Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators

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Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators Wajdi Chaâbani, Julien Proust, Artur Movsesyan, Jérémie Béal, AnneLaure Baudrion, Pierre-Michel Adam, Abdallah Chehaidar, and Jérôme Plain ACS Nano, Just Accepted Manuscript • Publication Date (Web): 18 Mar 2019 Downloaded from http://pubs.acs.org on March 18, 2019

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Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators

Wajdi Chaâbani,1,2 Julien Proust,2,# Artur Movsesyan,2 Jérémie Béal,2 Anne-Laure Baudrion,2 Pierre-Michel Adam,2 Abdallah Chehaidar,1 Jérôme Plain2,#

1 - Laboratoire de Physique-Mathématiques et Applications, Université de Sfax, Faculté des Sciences de Sfax, B.P. 1171, 3000 Sfax, Tunisia.

2 - L2n (Light, Nanomaterials and Nanotechnologies), Institut Charles Delaunay CNRS FRE 2019, Université de Technologie de Troyes, 12 rue marie Curie-CS 42060 – 10004 Troyes Cedex, France.

ACS Paragon Plus Environment

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#Corresponding authors [email protected], [email protected]

Abstract

High index dielectric nanoparticles have been proposed for many different applications. However, widespread utilization in practice also requires large-scale production methods for crystalline silicon nanoparticles, with engineered optical properties in a low-cost manner. Here, we demonstrate a facile, low-cost, and large-scale fabrication method of crystalline silicon colloidal Mie resonators in water, using a blender. The obtained nanoparticles are polydisperse with an almost spherical shape and the diameters controlled in the range 100-200 nm by centrifugation process. Then, the size distribution of silicon nanoparticles enables broad extinction from UV to near infrared, confirmed by


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Mie theory when considering the size distribution in calculation. Thanks to photolithographic and drop-cast deposition techniques to locate position on a substrate of the colloidal nanoparticles, we experimentally demonstrate that the individual silicon nanoresonators show strong electric and magnetic Mie resonances in the visible range.

Keywords: Colloidal solution, large-scale, low-cost, high-index dielectric, Mie resonances, silicon nanoparticles

Efficient control of the visible light at the nanoscale is a key issue for integrated photonics devices. Surface Plasmon Resonance (SPR)1 excited in noble metal is recognized as a promising way to control the light at the nanoscale. Such unique optical property has been widely used for many different applications as surface enhanced


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Raman scattering,2 biological sensing,3 photovoltaic devices,4 and metamaterials.5 However, metals suffer from non-negligible intrinsic Ohmic losses limiting the field of potential application.6 Contrarily to plasmon-based light confinement at the nanoscale, high-refractive index dielectric nanoparticles offer a novel paradigm for light enhancement and manipulation at the nanoscale. Indeed, excitation of Mie resonances in such nanoparticles results in strong light scattering and an optical near-field enhancement, along with low Ohmic losses and thermal stability. However, silicon nanoparticles show multiple magnetic and electric resonances in the visible and the near-infrared spectral regions.7-9 Then, the overlapping between their electric and magnetic resonance modes provides to Mie resonators unique light scattering properties like Kerker-type high directional scattering.9,10 All these above optical properties make that silicon nanoparticles are used in many applications like nonlinear optics,11-13 Raman scattering enhancement,14 directional optical sorting,15 color printing,16-18 ultrafast optical switching,19 wavefront manipulation,20 optical heating (with sub-micronic particles),21 and many others.


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The wide range of applications already proposed based on Mie resonators underlines the need for flexible, low-cost fabrication methods. Electron beam lithography associated with chemical etching22 has been demonstrated as an efficient method to fabricate nanoparticles of different shapes with very sharp edges. A modified version of hole-mask colloidal lithography associated with a chemical etching of the substrate is an original technique that leads to silicon nanostructures well adapted to large area fabrication.23 The major drawback of such methods is its very high cost. Moreover, they do not allow the fabrication of spherical-shaped colloidal nanoparticles. Recently, femtosecond laser printing24,25 has been introduced by the Chichkov’s team. They demonstrate the possibility to induce spherical crystalline nanoparticles of silicon. Moreover, they show the possibility to pattern the nanoparticles onto any substrate. Despite all these major advances, large-scale and low-cost processes to produce colloidal silicon nanospheres26–30 remained challenging for the community. The lack of research related to colloidal silicon nanoparticles may be attributed to several problematic issues: no economical synthesis ways, inability to control the size and size distribution. However, colloidal silicon microparticles have been fabricated by different methods like


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laser ablation in liquid,31 chemical vapor deposition (CVD),28,32 bottom-up process,30 reactive thermal arc plasma,33 double tube reactor and inductive coupled plasma34 methods. L. Shi et al.

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have successfully synthesized submicrometer silicon colloids

based on a solution process on a large-scale. The obtained solution shows an excellent distribution in size and appropriate optical properties. However, the above mentioned Si nanoparticles are amorphous. It is well known that optical properties are directly correlated with the crystalline purity. Very recently, crystalline silicon nanoparticles, showing a strong magnetic response, have been fabricated using a bottom-up process.30 In this paper, we demonstrate the development of an aggregation-free colloidal dispersion of Si nanoparticles with spheroidal shape using a kitchen blender, based on exfoliation processes35,36 without adding any surfactant. We obtained crystalline Si nanoparticles with diameters controlled in the range of 100 nm to 200 nm. In the size range, both experimental results and theoretical calculations clearly show that individual Si nanoparticles exhibit electric and magnetic well-defined Mie resonances in the visible region. Moreover, we addressed the complete range of visible colors just by varying the diameter.


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RESULTS AND DISCUSSION Colloid Fabrication of Si Nanoparticles The first stage of this work was to prepare a colloidal solution of Si nanoparticles in deionized water using a kitchen blender, as shown in Figure 1a (see the Methods for more details). The obtained colloidal solution turns a brown/gray color as the silicon lumps are fully exfoliated in deionized water. Then, this colloidal solution is left to settle for three days without any centrifugation at temperature 5 °C and one day at 25 °C to allow the biggest nanoparticles to settle down. Thus, the liquid dispersion slowly turns lighter brown color after this storage. The supernatant is then separated from precipitate by removing the top 75 % of the dispersion by pipette and then centrifuged at 50 g RCF for 5 min to remove all submicrometer size particles. A second centrifugation at controlled speed is performed on the previous supernatant (speed tunable from 400 g RCF to 2570 g RCF for 10 min) to settle the last big particles. The new supernatant obtained finally contains the targeted colloidal silicon nanoparticles (Si NP), with a diameter depending on the centrifugation speed as explained below. The colloidal solution presents no visible aggregation and is stable for several months. The colloidal stability arises from negative


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surface potential (zeta-potential about -23±9 mV), indicated the presence of a negatively charged oxide layer at the particle surfaces (Figure S1 in Supporting Information). Several fabrication methods of silicon nanoparticles

51,33,49

mentioned that the thin amorphous

shell at the nanoparticle surface is the inevitable consequence of the oxygen exposition of the nanoparticles. Moreover, the oxide shell thickness is a linear function of the particle size ranging from 1 nm to 3 nm.52

Figure 1. a) Schematic representation of the process (grinding, clarification) used to prepare colloidal silicon nanoparticles (for further details, see scheme S2 in Supporting


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Information). b) high-magnification SEM image of a typical crystalline Si nanoparticle deposited onto a silicon substrate. c) XRD pattern of Si nanoparticles powder where the indices show Si phase.

Besides, Figure 1c shows X-ray diffraction (XRD) pattern with clear, shaped, strong peaks indicating that the particles have high crystallinity. Diffraction peaks for the (111), (220), (311), (400), (331) and (422) planes of Si are clearly present and are consistent with cubic structure (JCPDS No.27-1402).37 Moreover, there are diffraction peaks with a weak intensity in XRD pattern at highest angles. Such as effect is due to the presence of the native oxide layer (SiOx) at the surface of the nanoparticles. This layer has no effect core crystallinity of Si nanoparticles. Additionally, Raman and infrared spectra are presented in Figures S2 and S3 (Supporting Information); they evidenced that the asproduced Si nanoparticles are poorly oxidized at their surfaces. These characterizations prove that the Si nanoparticles (fabricated using a kitchen blender) present a high purity and an excellent crystallinity.


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Controlled-Size of Silicon Nanoparticles As explained before, in order to improve the average particle size and size distribution, the colloidal solution is centrifuged a second time with different rotation speeds at fixed time of 10 min. Eight samples (denoted from A to H) of size-purified Si nanoparticles have been obtained. The procedure for the size separation of colloidal solution of Si nanoparticles is briefly described in scheme S1 and scheme S2 (Supporting Information). The biggest nanoparticles settle in the bottom of the tube while the targeted nanoparticles stay in the supernatant. Thus, by selecting about the top 70% of the supernatant, we are able to remove the undesirable nanoparticles (see the movie in Supporting Information). A photograph of the vials containing Si nanoparticles for all samples is illustrated in Figure 2a. It is clearly observed that the color of the solution changes from dark brown to clear brown depending on the centrifugation speed (from 100 g RCF for big nanoparticles to 2570 g RCF for the smallest nanoparticles), which may be explained by the variation of nanoparticles sizes and concentrations. Then, the size of obtained nanoparticles was analyzed using dynamic light scattering (DLS) to measure the average hydrodynamic


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particle diameter and size distribution. According to DLS results, the average particle diameters decrease from 190 nm to 105 nm as the relative centrifugal force is increased from 100 g (sample A) to 2570 g (sample H), as shown in Figure 2c. The error bars are the standard deviations at one sigma obtained from size distributions analyses, which reduced from 39 % to 19 % when the relative centrifugal force increases. All DLS data are summarized in Table S1 (Supporting Information) and a typical DLS plot of sample H is shown in Figure 2b. We can conclude an improvement of the size distribution of the sample H compared to sample A. Furthermore, the concentrations of final suspensions as a function of relative centrifugal force were calculated using Beer-Lambert law (for more details see Section 2, Supporting Information) and summarized in the Table S1. It is seen from Figure 2d, that the concentration of final suspensions slightly decreases with relative centrifugal force from 3.9.1012 NP.L-1 for the sample A to 1.7.1012 NP.L-1 for the sample H. So the important color change doesn't come only from the nanoparticles concentration, but also from the scattering cross section of the biggest nanoparticles especially present in sample A.


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Figure 2. Size control of silicon nanoparticles. a) Photograph of vials containing Si nanoparticles dispersed in deionized water at different centrifugation speed from 100 g RCF (sample A) to 2570 g RCF (sample H). b) Typical hydrodynamic diameter of silicon nanoparticles dispersed in deionized water of the sample H measured with DLS. c) Average diameters of nanoparticles as a function of relative centrifugal force for different samples obtained with DLS measurements. Error bars indicate standard deviations


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around the average diameter for each point. d) Average concentrations (NPs/mL) as a function of relative centrifugal force for different final suspensions (samples A-H).

To confirm the average diameter of Si nanoparticles measured by DLS, the diameter of several decades of the nanoparticles have been measured from scanning electron microscopy (SEM) images. Typical high-resolution SEM images of Si nanoparticles for sample H are shown in Figure 3a. It is shown that the suspension is rich in Si nanoparticles with a slightly nonspherical shape. The average circularity factor has been estimated to be 81% (see the histogram in Figure S5b of the Supporting Information). This value is compared with the best particles circularity of 96% 38 for gold nanoparticles at the same diameters, but lower than the circularity factor of the quasi perfect circular shape obtained by laser ablation.49 A broad size NPs distribution, ranging from 80 nm to 200 nm, has been measured on SEM images as shown in Figure 3b for sample H. The average size of 120±30 nm (estimated from Gaussian fit) is slightly higher than the diameter measured by AFM: 92±22 nm as shown in Figure S4 (Supporting Information). Note that this value is consistent with the diameter obtained from DLS (105 nm).


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Figure 3. SEM analysis for the sample H. a) Typical SEM images of the Si nanoparticles. b) Statistical histogram of the nanoparticle sizes. The data were collected from 68 Si NPs in SEM images. The dashed line is a Gaussian fit to histogram plot.

Optical Characterization Extinction of Silicon Nanoparticles Dispersions As illustrated above in Figure 2, the diameter of the Si nanoparticles dispersed in deionized water can be precisely controlled via relative centrifugal force. Figure 4a shows the experimental extinction spectra of these dispersions for different relative centrifugal


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force. The extinction spectra reveal a moderate change in shape of the spectrum. We can see a narrowing of the spectrum and blueshift of the extinction peak when the relative centrifugal force increases.30,31 The peak is much narrower in the sample centrifuged at 2570 g (sample H) especially in the long wavelength side, which suggests narrow size distribution of Si nanoparticles as previously reported using microscopies. In the following, we will focus on the sample H.

Figure 4.

Extinction spectra of Si nanoparticles dispersed in deionized water. a)

Normalized extinction spectra of the Si nanoparticles dispersed in water for all samples (A-H). The spectra are stacked one above the other. b) Measured (solid line) and


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simulated (dashed line) normalized extinction spectra of the Si nanoparticles dispersed in deionized water for sample H.

The extinction spectrum of the sample H is rather flat and shows a broad extinction from UV to near infrared (NIR) due to broad size distribution of nanoparticles

28,30,39.

However, since the fabricated Si nanoparticles had a wide size distribution, the overall extinction present a wide-band spectrum due to the overlapping of the narrow extinction peaks of the different sizes family of Si NP. To confirm this prediction, the extinction spectrum of the Si nanoparticles for sample H was analytically calculated using the Mie theory considering the size distribution obtained through AFM morphological analysis (see Figure S4, Supporting Information). The prediction is based on a LogNormal distribution of Mie calculations for each diameter (from d,min for the smaller diameter to d,max for the bigger diameter), written as follows: 𝑑,𝑚𝑎𝑥

𝑄𝑒𝑥𝑡,𝑡𝑜𝑡 = 𝐴

∑𝑄

𝑑,𝑚𝑖𝑛

𝑒𝑥𝑡(𝑑).exp

(

―

(ln (𝑑) ― 𝑑0)2 2∆𝑑2

)


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Figure 4b shows the experimental extinction spectrum and the calculated one. The experimental one shows two small features at 300 nm and 400 nm. A good agreement is found for the wavelength positions of the overlapping electric and magnetic dipolar modes around 400 nm.40 Nevertheless, significant differences appear at low (< 350 nm) and high (> 500 nm) wavelengths, respectively. At low wavelengths, the difference is attributed to intrinsic interband transition inducing absorption in silicon50 and which is not modelized in the scattering spectrum obtained through the Mie theory based calculations. On the other hand, at higher wavelengths, the difference comes from the major contribution of big nanoparticles present in the solution in the scattering spectra. Such big nanoparticles are not found onto the AFM images due to the very low concentration and consequently not taking into account in the calculation.

Scattering Properties of Individual Silicon Resonator To study the scattering properties of individual Si nanoparticle, a drop containing Si nanoparticles was deposited onto a glass substrate. The prepared Si nanoparticles shine colors spanning the whole visible spectrum, which are successively depicted in Figure 5a


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from the dark field microscope images.7,9,41 The corresponding SEM images with their average diameter are shown below. The color is tuned form dark blue for the 84 nm diameter Si NP, to magenta for the 220 nm diameter Si NP through the green and yellow color. The scattering of the biggest NP seems to be a warm white color. The obtained dark-field images of Si NPs were converted into the CIE colorspace, as shown in Figure 5b. Wide-range colors, highly saturated on a dark background, tuning over RGB can be achieved with various diameters of Si Mie resonators. The different colors are obtained from the different diameters of Si NPs. By comparing our results with silicon nanostructures arrays also observed in dark field,16,18 our Si nanoparticles enable a higher colorimetric quality, an improvement in brightness, and a wider gamut of colors. The color space took up by our crystalline silicon nanoparticles represent a large triangle very close to the standard RGB triangle, demonstrating that they can be used as pixels for screens. Such nice result is attributed to the quasi-spherical shape and the crystalline features of Si our nanoparticles. So, the Si NPs could contribute in color purity for all-dielectric printing.


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Figure 5. Dark field images. a) Experimental scattering color visible range of selected Si resonators (top panel) and their corresponding SEM images (bottom panel) for different values of diameters from 84 nm to 220 nm. Inset of each top panel is the average particle diameter. The scale bar is 100 nm. b) CIE1931 chromaticity diagram and experimental colorspace values for light scattering in dark-field for selected Si NPs with different diameters. The standard RGB color gamut triangle values are connected with solid line, and the experimental Si NPs RGB values are connected with dashed line.

Since the positions of Si nanoparticles on a substrate are random when the colloidal solution was drop casted onto a glass substrate, it is therefore necessary to locate their positions to correlate between the scattering spectra and the SEM images. For this purpose, we have developed on the substrate a mesh grid using photolithographic technique (see the Methods for more details) and then we have deposited a droplet of the colloidal solution on the substrate. The main steps are sketched in Figure 6a.


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We selected four different single nanoparticles in each case, and measured their backward and forward scattering spectra by dark-field spectroscopy. Results of these measurements are displayed in figure 6b and figure 6d respectively. The scattering spectra of the corresponding individual Si nanospheres with the diameters obtained from SEM images are computed using Mie theory,42 and are also displayed close to the experimental spectra for parallel analyses. The calculations were performed in effective surrounding medium of refractive index 1.25, given by the average between the air refractive index (n=1.0) and the glass substrate refractive index (n=1.5), and taking into account a 2 nm thick SiO2 layer around the nanoparticle.43 The dark-field and SEM images confirm that the scattering color changes from blue to red with increasing the diameter from 90 to 155 nm. The backward scattering of the smallest nanoparticle, with diameter of 90 nm, shows a unique resonance in the blue part of the spectrum. This resonance wavelength is theoretically associated to the overlapping of both dipolar magnetic (MD) and electric (ED) modes, but dominated by MD resonance. As the diameter increases, the MD peak shifts toward longer wavelengths and become broader.


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Additional resonances appear for bigger NP theoretically attributed to the electric dipole (ED), the magnetic quadrupole (MQ), and the electric quadrupole (EQ) modes.7 The measured forward scattering spectra of four selected single Si nanoparticles with diameters ranging from 110 to 144 nm are shown in Figure 6d. For comparison, the simulation results of forward scattering spectra of spherical Si nanoparticles, under the same conditions as the backward scattering case are also shown. Two resonance modes dominate the forward scattering spectrum, assigned theoretically to MD and ED modes. Quadrupolar modes are not visible experimentally in these conditions. All resonance modes for both backward and forward scattering configurations are found to shift to longer wavelengths with increasing the nanoparticle diameter. This behavior is well accounted by our simulation results as clearly shown in Figure 6c and 6e, respectively. As a matter of fact, the comparison between experiment and theory shows, however, a slight disagreement which manifests itself in the width of the peaks of the aforementioned modes as well as their relative magnitude. This discrepancy arises mainly from the slightly nonspherical shape of nanoparticles (See Figure S5, Supporting Information).9,44-46 A


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nonspherical shape provides different resonances depending on the polarization of the excitation. The global scattering, resulting of the sum of all the polarizations (i.e. all the modes), shows then larger peaks. The Mie theory calculations using a homogeneous medium can also screens the substrate effect, especially in scattering measurements. Indeed, some modes have a higher scattering intensity in a high refractive index medium. Finally, the scattering spectra are collected with 0.8 numerical aperture air objective, giving an incomplete collection of the scattered light.47


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Figure 6. Scattering properties of isolated Si resonators. a) Schematic for the correlation link measurement setup between vivid colors and SEM images of Mie resonators using mesh grid photolithographic technique and drop-casting deposition. b) Measured and


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simulated backward scattering of four different single nanoparticles with diameters ranging between 90 and 155 nm. The inset experiments panel is the dark-field images in reflection mode for each resonator. c) Experimental Mie modes wavelength (dots) as a function of the diameter of the different NPs. The experimental data are compared with simulations (dashed lines) for the magnetic dipole (MD), electric dipole (ED), magnetic quadrupole (MQ), and electric quadrupole (ED) resonances using Mie theory depending on the diameter of Si nanoparticles for backward scattering configuration. d) Measured and simulated forward scattering of four different single nanoparticles with diameters ranging between 110 and 144 nm. The inset experiments panel is the dark-field images for each resonator and the dashed lines follow the evolution of the peaks when the nanoparticle size increases. e) Experimental Mie modes wavelength (dots) as a function of the diameter of the different NPs. The experimental data are compared with simulations (dashed lines) for the magnetic dipole (MD), electric dipole (ED) resonances using Mie theory depending on the diameter of Si nanoparticles for forward scattering configuration.


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CONCLUSIONS We have demonstrated a simple low-cost method for efficient large-scale production of an agglomeration-free colloidal aqueous solution of crystalline silicon nanoparticles with tunable average diameter from 100 nm to 200 nm, using a commercial kitchen blender. The average diameter size and size distribution were controlled by centrifugation process. The optical extinction spectra of silicon nanoparticles colloids were characterized, revealing a broad band from UV to near infrared, due to size distribution. By the dispersion of Si nanoparticles on a glass substrate, the backward and forward scattering properties of single nanoparticles were measured and well-reproduced by the Mie theory in a wide size range. Moreover, the careful study of the colors scattered by the Si-NPs shows that it is possible to address the complete visible colors using our Si resonators. The low-cost fabrication method developed here could be extended to other materials by simply changing the starting bulk materials or adding a surfactant to change the shape of nanoparticles. METHODS


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Preparation of Colloidal Si Nanoparticles and Materials. The silicon lumps (99.9999 % purity) were purchased from Alfa Aesar. The deionized water (DI) produced by a Veolia system with a resistivity at 18.2 MΩ.cm was used throughout all the experiments. Moreover, no surfactant has been used in this work. To simplify the production and minimize cost, the equipment used for silicon nanoparticles fabrication should be as simple as possible. In this work, we propose to use a kitchen blender (ProBlend 6, Philips) to disperse and exfoliate bulk silicon in deionized water in order to obtain silicon nanoparticles. This blender is fitted with a 700 W motor with variable speed control and their impeller consists of six steel blades. A sharpening of the blades can be performed before the grinding to ensure the smallest Si NP diameter. Such blenders are not designed for continuous operation at high speeds for long times due to excess heater. To reduce the increase of temperature and pressure in the glass jar caused by blending at higher revolution speed, the mixer was turned off for two minutes after every three minutes of mixing (see the movie in Supporting Information). 5 g of silicon lumps was weighed and added to the jug. Then, 300 mL of deionized water was also poured onto the jug. The total time of grinding/cooling cycles (3 min ON


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followed by 2 min OFF) It is the optimized parameters to produce agglomeration-free Si NP dispersed in water with an initial concentration around 16 g.L-1. The resultant dispersions were centrifuged using a Sigma 2-16P centrifuge to remove any exfoliated material. The rotor was used at variable speed from 100 g RCF to 2570 g RCF, with a fixed angle (rotor 12151). DLS Measurements. Particle sizes and zeta-potential (ζ) were carried out by dynamic light scattering (DLS) measurements (Zetasizer Nano, Malvern Instruments) using 532 nm Nd:Yag laser opening at backscatter mode at an angle of 173° between sample and detector. The measurements were performed at room temperature. The cuvettes used are the DTS 1070 from Malvern. Morphological and Structural Characterization. Scanning electron microscope (SEM) has been done in a FEG system (Hitachi SU 8030) to characterize the morphological properties of the silicon nanoparticles. The SEM sample was prepared by dropping dispersion of Si colloids on a clean silicon substrate. Atomic Force Microscope (AFM) was carried out on an Agilent 5100 system operated in tapping mode using a silicon AFM tip (Nanosensors, PPP-NCLR-50, force


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constant: 21-98 N/m, resonance frequency: 146-236 kHz). Sample for AFM image were prepared by drop-casting deposition of dispersion on a glass substrate and left to dry in ambient conditions. The crystal phase of the silicon powders was investigated using X-ray diffraction (XRD) with an INEL Equinox 100 diffractometer using CuKα X-ray source radiation (30 kV, 1.5406). Diffraction pattern was collected to 2θ values from 10° to 90°. Optical Characterization. The forward and backward scattering spectra of individual Si nanoparticles were performed with a dark-field optical microscope (Zeiss Axio Imager Z2). In backward-scattering geometry, a white lamp (Halogen 4100K, Philips) was focused on the sample using a 50x dark field objective (numerical aperture, NA = 0.8, Zeiss) to illuminate a single Si nanoparticle. The collection of the signal was performed by the same objective. The collected light is confocally filtered using an optical fiber coupled to a lens. The fiber has a 50 µm core size and the collection zone corresponds to a circle of 3 µm diameter on the substrate. The fiber is connected to the spectrometer Ocean Optics QE65000. The schematic of the dark field optical spectroscopy setup is pictured in ref. [47]. While, in the forward scattering geometry, an oil-immersion dark-field


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condenser with a numerical aperture up to 1.4 was used to illuminate the sample from the substrate side, and an objective (50x, NA=0.8) was used to collect the scattered light in air. As a result, the forward and backward scatterings were measured separately. The scattering spectra were background substrated and normalized by the lamp spectrum. All the scattering experiments were carried out under the same temperature (25 °C) in dark environment. FTIR measurement was performed on PerkinElmer in the wavenumber range 4004000 cm-1 and a Horiba-Jobin Yvon spectrometer was employed to record the Raman spectrum in backscattering geometry with an excitation source at 632.8 nm line of a HeNe laser through a 100×microscope objective (Numerical Aperture, NA=0.9) to the sample surface. Optical UV-Vis extinction spectra were recorded with a Varian Cary-100 spectrometer in quartz cuvettes with a path length of 1 cm over the wavelength range of 300 nm to 850 nm. Two light sources have been used namely tungsten-halogen visible source with quartz window and a deuterium arc ultraviolet source, respectively. The light detection


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was recorded using high performance R928 photomultiplier tube detector. Cuvette with deionized water was used as a reference for calibrating extinction colloidal measurement. Photolithography Technique. To locate position of the silicon nanoparticles on a substrate, we have developed a grid mesh on a glass substrate by photolithographic technique. We use photoresists S1813 with under-cut structures by mask aligner MJB4 (Suss MicroTec) and a MF319 developer. Finally, the residual photoresist could be removed by acetone and sonication. Numerical Simulations. All the numerical calculations have been made the Mie theory. The dielectric function of silicon was obtained from Palik.48

ASSOCIATED CONTENT Supporting Information.

This Supporting Information is available free of charge via the Internet at http://pubs.acs.org


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The supporting information file contains: Section 1: Size separation process by centrifuge, Section 2: Determination of the particles concentration in the final suspensions, Section 3: Zeta-potential distribution of sample H, Section 4: Raman spectroscopy of individual Si nanoparticle, Section 5: FTIR analysis of Si NPs powder, Section 6: AFM measurement. Section 7: Shape analysis of Si NPs.

Also available: A short movie clearly explaining all the procedure to produce our Si Mie resonators.

AUTHOR INFORMATION Corresponding Authors

#E-mail: [email protected]

#E-mail : [email protected]

ACKNOWLEDGEMENTS

Financial support of Nano’Mat (www.nanomat.eu) by the Ministère de l’enseignement supérieur et de la recherche, the “Fonds Européen de Développement Régional (FEDER)


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fund”, the “region Grand-Est”, and the “Conseil général de l’Aube” are acknowledged. Parts of this project were supported by the Tunisia Alternation Scholarship, the Fondation UTT, and the Agence nationale de la recherche (ANR), Contract NATO (ANR-13-BS100013). This work has been supported by the EIPHI Graduate School (contract "ANR-17EURE-0002").

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Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators

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