Plasmonic nanoparticle layer with controlled orientation

Abstract

An article is disclosed comprising one or more layers of plasma nanoparticles located between opposing dielectric material layers. A method for manufacturing an article having plasma nanoparticles is also disclosed.

Description

[0001] This application is a divisional application of the invention patent application with international application number PCT / US2018 / 014747, international application date of January 22, 2018, Chinese national phase application number 201880007797.4, and invention title "Plasma Nanoparticle Layer with Controlled Orientation".

[0002] Related applications

[0003] This application claims the benefit of U.S. Provisional Application No. 62448581, filed January 20, 2017. Background Technology

[0004] Plasma nanoparticles are particles whose electron density can couple with electromagnetic radiation at wavelengths much larger than the particle's due to the dielectric-metal interface properties between the medium and the particle. Products incorporating plasma nanoparticles can be used in applications ranging from solar cells, sensing, and spectroscopy to cancer therapy. Invention Overview

[0005] In one embodiment, the present invention provides a method for providing an article having plasma nanoparticles by applying particles using a layer-by-layer technique. This method results in the formation of a composite film of polyelectrolytes and plasma nanoparticles.

[0006] In other embodiments, the present invention provides a method for forming nanoprisms with plasma properties.

[0007] In other embodiments, the present invention provides a layer of plasma nanoparticles located between opposing dielectric material layers. The plasma nanoparticles may be at least two different metals with different plasma resonance wavelengths.

[0008] In other embodiments, plasma nanoparticles can be configured to absorb, reflect, scatter, and transmit light.

[0009] In other embodiments, the plasma nanoparticle layer may comprise oriented nanoparticles, randomly oriented nanoparticles, or a combination thereof.

[0010] In other embodiments, the present invention provides an article of manufacture comprising a plurality of plasma nanoparticle layers located between opposing dielectric material layers. In other embodiments, at least two layers have plasma nanoparticles having different plasma resonance wavelengths. In still other embodiments, at least two layers have plasma nanoparticles having the same plasma resonance wavelength.

[0011] In other embodiments, each layer has plasma nanoparticles configured to absorb, reflect, scatter, and transmit light.

[0012] In other embodiments, the plasma nanoparticle layer is parallel to the substrate or layer orientation, randomly oriented in all directions, or a combination thereof.

[0013] In other embodiments, the present invention provides an article comprising layers of nanoparticles, wherein one layer has oriented plasma nanoparticles and at least one other layer has randomly oriented nanoparticles.

[0014] In other embodiments, the present invention provides an article comprising a plurality of plasma nanoparticle layers sandwiched between dielectric material layers, the dielectric material layers having different thicknesses, the same thickness, or a combination thereof.

[0015] In other embodiments, the present invention provides an article comprising multiple layers, wherein at least two plasma nanoparticle layers have different surface densities, the same surface density, or a combination thereof.

[0016] In other embodiments, the dielectric material is a polymer.

[0017] In other embodiments, the present invention provides an article comprising a plurality of plasma nanoparticle layers, wherein at least two plasma nanoparticle layers have plasma nanoparticles containing the same or different metals.

[0018] In other embodiments, the present invention provides an article comprising a plurality of plasma nanoparticle layers, wherein at least two plasma nanoparticle layers have the same or different metal oxides.

[0019] In other embodiments, the present invention provides an article comprising a plurality of plasma nanoparticle layers, wherein at least one plasma nanoparticle layer has metal plasma nanoparticles and another plasma nanoparticle layer has metal oxide plasma nanoparticles. Brief description of the attached figures

[0020] In drawings that are not necessarily drawn to scale, the same reference numerals may describe substantially similar components in several views. The same numbers with different letter suffixes may represent different instances of substantially similar components. The drawings broadly illustrate, by way of example rather than limitation, the detailed descriptions of certain embodiments discussed in this document.

[0021] Figure 1 A, 1B, 1C, and 1D are schematic diagrams illustrating layer-by-layer assembly used in one embodiment of the invention.

[0022] Figure 2 This is a top view of the detector assembly used to measure the optical properties (%T, %R, and %A) of embodiments of the present invention.

[0023] Figure 3A , 3B 3C is a scheme in which nanosheets are randomly distributed in a polymer matrix, the corresponding optical images of the film and SEM images of the film cross-section showing nanoparticles.

[0024] Figure 3D , 3E The 3F scheme is a method of preparing oriented nanosheets on a substrate by layer-by-layer assembly, and the corresponding optical and SEM images show that, for embodiments of the present invention, most particles lie flat on the substrate.

[0025] Figure 3G and 3H The diagram shows %T, %R, and %A spectra plotted at different angles (6° to 75°) in 1° increments as a function of wavelength (400-2000 nm) for embodiments of the present invention.

[0026] Figure 4A Optical images of colloidal solutions of Ag nanoparticles with increasing ah size according to embodiments of the present invention are shown.

[0027] Figure 4B This displays a representative TEM image of the colloidal nanoparticles, showing an increase in size for embodiments of the present invention.

[0028] Figure 4C The following is shown for use in embodiments of the present invention. Figure 4A The extinction spectra of the corresponding nanoparticles.

[0029] Figure 4D An optical image of an Ag nanoparticle monolayer on a glass slide, showing various colors and sizes increasing from a–h, is displayed according to one embodiment of the invention.

[0030] Figure 4E The following is shown for use in embodiments of the present invention. Figure 4D Representative scanning electron microscope (SEM) images of Ag nanoparticles deposited in the medium.

[0031] Figure 4F The percentage transmittance, reflectance, and absorptivity of the nanoparticle film used in embodiments of the present invention are shown.

[0032] Figure 5A An incubation time study according to an embodiment of the present invention is shown, which displays optical images of glass slides placed in a nanoparticle solution for different times.

[0033] Figure 5B It is used in the embodiments of the present invention. Figure 5A The corresponding SEM image of the nanoparticles deposited on the glass slide shown.

[0034] Figure 5C and 5D The percentage transmittance and reflectance of the corresponding samples used in embodiments of the present invention are shown respectively.

[0035] Figure 6 The maximum percentage transmittance was plotted at different angles for all the different growth times shown in Figure 5.

[0036] Figure 7 The percentage coverage, transmittance, and reflectance vary with the cultivation time of embodiments of the present invention for three different sizes of nanoparticles.

[0037] Figure 8A It is an optical image of a glass slide containing a selected sample of Ag nanoparticles, which has a different number of layers stacked on top of each other, with the color becoming denser as the number of layers increases.

[0038] Figure 8B yes Figure 8A The corresponding SEM image of the selected layer is shown, where the top layer is not coated with polymer.

[0039] Figure 8C The corresponding SEM image of the selected layer ( Figure 8B ), in which the top layer is coated with a thin polymer layer.

[0040] Figure 8D These represent the percentage transmittance, reflectance, and absorptivity of Ag nanoparticle films with different numbers of layers.

[0041] Figure 9A These are optical images of two different sizes of nanoparticles, where a represents a larger nanosheet, b represents a smaller nanosheet, and a + b represents a combination of these particle layers.

[0042] Figure 9B express Figure 9A The corresponding SEM image.

[0043] Figure 9C The percentage transmittance, reflectance, and absorptivity of two nanoparticle layers (a + b) of different sizes are shown.

[0044] Figure 10A , 10B 10C, 10D, 10E, and 10F are p polarized light and s 3D contour plot of polarized light passing through a composite film of Ag nanoparticles and PAH. The thermal map shows the intensity of the wavelength of light that is most blocked and defines its range.

[0045] Figure 11A and11B An article having multiple plasma nanoparticle layers is shown. Invention Details

[0046] Detailed embodiments of the invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely examples of the invention, which can be embodied in various forms. Therefore, the specific structural and functional details disclosed herein should not be construed as limiting, but rather as a representative basis for guiding those skilled in the art to use the invention differently in virtually any appropriately detailed manner, structure, or system. Furthermore, the terminology and phrases used herein are not intended to be limiting, but rather to provide an understandable description of the invention.

[0047] like Figure 1 As shown in A-1D, some embodiments of the present invention provide a layer-by-layer technique for preparing composite films of polyelectrolytes and plasma nanoparticles on an article of manufacture or substrate. In a preferred embodiment, Ag plasma nanoparticles may be used.

[0048] As shown in one embodiment, the substrate or article 100 (which may be a clean glass slide) is first immersed in a diluted polyelectrolyte solution (10 mM). Figure 1 A), then wash with deionized (DI) water. Figure 1 B). Then it was immersed in nanoparticle solution 110 for different times ( Figure 1 C), then wash with deionized water (Figure D).

[0049] The use of polyelectrolytes in thin films is known to those skilled in the art. In one embodiment, a poly(allylamine hydrochloride) cationic polymer and a poly(acrylic acid) (PAA) anionic polymer are used in the fabrication of multilayer thin films, producing results such as... Figure 1 The deposition of plasma nanoparticles 120-124 is shown in Figure D.

[0050] Si-O on the glass slide or other substrate provides a negative charge, allowing the PAH, as a cationic polymer, to electrostatically adhere to the slide or substrate. Strong oxidizing agents such as RCA can also be used to increase the negative charge on the slide or substrate. The PAH can be a monolayer saturated surface, thus generating a positive surface charge overall. Ag nanoparticles can carry a negative charge. In other embodiments, Ag nanoparticles are coated with citrate and therefore negatively charged, enabling electrostatic deposition onto the PAH layer. The slide or substrate can be washed with water between all deposition steps.

[0051] The orientation of plasma nanosheets has a significant impact on their optical properties. Figure 3A -F shows two different scenarios, where the nanoparticles are randomly distributed in the PMMA matrix or oriented on the matrix using PAH. Figure 3G The optical properties in -H show that randomly distributed nanoparticles (G) have the lowest % reflectance, while oriented nanoparticles (H) have an increased % reflectance. For example... Figure 3A As shown, the plasma nanoparticles 130-135 are randomly oriented in all directions relative to layer 140. Figure 3D As shown, plasma nanoparticles 160-165 are oriented parallel to layer 170.

[0052] In a preferred embodiment, Ag nanoprisms are synthesized in an aqueous medium using a seed-mediated method. Figure 4A and 4C Optical images and extinction peaks of the colloidal solution are shown. Within the visible light range (400-700 nm), a bright color is observed in sheet-like nanoparticles due to in-plane dipoles. Above 700 nm, the in-plane dipoles do not produce a strong color; instead, a lighter color is observed due to in-plane quadrupoles associated with the sheet-like structure. In-plane quadrupoles are characteristic of sheet-like nanoparticles. Figure 4B Typical TEM images of the selected nanoparticles are shown, revealing that most nanoparticles are prismatic in shape, except for the smaller nanoparticles, which are more rounded.

[0053] In other embodiments, an impregnation machine can be used. Using an impregnation machine, these nanoparticles are deposited onto a glass slide or substrate using a layer-by-layer technique. Figure 4D Optical images of a glass slide are shown after nanoparticles have been deposited on it. The samples were immersed (i.e., cultured) for 120 minutes, resulting in a dark color on the slide due to the high density of nanoparticles. Figure 4E This was confirmed in the SEM images. Based on the nanoparticle size, the transmission spectrum is as follows: Figure 4F As shown in the diagram. Optical measurements are performed using the Cary Universal Measurement Accessory (UMA) with the Cary 5000. Figure 2 As shown. Unpolarized light is used here. The transmittance distribution shows that the wavelength of light blocked by nanoparticles of various sizes depends on the location of their local surface plasmon peaks. It was also found that smaller nanoparticles have lower reflectance compared to larger nanoparticles, such as... Figure 4F As shown. As reported in previous studies, the reflectivity of light increases with the size of the sheet. The % absorption spectrum can be represented as follows. Figure 4F As shown, these nanoparticles have a higher absorption rate than reflectivity.

[0054] The growth time also plays a role in the deposition of plasma nanoparticles using polyelectrolytes. Figure 5AShows optical images of the nanoparticles deposited on the substrate at different time intervals. As the cultivation time increases, the color becomes stronger. Figure 5B The corresponding FE-SEM images in Figure 5C show an increase in nanoparticle density from 10 - 300 minutes. Physically, from the optical and SEM images, it can be seen that the film becomes saturated around 120 minutes, but observing Figure 5C the % transmittance (%T) and % reflectance (%R) in Figure 6 shows an increase in the shoulder peak. The appearance of the shoulder peak can be attributed to the decrease in inter-particle spacing and in some cases overlap, leading to the local surface plasmon coupling (LSPC) effect. Thus, as the cultivation time increases, more and more particles come closer and overlap with each other, resulting in this coupling phenomenon. The % transmittance also indicates that as the density of the nanoparticles increases, more light is blocked at the local surface plasmon resonance (LSPR) of the nanoparticles. Reaching a point, the maximum transmittance at the LSPR of the nanoparticles stops, while the coupling effect continues to increase. Similarly, the % reflectance increases as the density of the nanoparticles increases. The coupling effect also leads to the reflection of light at higher wavelengths, as Figure 7 visible in

[0055] In Figure 8A the maximum transmittance of sample 5 is plotted against the angle of incidence. In Figure 8B and 8C for three different sizes (a < b < c), the surface coverage %T and %R are plotted against the cultivation time. It can be seen quantitatively that at around 90 minutes, the surface starts to saturate and the surface coverage does not increase significantly. For the 300-minute sample in Fig. 5, the maximum surface coverage is about 55%, so 45% of the surface is still empty, which is useful for light transmittance.

[0055] The transmittance can be reduced by using a longer cultivation time or using multiple layers of nanoparticles stacked on top of each other. Figure 8A Shows optical images of the multi-layer samples. The corresponding SEM images of the selected samples are also shown separately in Figure 8B and 8C PMMA is used as a spacer between the two nanoparticle layers, which helps to keep the nanoparticles separated and helps to avoid unwanted coupling. If PMMA is not used and only PAH-PAA is used, then we will see many unwanted coupling effects. As Figure 8D shown, for LSPR, the transmittance is reduced and the reflectance and absorbance increase. Thus, increasing the number of layers also results in blocking light at other higher wavelengths.

[0056] This multi-layer strategy can also be used to prepare samples with two different types of nanoparticles. For example, shown in Fig. 9 is an example of large nanoparticles in the NIR range and another layer of smaller nanoparticles with absorption in the visible range. The large nanoparticles can be used for heat-reflective windows, and the addition of the smaller nanoparticle layer is for aesthetic purposes. This filtering function can be applied to many useful applications. In Figure 9B In the SEM images, the nanoparticles are well separated, and Figure 9C The plasma peaks were well separated.

[0057] In coating applications, it is important to know the film's absorptivity, as it defines the imparted color. Therefore, the optical properties of these films and their polarization dependence are plotted on... Figure 10A-10F In. Figure 10A In -C, use p Polarization was investigated, and transmittance, reflectance, and absorptivity were measured at different angles from 6° to 58° in 1° increments. Similarly, s Polarization plotting Figure 10D -F in. These three-dimensional contour maps show the exact range of wavelengths of light that are not transmitted but reflected or absorbed.

[0058] Materials and methods

[0059] Materials: Silver nitrate (> 99.9999%) (204390), sodium borohydride (> 99.99%) (480886), trisodium citrate dihydrate (> 99.0%) (S4641), ascorbic acid (> 99.0%) (A5960), poly(allylamine hydrochloride) (PAH) (average M w -17,500g mol")(283215), Poly(acrylic acid)((PAA)(M v -450,000 g mol) and sodium poly(4-styrene sulfonate) (PSSS) (average M w -1,000 Kg mol -1 (434574) was purchased from Sigma-Aldrich and used as is. A standard glass microscope slide (25 × 75 mm) (catalog number 12-544-4) was purchased from Fisher Scientific and used as a substrate or article. Other substrates of various materials, sizes, and shapes may also be used. Nanoparticles were synthesized in ultrapure deionized (DI) water obtained from the Thermo Scientific™ Barnstead™ GenPure™ Pro water purification system at 17.60 MQ-cm, followed by a slide washing step with deionized water after deposition in a polyelectrolyte or nanoparticle solution.

[0060] Synthesis of Ag Nanoparticles: Ag nanoparticles were synthesized using a seed-mediated method. Ag seeds were synthesized as follows: First, under constant stirring, 0.25 mL of PSSS (5 mg / mL) and 0.3 mL of ice-cold NaBH4 (10 mM) aqueous solution were added to 5 mL of sodium citrate (2.5 mM) solution. Then, 5 mL of AgNO3 (0.5 mM) was added to the solution at a rate of 2 mL / min using a Cole-Parmer syringe pump (catalog number 78-8210C). The seed solution was then immediately covered with an Al foil to prevent exposure. After 5 minutes, stirring was stopped.

[0061] To synthesize Ag nanoparticles, 1.5 mL of 10 mM ascorbic acid solution was added to 254 mL of water under vigorous stirring, followed by the addition of a seed solution (ranging from 200 to 2000 µL) to prepare nanoparticles of various sizes. Then, 6 mL of AgNO3 (5 mM) solution was added to the mixture at a rate of 2 mL / min. A color change in the solution indicated the growth of Ag nanoparticles. Finally, 10 mL of sodium citrate (25 mM) solution was added to the product solution to stabilize the nanoparticles. To obtain large Ag nanoparticles with resonance peaks above 800 nm, small Ag nanosheet seeds were prepared by adding 75 µL of LAA and 10 µL of Ag spherical seeds to 10 mL of water. Then, 3 mL of 0.5 mM AgNO3 was added at a rate of 1 mL / min. Once the nanoparticles were prepared, they were used as seeds to grow into larger nanosheets. To prepare large Ag nanoparticles, 150 µL of LAA was added to 20 mL of water, followed by various amounts (0.5–1 mL) of Ag nanosheets. Then, 6 mL of 0.5 mM AgNO3 was added to the mixture at a rate of 2 mL / min. Once synthesis was complete, 1 mL of sodium citrate was added to stabilize the nanoparticles.

[0062] Transmission electron microscopy (TEM): TEM samples were prepared by drop-coating 5-10 μL of Ag nanoparticles onto a copper grid. The samples were dried overnight at room temperature and imaged using a Philips EM420 transmission electron microscope at an accelerating voltage of 120 keV.

[0063] Layer-by-Layer Fabrication of Ag Nanoparticles and Polyelectrolytes: Thin films of nanoparticle-polymer nanocomposites were prepared using a layer-by-layer (LbL) technique with an impregnation machine. First, dilute solutions of cationic PAH and anionic PAA polyelectrolytes at 10 mM (monomer-based) concentrations were prepared in deionized water. The pH of both solutions was neutralized (i.e., 7) by adding hydrochloric acid (HCl) or sodium hydroxide (NaOH). A neutral pH helps prevent degradation of the nanoparticles. Two 120 mL beakers were filled with 100 mL of PAH solution and 100 mL of a colloidal solution of the synthesized Ag nanoparticles for deposition. Six other beakers were filled with deionized water for washing. All eight beakers were placed on the rotating stage of the impregnation machine. The PAH solution and Ag nanoparticles were separated by three beakers containing deionized water. A glass slide was immersed in the PAH solution for 5 minutes, resulting in the deposition of positively charged PAH due to electrostatic interactions. To remove any potentially accumulated polyelectrolytes, the slide was washed in deionized water for 40 seconds, and this process was repeated three times. After washing, the glass slides were immersed in a colloidal solution of Ag nanoparticles for varying times (10-300 minutes). Due to the adsorption of sodium citrate molecules, the Ag nanoparticles have a negatively charged surface, allowing them to adhere to the positively charged PAH layer attached to the glass slide. The slides were then washed three times in deionized water for 30 seconds each time. The deposition cycle was repeated as needed.

[0064] Random orientation of Ag nanoparticles: Ag nanoparticles were centrifuged at 10,000 rpm for 30 minutes in an aqueous medium and redispersed in DMF. The nanoparticles were functionalized in DMF with 1 wt% mercapto-terminated poly(methyl methacrylate) (PMMA-SH) for 24 hours and centrifuged again at 10,000 rpm for 30 minutes. The supernatant was removed, and the nanoparticles were redispersed in 5 wt% PMMA-SH in toluene. The nanocomposite film was coated on a glass surface and then kept in a fume hood for 24–48 hours to allow the solvent to evaporate.

[0065] Field emission scanning electron microscopy (FE-SEM): To image the nanoparticles on a glass slide, the sample was coated with high-resolution iridium at a thickness of 1.5–3 nm. They were then imaged using SEM with a WD of 4 mm, an EHT of 10 kV, and an InLens detector.

[0066] Optical measurements were performed using UV-Vis-NIR spectroscopy with a Carly Universal Measurement Aid (UMA): To perform optical measurements including % absorptivity, transmittance, and reflectance, we used a Universal Measurement Aid (UMA) and an Agilent Carly 5000 UV-Vis-NIR spectrophotometer. A schematic diagram of the setup is shown below. Figure 2As shown. Here, a glass slide with nanoparticles is mounted on a stage through which the full beam can pass. For Figures 4 and 5, the sample angle is 6° for % reflectance and % transmittance. In Figure 3, the angle varies from 6° to 75° in 1° increments, and these data are plotted in Origin.

[0067] Figure 11A and 11B Other embodiments of the invention relating to the manufacture of articles are shown. For example... Figure 11A As shown, the article 200 includes multiple layers 201-204, which may optionally be located on the substrate 210. Sandwiched between layers 200-201 are layers of plasma nanoparticles 220-224, 230-234, and 240-244.

[0068] As shown in the figure, the plasma nanoparticles 220-224, 230-234, and 240-244 can have the same size. Furthermore, the plasma nanoparticles can be configured as described above. For example, the plasma nanoparticles 220-224, 230-234, and 240-244 can be configured as follows: Figure 3A The random orientation shown, or it can be as follows Figure 3D They have the same orientation.

[0069] In other embodiments, the plasma nanoparticles 220-224, 230-234, and 240-244 may have different plasma resonance wavelengths, the same plasma resonance wavelength, or combinations thereof. In other embodiments, each layer of the article 200 has plasma nanoparticles configured to absorb, reflect, and transmit light, and combinations thereof. In other embodiments, the plasma nanoparticle layers of the article 200 have the same orientation, random orientation, or combinations thereof.

[0070] Plasma nanoparticles 220-224, 230-234, and 240-244 can be composed of the same metal, different metals, the same metal oxide, or different metal oxides, as well as combinations thereof. Plasma nanoparticles 220-224, 230-234, and 240-244 can also have different surface densities or the same surface density.

[0071] In other embodiments, layers 201-204 of article 200 may have different thicknesses, the same thickness, or combinations thereof. In other embodiments, the dielectric material is a polymer, a metal oxide, or a combination thereof.

[0072] like Figure 11BAs shown, the article 300 includes multiple layers 301-304, which may optionally be located on the substrate 310. Sandwiched between layers 300-301 are layers of plasma nanoparticles 320-328, 330-336 and 340-343.

[0073] As shown in the figure, the plasma nanoparticles 320-328, 330-336, and 340-343 can have different sizes. Furthermore, the plasma nanoparticles can be configured as described above. For example, the plasma nanoparticles 320-328, 330-336, and 340-343 can be configured as follows... Figure 3A The random orientation shown, or it can be as follows Figure 3D They have the same orientation.

[0074] In other embodiments, the plasma nanoparticles 320-328, 330-336, and 340-343 may have different plasma resonance wavelengths, the same plasma resonance wavelength, or combinations thereof. In other embodiments, each layer of the article 300 has plasma nanoparticles configured to absorb, reflect, and transmit light, and combinations thereof. In other embodiments, the plasma nanoparticle layers of the article 300 have the same orientation, random orientation, or combinations thereof.

[0075] Plasma nanoparticles 320-328, 330-336, and 340-343 can be composed of the same metal, different metals, the same metal oxide, or different metal oxides, as well as combinations thereof. Plasma nanoparticles 320-328, 330-336, and 340-343 can also have different surface densities or the same surface density.

[0076] In other embodiments, layers 301-304 of article 300 may have different thicknesses, the same thickness, or combinations thereof. In other embodiments, the dielectric material is a polymer, a metal oxide, or a combination thereof.

[0077] While the foregoing written description enables those skilled in the art to prepare and use the content currently considered to be in its best mode, those skilled in the art will understand and recognize that variations, combinations, and equivalents of specific implementations, methods, and examples exist. Therefore, this disclosure is not limited to the foregoing implementations, methods, and examples, but rather to all implementations and methods within the scope and spirit of this disclosure.

Claims

1. A method for manufacturing articles having plasma nanoparticles, the method comprising: Deposit a polyelectrolyte layer on the substrate; A first plasma nanoparticle layer is deposited on the polyelectrolyte layer, the first plasma nanoparticle layer having first plasma nanoparticles oriented parallel to the polyelectrolyte layer; and A second plasma nanoparticle layer is deposited on the polyelectrolyte layer, the second plasma nanoparticle layer having second plasma nanoparticles randomly oriented in multiple directions relative to the polyelectrolyte layer.

2. The method as described in claim 1, wherein, The first plasma nanoparticle or the second plasma nanoparticle has a prismatic shape.

3. The method of claim 1, further comprising: Before depositing the first plasma nanoparticle or the second plasma nanoparticle onto the polyelectrolyte layer, the first plasma nanoparticle or the second plasma nanoparticle is grown into a prismatic shape.

4. The method of claim 1, wherein, The first plasma nanoparticle is made of a first metal, and the second plasma nanoparticle is made of a second metal.

5. The method of claim 1, wherein, The first plasma nanoparticle has a first plasma resonance wavelength, and the second plasma nanoparticle has a second plasma resonance wavelength.

6. The method of claim 1, wherein, The polyelectrolyte layer is made of an anionic polymer.

7. The method of claim 6, wherein, The anionic polymer is polyacrylic acid.

8. The method of claim 1, wherein, The polyelectrolyte layer is made of a cationic polymer.

9. The method of claim 8, wherein, The cationic polymer is polyallylamine hydrochloride.

10. The method of claim 1, wherein, One of the first plasma nanoparticles and the second plasma nanoparticles is made of metal, and the other of the first plasma nanoparticles and the second plasma nanoparticles is made of metal oxide.

11. The method of claim 1, wherein, Depositing a first plasma nanoparticle layer on the polyelectrolyte layer includes: electrostatically depositing a solution of gold nanoparticles, the gold nanoparticles having a negatively charged surface due to adsorbed sodium citrate.

12. A method for manufacturing an article having plasma nanoparticles, the method comprising: Deposit a first dielectric layer on the substrate; A first plasma nanoparticle layer is deposited on the first dielectric layer, the first plasma nanoparticle layer having first plasma nanoparticles made of metal; A second dielectric layer is deposited on the first plasma nanoparticle layer; as well as A second plasma nanoparticle layer is deposited on the second dielectric layer, the second plasma nanoparticle layer having second plasma nanoparticles made of metal oxide, wherein at least one of the first dielectric layer or the second dielectric layer comprises a polymer.

13. The method of claim 12, wherein, The first plasma nanoparticle or the second plasma nanoparticle has a prismatic shape.

14. The method of claim 12, further comprising: Prior to deposition, the first plasma nanoparticle or the second plasma nanoparticle is grown into a prismatic shape.

15. The method of claim 12, wherein, The first plasma nanoparticle has a first plasma resonance wavelength, and the second plasma nanoparticle has a second plasma resonance wavelength.

16. The method of claim 12, wherein, The first plasma nanoparticles are oriented parallel to the first dielectric layer.

17. The method of claim 16, wherein, The second plasma nanoparticles are randomly oriented in multiple directions relative to the second dielectric layer.

18. The method of claim 12, wherein, Depositing a first plasma nanoparticle layer on the first dielectric layer includes: electrostatically depositing a solution of gold nanoparticles, the gold nanoparticles having a negatively charged surface due to adsorption of sodium citrate.

19. A method for manufacturing an article having plasma nanoparticles, the method comprising: Deposit a first dielectric layer on the substrate; A first plasma nanoparticle layer is deposited on the first dielectric layer, the first plasma nanoparticle layer having first plasma nanoparticles made of metal; A second dielectric layer is deposited on the first plasma nanoparticle layer; as well as A second plasma nanoparticle layer is deposited on the second dielectric layer, the second plasma nanoparticle layer having second plasma nanoparticles made of metal oxide, wherein at least one of the first dielectric layer or the second dielectric layer comprises metal oxide.

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