5A for an embodiment of the present invention.
  • FIG. 5C shows percentage transmittance and reflectance of the corresponding samples for an embodiment of the present invention.
  • FIG. 6 depicts the maximum percentage transmittance plotted for all the different incubation times shown in FIG. 5 at different angles.
  • FIG. 7 shows the percentage coverage, transmittance, and reflectance as a function of incubation time for an embodiment of the present invention for three different sizes of nanoparticles.
  • FIG. 8A is an optical image of glass slides with selected samples of Ag nanoparticles having different number of layers deposited on top of each other depicting a more dense color as the number of layer increases,
  • FIG. 8B is a corresponding SEM images of selected layers shown in FIG. 8A where the top layer is not coated with polymer.
  • FIG. 8C is a corresponding SEM images of selected layers ( FIG. 8B ) where the top layer is coated with a thin polymer layer.
  • FIG. 8D is percentage transmittance, reflectance, and absorptance respectively through Ag nanoparticles films having various number of layers.
  • FIG. 9A is an optical image of two different size of nanoparticles where is a represents bigger nanoplates, b represents smaller nanoplates, and a+b represents combination of these layers of particles.
  • FIG. 9B represents the corresponding SEM images of FIG. 9A .
  • FIG. 9C shows the percentage transmittance, reflectance, and absorptance of the two layers of different sizes of nanoparticles (a+b).
  • FIGS. 10A, 10B, 10C, 10D, 10E and 10F are 3D contour plots for p- and s-polarized light passing through a composite film of Ag nanoparticle and PAH.
  • the heat maps show the intensity of light wavelengths stopped most and defines the range.
  • FIGS. 11A and 11B illustrate an article having multiple layers of plasmonic nanoparticles.
  • some embodiments of the present invention provide a layer-by-layer technique used to prepare composite films of polyelectrolytes and plasmonic nanoparticles on articles or substrates.
  • Ag plasmonic nanoparticles may be used.
  • a substrate or article 100 which may be a clean glass slide, is first dipped in dilute solution (10 mM) of polyelectrolyte solution ( FIG. 1A ) followed by rinsing step with deionized (DI) water ( FIG. 1B ). It is then dipped in nanoparticles solution 110 for various times ( FIG. 1C ) and rinsed afterwards with DI water (FIG. D).
  • dilute solution (10 mM) of polyelectrolyte solution FIG. 1A
  • DI deionized
  • polyelectrolytes in thin films is known to those of skill in the art for one embodiment poly (allylamine hydrochloride) (PAH) cationic polymer and poly (acrylic acid) (PAA) anionic polymer were used for multiplayer thin film fabrication resulting in the deposition of plasmonic nanoparticles 120 - 124 as shown in FIG. 1D .
  • PAH allylamine hydrochloride
  • PAA poly (acrylic acid) anionic polymer
  • the Si-O on glass slides or other substrates provides a negative charge and PAH which is cationic polymer can electrostatically attach to the glass slides or substrates. Strong oxidation agents like RCA can also be used to increase the negative charge on glass slides or substrates. PAH can saturate the surface with a monolayer, hence giving rise to a positive surface charge overall.
  • the Ag nanoparticles may be negatively charged. In other embodiments, the Ag nanoparticles are citrate-capped and hence negatively charged and can be electrostatically deposited on the PAH layer.
  • the glass slides or substrates may be rinsed with water between all deposition steps.
  • FIGS. 3A-F show two different cases where the nanoparticles are either randomly distributed in a PMMA matrix or they are oriented on substrate using PAH.
  • the optical properties in FIG. 3G-H show that the % reflectance is minimum for randomly distributed nanoparticles (G) while it increases for the oriented nanoparticles (H).
  • plasmonic nanoparticles 130 - 135 are randomly oriented in all directions to layer 140 .
  • plasmonic nanoparticles 160 - 165 are oriented parallel to layer 170 .
  • FIGS. 4A and 4C show the optical image and extinction peaks of the colloidal solution.
  • the in-plane dipole For plate like nanoparticles in the visible range (400-700 nm), sharp colors can be seen owing to the in-plane dipole. When the in-plane dipole is above 700 nm, it does not impart the intense color, instead light colors are observed because of the inplane quadrupole peaks associated with plate like structures. The in-plane quadrupole is a characteristic of plate like nanoparticles.
  • FIG. 4B shows a typical TEM images for selected nanoparticles and it was observed that majority of nanoparticles were prismatic in shape except the smaller nanoparticles which were more rounded.
  • a dipping machine may be used. Using a dipping machine, these nanoparticles were deposited on glass slides or substrates using a layer-by-layer technique.
  • FIG. 4D shows the optical image of the glass slides after the nanoparticles were deposited on it.
  • the dipping time i.e. incubation
  • the dipping time was 120 min for these samples and therefore the glass slides have dark colors due to high density of nanoparticles as can be evidenced from the SEM images in FIG. 4E .
  • the transmittance spectrum can be seen in FIG. 4F .
  • the optical measurements were taken using Cary Universal Measurement Accessary (UMA) with Cary 5000, the schematic of which is shown in FIG. 2 . Here non-polarized light was used.
  • UMA Cary Universal Measurement Accessary
  • Transmittance profiles revealed that the wavelength of light being stopped by various size of nanoparticles is dependent on their localized surface plasmonic peak position. It was also revealed that the smaller nanoparticles have lower reflectance compared to bigger nanoparticles as can be seen in FIG. 4F . Reflectance of light increases as the size of plate as reported in previous studies. The % absorptance spectrum can be seen in FIG. 4F . These nanoparticles have higher absorptance than reflectance.
  • Figure SA shows the optical image of the nanoparticles deposited on substrates for different time intervals. The color becomes more and more intense as the incubation time is increased.
  • Corresponding FE-SEM image in Figure SB revealed that the nanoparticles density increases from 10-300 min. Physically from the optical image and SEM images it can be witnessed that the films become saturated around 120 min but looking at the % transmittance (% T) and % reflectance (% R) in FIG. 5C , which show a shoulder peak increasing. The shoulder peak appearance may be attributed to the interparticle spacing being decreased and in some cases overlapping, leading to localized surface plasmon coupling (LSPC) effect.
  • LSPC localized surface plasmon coupling
  • the % transmittance also reveals that as the density of nanoparticles increases, more light is being stopped at the localized surface plasmon resonance (LSPR) of nanoparticles. A point is reached where the maximum transmittance at the LSPR of nanoparticles stops while the coupling effect keeps increasing. Similarly, % reflectance increases as the density of the nanoparticles increases. The coupling effect also leads to reflectance of higher wavelength light as can be witnessed in FIG. 5C .
  • the maximum transmittance of sample 5 is plotted as function of incidence angle in FIG. 6 .
  • the surface coverage, % T, and % R is plotted as a function of incubation time for three different sizes (a ⁇ b ⁇ c) in FIG. 7 . It can be quantitatively seen that around 90 min the surface starts to saturate with no significant increase in the surface coverage. The maximum surface coverage is around 55% for FIG. 5 , 300 min sample and hence still 45% of the surface is empty which can be useful for light transmittance.
  • FIG. 8A show optical images of multilayer samples. Their corresponding SEM images for selected samples are also shown in FIG. 8B and 8C respectively.
  • PMMA is used as a spacer between two layers of nanoparticles which helps in keeping the nanoparticles apart and helps in avoiding undesirable coupling. If PMMA is not used and only PAH-PAA are used, then we will see a lot of undesirable coupling effects.
  • Decreasing transmittance and increasing reflectance and absorptance for a LSPR are shown in FIG. 8D . Thus, increasing the number of layers also leads to blocking other higher wavelengths of light.
  • This multiple layer strategy can also be applied to prepare samples with two different types of nanoparticles.
  • FIG. 9 shown in FIG. 9 is an example of big nanoparticles in NIR range which are useful for heat reflecting windows and another layer of smaller nanoparticles absorbing in visible region can be added for aesthetic purposes.
  • This filtering ability can be applied to many useful applications.
  • the nanoparticles are well separated in SEM images in FIG. 9B and the plasmonic peaks are well separated in FIG. 9C .
  • FIGS. 10A-10F polarization dependence of the optical properties of these films was plotted in FIGS. 10A-10F .
  • FIGS. 10A-C p-polarized was used and the transmittance, reflectance, and absorptance was measured at different angles from 6° to 58° with 1° increment.
  • s-polarized was plotted in FIGS. 9D-F .
  • Plain glass microscope slides (25 ⁇ 75 mm) (Cat. No. 12-544-4) were bought from Fisher Scientific and used as the substrate or article. Other substrates of various materials, sizes and shapes may also be used. Nanoparticle synthesis was carried out in ultrapure deionized (DI) water obtained from Thermo ScientificTM BarnsteadTM GenPureTM Pro water purification system at 17.60 MQ-cm, while rinsing steps of the glass slides after deposition in polyelectrolyte or nanoparticles solutions were carried out with DI water.
  • DI ultrapure deionized
  • Ag nanoparticles were synthesized following a seed-mediated method.
  • Ag seeds may be synthesized as follows. First, 0.25 mL of PSSS (5 mg/mL) and 0.3 mL of ice-cold NaBH 4 (10 mM) aqueous solutions were added to a 5 mL solution of sodium citrate (2.5 mM) under constant stirring. Afterwards, 5 mL of AgNO 3 (0.5 mM) was added to the solution at a rate of 2 mL/min using Cole-Parmer syringe pump (Cat. No. 78-8210C). The seed solution was then immediately covered in an Al foil to prevent from light exposure. After 5 min, the stirring was stopped.
  • small Ag nanoplate seeds were prepared by the addition of 75 ⁇ L of AA and 10 ⁇ L of Ag spherical seeds to 10 mL of water. This was followed by the addition of 3 mL of 0.5 mM AgNO 3 at 1 mL/min. Once the nanoparticles were prepared they were used as seeds to be grown into larger nanoplates.
  • TEM Transmission Electron Microscopy
  • Layer-by-Layer Fabrication of Ag Nanoparticles and Polyelectrolytes Thin films of nanoparticle-polymer nanocomposites were prepared using a layer-by-layer (LbL) technique using dipping machine. First, two dilute solutions of cationic PAH and anionic PAA polyelectrolytes with a concentration of 10 mM (based on the monomer) were prepared in DI water. The pH of both solutions was brought to neutral (ie. 7) by adding either hydrochloric acid (HCl) or sodium hydroxide (NaOH). The neutral pH helped in not degrading the nanoparticles.
  • HCl hydrochloric acid
  • NaOH sodium hydroxide
  • Two 120 mL beakers were filled with 100 mL PAH solution and 100 mL colloidal solution of as-synthesized Ag nanoparticles for deposition.
  • Six additional beakers were filled with DI water for rinsing. All eight beakers were placed on the rotating stage of a dipping machine.
  • the PAH solution and Ag nanoparticles were separated by three beakers of DI water.
  • the glass slides were dipped in the PAH solution for 5 min which led to the deposition of positively charged PAH onto the glass slides due to electrostatic interaction. To remove any potentially accumulated polyelectrolyte, the glass slides were rinsed in DI water for 40 sec and this process was repeated three times.
  • the glass slides were immersed in the colloidal solution of Ag nanoparticles for various amount of time (10-300 min). Ag nanoparticles had negatively charged surface due to adsorbed sodium citrate molecules therefore the nanoparticles were able to adhere onto the positively charged PAH layers attached on the glass slides. Afterwards, the glass slides were rinsed three times in DI water for 30 sec each. The deposition cycle was repeated as needed.
  • FE-SEM Field Emission Scanning Electron Microscopy
  • Optical Measurement using UV-Visible Near-Infrared (NIR) Spectroscopy with Cary Universal Measurement Accessory (UMA) To perform optical measurement including % absorptance, transmittance, and reflectance, we used universal measurement accessary (UMA) with Agilent Cary 5000 UV-visible-NIR spectrophotometer. A schematic of the setup is shown in FIG. 2 . Here the glass slide with nanoparticles was mounted on the stage where the full light beam could pass through it. For FIGS. 4 and 5 the sample angle was 6° for % reflectance and % transmittance. In FIG. 3 the angle was changed from 6° to 75° with 1° increment step and the data was plotted in Origin.
  • NIR Near-Infrared
  • UMA UV-visible-NIR spectrophotometer
  • FIGS. 11A and 11B illustrate other embodiments of the present involving an article of manufacture.
  • article 200 is comprised of a plurality of layers 201 - 204 which may optionally be located on substrate 210 .
  • Sandwiched between layers 200 - 201 are layers of plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 .
  • Plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 may be of the same size as shown.
  • the plasmonic nanoparticles may be configured as described above.
  • plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 may be randomly orientated as shown in FIG. 3A or may have the same orientation as shown in FIG. 3D .
  • plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 may have different plasmon resonance wavelengths, the same plasmon resonance wavelengths, or combinations thereof.
  • each layer of article 200 has plasmonic nanoparticles configured to absorb, reflect, and transmit light as well as combinations thereof.
  • the layers of plasmonic nanoparticles of article 200 are orientated the same, randomly orientated or are combinations thereof.
  • Plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 may be comprised of the same metal, different metals, the same metal oxide or different metal oxides as well as combinations thereof. Plasmonic nanoparticles 220 - 224 , 230 - 234 and 240 - 244 may also have different surface densities or the same surface densities.
  • layers 201 - 204 of article 200 may have different thicknesses, the same thicknesses or combinations thereof.
  • the dielectric material is a polymer, metal oxides as well as combinations thereof.
  • article 300 is comprised of a plurality of layers 301 - 304 which may optionally be located on substrate 310 .
  • Sandwiched between layers 300 - 301 are layers of plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 .
  • Plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 may be of varying sizes as shown.
  • the plasmonic nanoparticles may be configured as described above.
  • plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 may be randomly orientated as shown in FIG. 3A or may have the same orientation as shown in FIG. 3D .
  • plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 may have different plasmon resonance wavelengths, the same plasmon resonance wavelengths, or combinations thereof.
  • each layer of article 300 has plasmonic nanoparticles configured to absorb, reflect, and transmit light as well as combinations thereof.
  • the layers of plasmonic nanoparticles of article 300 are oriented the same, randomly oriented or are combinations thereof.
  • Plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 may be comprised of the same metal, different metals, the same metal oxide or different metal oxides as well as combinations thereof. Plasmonic nanoparticles 320 - 328 , 330 - 336 and 340 - 343 may also have different surface densities or the same surface densities.
  • layers 301 - 304 of article 300 may have different thicknesses, the same thicknesses or combinations thereof.
  • the dielectric material is a polymer, metal oxides as well as combinations thereof.

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