Size Dependent Plasmonic Mode Evolution and SERS Performance of

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C: Plasmonics; Optical, Magnetic, and Hybrid Materials

Size Dependent Plasmonic Mode Evolution and SERS Performance of #-Sn Nanoparticles Bin Li, Han-Han Wu, Paifeng Luo, Kui Lin, Jigui Cheng, Honghai Zhong, Yang Jiang, and Ying-Wei Lu J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b10851 • Publication Date (Web): 07 Dec 2018 Downloaded from http://pubs.acs.org on December 18, 2018

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The Journal of Physical Chemistry

Size Dependent Plasmonic Mode Evolution and SERS Performance of β-Sn Nanoparticles Bin Li†, Han-Han Wu†, Pai-Feng Luo†, Kui Lin‡, Ji-Gui Cheng†, Hong-Hai Zhong†, Yang Jiang†, and Ying-Wei Lu*,† †School

of Materials Science and Engineering, Hefei University of Technology, Hefei

230009, P. R. China ‡Analysis

Center, School of Materials Science and Engineering, Tianjin University,

Tianjin 300072, P. R. China

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ABSTRACT: Well crystallized β-Sn nanoparticles with different diameters have been prepared by a wet chemical method at different reaction temperatures. Both optical characterizations and finite element simulations confirmed that higher order resonance modes will appear when the size of nanoparticles is getting bigger and the plasmon resonance absorption peaks resulting from all resonance modes will keep red-shifting with the increasing of the size of nanoparticles. In addition, surface enhanced Raman scattering measurements and corresponding calculations indicate that β-Sn nanoparticles could reveal near-field enhancement effect and therefore could be an alternate efficient plasmonic material for the Si-based optoelectronic and/or photovoltaic devices.

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INTRODUCTION It is well known that the novel metal nanoparticles (NPs), such as Au and Ag NPs, have been studied intensively due to their potential applications in the fields of chemical and biologic sensors, optoelectronic and photovoltaic devices and so on, thanks to their localized surface plasmon resonance (LSPR) performance, especially the ability to near-field enhancement (NFE).1-4 However, the commonly used plasmonic Au and Ag NPs are suffering from either the high loss due to interband transitions in the visible range (Au NPs) or the poor chemical stability and high toxicity (Ag NPs).5,6 In addition, the incompatibility with the standard Si manufacturing processes restricts their applications in microelectronics since the plasmonic materials are required to be embedded in Si as NFE works.7 Intuitively, metallic Sn (β-Sn) could be a perfect alternative candidate because it not only shows metallic characteristics, but also is electrically neutral in Si. Some theoretical and experimental works have been carried out and confirmed that β-Sn NPs could support the size- and shape-dependent LSPR and therefore could be employed as surface enhanced Raman scattering (SERS) detections.8-13 However, the near-field effect and the mode evolution of such unconventional plasmonic material have not been sufficiently studied yet, let alone the explorations of correlativity between the near-field effect and the SERS performance. In this work, well-crystallized β-Sn NPs with different diameters have been synthesized at different temperatures through a facile liquid phase method. Both optical characterizations and finite element simulations reveal the size-dependent LSPR and corresponding mode evolution performance of β-Sn NPs. Furthermore, in the presence of β-Sn NPs, the SERS signals from R6G due to near-field effect have been detected, implying that the tunable plasmonic β-Sn NPs could play an important role in the Sibased optoelectronic and/or photovoltaic devices. 3 / 14



EXPERIMENTAL SECTION Chemicals. Tin (II) chloride (SnCl2·2H2O, 98%, AR), diethylene glycol (DG, C4H10O3, 99%, AR), polyvinylpyrrolidone (PVP, NW=40000), and sodium borohydride (NaBH4, 99%, AR) were purchased from Sinopharm and used without further purification. Synthesis of β-Sn NPs. The typical synthesis process was started with the preparation of a DG solution by dissolving 0.3 g of SnCl2·2H2O and 1.5 g of PVP in 30 ml of DG at room temperature. Then the solution was heated up to a certain temperature in Ar atmosphere. Subsequently, 20 ml of NaBH4 solution with a concentration of 0.02 mol/L was added dropwise into the heating solution under stirring. After 30 min of reaction at the given temperature, the resulting solution was cooled down and then was centrifuged at 8000 rpm for 3 times (each time for 20 min) to obtain the nanoparticles. During the whole procedure, several reaction temperatures, which were 75, 85, 105 and 120 ˚C, respectively, were employed, and thus the corresponding samples were named as Sn75, Sn85, Sn105 and Sn120, respectively. Determination of near-field and far-field performance of β-Sn NPs. In order to verify the accuracy of the optical characterizations, finite element method (FEM) was performed to calculate the absorption cross-sections of β-Sn NPs with different sizes by integrating the time-averaged extinction Poyting vectors over an auxiliary surface enclosing the NPs and the needed optical parameters were derived from Reference 14. As for the near-field effect, a NFE spectroscopy defined in Reference 15, 16 had been applied to extract the resonance energy where a maximum NFE can be achieved. As the results, the average local near-field enhancement factor (NFEF) and typical surface charge distributions at the resonance energies could be obtained. RESULTS AND DISCUSSION 4 / 14


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XRD patterns of all samples along with a standard pattern of β-Sn (PDF#89-2761) have been shown in Figure 1, where can be clearly seen that all samples are wellcrystallized and their diffraction peaks perfectly agree with those of standard β-Sn. In addition, among all samples, Sn105 presents sharpest diffraction peaks, implying that β-Sn NPs in Sn105 might have largest average size and best crystallinity. Taking advantage of Scherrer equation, Table 1 summarized the calculated diameters of β-Sn NPs in different samples, and the results indicate that the average size of β-Sn NPs will increase with the reaction temperature in the beginning and reach the maximum of around 126 nm when the reaction temperature is 105 ˚C.

Figure 1. XRD patterns of all samples. Table 1. Average diameters of β-Sn NPs synthesized at different temperatures

sample IDs

Sn75

Sn85

Sn105

Sn120

calculated diameters (nm)*

4.3±0.4

38.1±3.0

126.3±11.2

77.4±3.0

statistic diameters (nm)

13.2±0.4

-

-

92.4±3.1

* The calculated diameters were carried out by the XRD equipped software (JADE).

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Figure 2. TEM images of Sn75 (a, b) and Sn120 (c, d). The insets in (a) and (d) are the size distributions of Sn75 and Sn120, respectively. The inset in (d) is the SAED pattern of Sn120.

Figure 2(a) and 2(c) show the morphologies and size distributions of Sn75 and Sn120, which were obtained at the lowest (75 ˚C) and highest (120 ˚C) reaction temperatures, respectively. It can be seen that there are many sphere-like nanoparticles in the two samples, and the average diameters of both samples are larger than the calculated values shown in Table 1. Such deviation could be due to the oxidation of βSn NPs and have been confirmed by the high resolution TEM (HRTEM) images. Figure 2(b) and 2(d) show that both Sn75 and Sn120 were surrounded by an oxide layer with a constant thickness of around 5 nm. Taking this amorphous layer into account, the statistic average diameters agree with the calculated values quite well, implying the obtained average sizes through two different ways are identical. Furthermore, the HRTEM images shown in Figure 2(b) and 2(d) reveal that the interplanar spacings in both Sn75 and Sn120 are 0.29 nm, which matches the (200) lattice plane of β-Sn well.

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In addition, the SAED pattern of Sn120 shown in the inset of Figure 2(d) further confirmed the single crystalline nature of β-Sn NPs.

Figure 3. (a) Measured absorption spectra of all samples. (b) Finite element simulated absorption spectra of β-Sn NPs with corresponding diameters. Size-dependent NFEF (c) and surface charge distributions (d) of β-Sn NPs.

It is well known that the frequency of LSPR of metallic NPs will change with their sizes. Plasmon absorption performance of all samples was therefore characterized and the spectra are shown in Figure 3(a). Clearly, for Sn75, the sample contains the smallest β-Sn NPs, there is only one broad absorption peak centered at around 200 nm, which can be attributed to the dipolar resonance mode of β-Sn.17 When the reaction temperature increases, the obtained samples (Sn85, Sn105 and Sn120) with larger NPs reveal at least two LSPR peaks, which is reasonable and can be attributed to dipole 7 / 14



(with lower energy) and quadrupole (with higher energy) resonance modes, respectively, according to Mie theory. In addition, both dipole and quadrupole resonance modes keep red-shifting when the size of NPs is getting bigger, which agrees with what finite element simulated well. Indeed, as shown in Figure 3(b), the simulated absorption spectra reveal the identical features and variation trend with the measured ones that shown in Figure 3(a). To further shed light on the size-dependent near-field effect and corresponding resonance mode evolution, the average near-field enhancement factor (NFEF) and surface charge distributions of β-Sn NPs with different diameters were simulated by finite element method (FEM) and the results are shown in Figure 3(c) and (d), respectively. Obviously, the variation trend of the features of resonance modes, including mode amount and corresponding resonance wavelength, shown in Figure 3(c) is similar to what has been shown in Figure 3(a) and (b), except for the spectrum extracting from the largest β-Sn NP with a diameter of 100 nm (the blue diamond line). It can be seen that there are one peak and two shoulders at 500, 280 and 200 nm, respectively (pointed by blue arrows), which can be assigned to dipole, quadrupole and octupole resonance modes, respectively.18 It is reasonable since different surface charge distributions will be induced under the resonance wavelengths from β-Sn NPs with different sizes.19 As shown in Figure 3(d), the largest β-Sn NP with a diameter of 100 nm reveals three kinds of surface charge distribution patterns when it is excited under three different resonance wavelengths of 500, 280, and 200 nm, respectively, which are extracted from Figure 3(c). As for the smallest β-Sn NP with a diameter of 13.2 nm, only typical dipole resonance mode can be induced. While for β-Sn NPs with diameters of 50 and 80 nm, two resonance modes can be excited, which can be attributed to dipole and quadrupole resonance modes, respectively. In addition, the wavelength that can 8 / 14


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induce the maximum of NFEF keeps red-shifting with the size of NP as well, implying that the tunable NFE ability can be achieved by adjusting the diameter of β-Sn NPs.

Figure 4. (a) Raman spectra of R6G solutions with and without β-Sn NPs. (b) Average enhancement factor (EF) and grain size as a function of all samples.

In order to test the near-field enhancement effect and explore the potential application of β-Sn NPs, Raman spectra of R6G solutions with and without β-Sn NPs were detected by using a laser confocal Raman spectrometer (LabRam HR Evolution, JOBIN YVON) with a excitation wavelength of 633 nm and the results are shown in Figure 4(a). It can be seen that the Raman signals from R6G solutions with β-Sn NPs are higher than that from the pure R6G solution with the same R6G concentration. Based on these spectra, the average enhancement factor, EF, was calculated as following equation20: EF = (𝐼𝑆𝑛 𝐼0)(𝑁0 𝑁𝑆𝑛)

(1)

where 𝐼𝑆𝑛 and 𝐼0 are the average intensities of three peaks at 613, 1364 and 1512 cm1

from R6G solutions with and without β-Sn NPs, respectively; while 𝑁𝑆𝑛 and 𝑁0 are

the R6G concentrations of solutions with and without β-Sn NPs, respectively.

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Considering the concentrations of R6G in both cases are identical, the above equation therefore can be simplified as following equation: EF = 𝐼𝑆𝑛 𝐼0

(2)

The calculated results are shown in Figure 4(b), where can be seen that the value of EF increases with the reaction temperature in the beginning, then reaches the maximum of 1.3±0.02 when the reaction temperature is 105 ˚C. Afterwards, when the temperature goes to higher, the EF value decreases again. Such EF variation tendency agrees with the size changing as shown in Figure 4(b), indicating that the larger β-Sn NPs was obtained, the better SERS performance could be achieved, which is reasonable since Figure 3(c) has shown that the larger β-Sn NPs could reveal stronger NFE at the wavelength of 633 nm. CONCLUSIONS In summary, well-crystallized β-Sn NPs with different diameters have been prepared through a solution route at different reaction temperatures and confirmed by XRD and TEM characterizations. Both optical measurements and finite element simulations indicate that the variation trend of LSPR performance and mode evolution with size agree with the classical Mie theory. In addition, SERS characterizations and corresponding calculations confirm that β-Sn NPs can reveal near-field enhancement effect and therefore could be an alternate efficient plasmonic material in the field of Sibased optoelectronics and/or photovoltaics. AUTHOR INFORMATION Corresponding Author 10 / 14


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*E-mail: [email protected] ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (61675061, 11774077 and U1532140) and the Project Funded by China Postdoctoral Science Foundation (2015M581978). REFERENCES (1) Ferhan, A. R.; Jackman, J. A.; Cho, N.-J. Probing Spatial Proximity of Supported Lipid Bilayers to Silica Surfaces by Localized Surface Plasmon Resonance Sensing. Anal. Chem. 2017, 89, 4301-4308. (2) Yuan, H.-Z.; Ji, W.; Chu, S.-W.; Qian, S.-Y.; Wang, F.; Masson, J.-F.; Han, X.-Y.; Peng, W. Fiber-Optic Surface Plasmon Resonance Glucose Sensor Enhanced with Phenylboronic Acid Modified Au Nanoparticles. Biosens. Bioelectron. 2018, 117, 637-643. (3) Takahata, R.; Yamazoe, S.; Koyasu, K.; Imura, K.; Tsukuda, T. Gold Ultrathin Nanorods with Controlled Aspect Ratios and Surface Modifications: Formation Mechanism and Localized Surface Plasmon Resonance. J. Am. Chem. Soc. 2018, 140, 6640-6647. (4) Tang, X.; Ackerman, M. M.; Guyot-Sionnest, P. Thermal Imaging with Plasmon Resonance Enhanced HgTe Colloidal Quantum Dot Photovoltaic Devices. ACS Nano. 2018, 12, 7362-7370. (5) Naik, G. V.; Shalaev, V. M.; Boltasseva, A. Alternative Plasmonic Materials: Beyond Gold and Silver. Adv. Mater. 2013, 25, 3264-3294. (6) Abramenko, N. B.; Demidova, T. B.; Abkhalimov, E. V.; Ershov, B. G.; Krysanov, E. Y.; Kustov, L. M. Ecotoxicity of Different-Shaped Silver Nanoparticles: Case of Zebrafish Embryos. J. Hazard. Mater. 2018, 347, 89-94. (7) Atwater, H. A.; Polman, A. Plasmonics for Improved Photovoltaic Devices. Nature Mater. 2010, 9, 205-213.

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(18) Huang, Y.; Ma, L.-W.; Hou, M.-J.; Li, J.-H.; Xie, Z.; Zhang, Z.-J. Hybridized Plasmon Modes and Near-Field Enhancement of Metallic Nanoparticle-Dimer on a Mirror. Sci. Rep. 2016, 6, 30011. (19) Kooij, E. S.; Ahmed, W.; Zandvliet, H. J. W.; Poelsema, B. Localized Plasmons in Noble Metal Nanospheroids. J. Phys. Chem. C. 2011, 115, 10321-10332. (20) Orendorff, C. J.; Gole, A.; Sau, T. K.; Murphy, C. J. Surface-Enhanced Raman Spectroscopy of Self-Assembled Monolayers: Sandwich Architecture and Nanoparticle Shape Dependence. Anal. Chem. 2005, 77, 3261-3266.

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Figure 2. TEM images of Sn75 (a, b) and Sn120 (c, d). The insets in (a) and (d) are the size distributions of Sn75 and Sn120, respectively. The inset in (d) is the SAED pattern of Sn120. 149x102mm (300 x 300 DPI)


Size Dependent Plasmonic Mode Evolution and SERS Performance of

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