Tunable Chiroptical Response of Chiral Plasmonic Nanostructures

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Tunable Chiroptical Response of Chiral Plasmonic Nanostructures Fabricated with Chiral Templates Through Oblique Angle Deposition Tong Fu, Yu Qu, Tiankun Wang, Gang Wang, Yongkai Wang, Hui Li, Juan Li, Li Wang, and Zhongyue Zhang J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b10833 • Publication Date (Web): 03 Jan 2017 Downloaded from http://pubs.acs.org on January 7, 2017

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The Journal of Physical Chemistry

Tunable Chiroptical Response of Chiral Plasmonic Nanostructures Fabricated with Chiral Templates Through Oblique Angle Deposition Tong Fu, Yu Qu, Tiankun Wang, Gang Wang, Yongkai Wang, Hui Li, Juan Li, Li Wang, Zhongyue Zhang* School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 China

ABSTRACT: Chiral plasmonic nanostructures (CPNs) with a strong chiroptical response in visible and near-infrared regions were fabricated with homemade SiO2 chiral templates through oblique angle deposition. The circular dichroism spectra of the CPNs showed that the chiroptical response was amplified with increased deposition thickness of silver. Simulation results demonstrated that only the magnetic dipole mode was excited when the deposition thickness was small. Magnetic and electric dipoles emerged and coupled with each other with increased silver deposition thickness. As a result, chiroptical enlargement occurred. This study provides a concise method of fabricating CPNs with a tunable chiroptical response.

*E-mail: [email protected]

ACS Paragon Plus Environment

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1. INTRODUCTION A structure is chiral when it cannot be overlapped with its mirror image. Chirality is a fundamental feature of living things and perhaps even a must for life. All amino acids are chiral except for glycine, and all of them exist in one possible handedness. Electromagnetic waves can also be chiral according to the photon spin, that is, left circularly polarized (LCP) and right circularly polarized (RCP) light. Circular dichroism (CD) is the difference in the absorption coefficient when a chiral structure interacts with a different chiral electromagnetic wave.1, 2 Most naturally occurring chiroptical systems originate from the coupling between the electric and magnetic dipoles in the chiral medium;1 this coupling is usually weak. Many studies have shown that chiral plasmonic nanostructures (CPNs) lead to significant chiroptical effects and have resulted in several completely new concepts and applications in physics, such as negative refraction,3–5 broadband circular polarization,6 and biosensing.7–9 The most straightforward image of chiral configuration is the helix,6,

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and a strict helix

presents broadband chiroptical properties in the near-infrared (IR) region because of standing wave superposition.6 Utilizing individual nanoparticles or nanorods to replace the helix is an insightful and easy approach to achieve 3D chiral configurations.11–15 The chiral plasmonic mode has been explored by tuning the inter-distance of particles.12 Another typical type of 3D CPNs is bilayer, twisted nanostructures, in which magnetic and electric resonances arise simultaneously; these structures present a remarkable chiroptical response.8,16 2D CPNs cannot be superposed with their mirror images through in-plane rotations and translations.17–20 The chiroptical response of 2D CPNs is comparably weak because they only have the electric or magnetic oscillation mode. Switching of chiroptical modes usually necessitates the remake of CPNs12 or modification of their configuration.21 According to a recent study, the magnetic and electric responses of


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stacked metallic U-shaped resonators can be switched by changing the polarization of incident light.16 However, the fabrication method (electron beam lithography) of such CPNs is time consuming and expensive.12, 16, 21 Oblique angle deposition (OAD) is regarded as an industrial technique to prepare CPNs due to its low cost and scalability. With the assistance of shadowing templates, diverse CPNs with chiroptical response located in visible and near-IR regions have been fabricated.14, 22–26 Yet, the chiroptical mode of such CPNs is monotonous, therefore the strength of chiroptical is hardly manipulated. A chiral template-assisted method was proposed in the present study. CPNs were fabricated with homemade chiral templates on polystyrene (PS) nanosphere through OAD. The chiroptical mode and the strength of the chiroptical response of CPNs can be adjusted easily by changing the deposition thickness of silver (Ag) because of the use of chiral templates. By increasing the deposition thickness of Ag, the chiroptical mode switched from magnetic dipole mode to electric and magnetic dipole coupled mode. As a result, the strength of the chiroptical response increased correspondingly. CPNs can be achieved with a wide choice of materials because of the versatility and tunability of chiral templates. Moreover, the CPNs are applicable in diverse areas due to the concise fabrication process. 2. EXPERIMENTAL SECTION The fabrication scheme is shown in Fig. 1. Self-assembled PS nanosphere monolayers with a diameter of 380 nm were prepared on glass substrates through the air–water interface technique. Details on PS nanosphere monolayer preparation are presented in Supporting Information Section S1. Three steps of deposition are needed to fabricate the CDNs. Depositions of SiO2 (two steps) onto the monolayer substrate were conducted through OAD to form the chiral templates. Both depositions adopted the same tilt angle of θ = 86° with respect to the normal substrate


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(Figs. 1a and 1b). The angle of substrate azimuthal orientation was defined as φ and shown in Fig. 1a. For right-handed templates, the rotation of ∆φ was ∆φ = −90° and that for left-handed templates was ∆φ = 90° (Fig. 1b). The deposition thicknesses were set as T1 = T2 = 60 nm for the first and second depositions. The last stage was the normal incident deposition of Ag on chiral templates to form the left-handed CPNs (L-CPNs), as shown in Fig. 1c, where the deposition thickness was set as T3. The set deposition thicknesses of T1, T2, and T3 were monitored by a quartz crystal microbalance positioned at normal incidence to the vapor source in OAD (refer to Supporting Information Section S1 for further details). 3. RESULTS & DISCUSSION The CPNs possessed a distinct morphology in the large-scale area; this is because they have different orientations at the micro-scale, details can be found in our previous study.26 Scanning electron microscopy (SEM) images with the typical morphology of L-CPNs are shown in Fig. 2 at various deposition thicknesses. The SEM image with T3 = 10 nm is shown in Fig. 2a. On one hand, the Ag on the chiral templates of SiO2 formed an L-shaped structure and separated with the Ag on the nanosphere (artificially colored light blue in the figure insets). On the other hand, the Ag on the nanosphere was not a strict film but separated Ag islands (artificially colored light red in the figure insets). Minimization of surface energy causes Ag atoms to condense onto the surface of the nanosphere; these atoms then present a tendency to form separated islands.27, 28 Subsequent Ag vapor flux was filled in the gap of Ag islands with increasing T3, and the Lshaped structure connected the Ag onto the nanosphere (Fig. 2b). The L-CPNs became a strict film when T3 = 20 nm, and almost all the Ag islands were connected with one another, as shown in Fig. 2c. Fig. 2d shows the transmission electron microscopy (TEM) image of a single L-CPN on nanosphere. The Ag film split in the outer edge of SiO2 chiral templates because the growth


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direction of SiO2 chiral templates is along the outward direction of nanosphere. This split is clearly identified from the TEM image (additional TEM images are provided in Fig. S1). All CD spectra were measured with photon normal incidence with respect to the substrate, as illustrated in Fig. 3a. The unpolarized absorption of the PS nonosphere, the SiO2 chiral templates, and CPNs with T1 = T2 = 60 nm and T3 = 10 nm are depicted in Fig. 3b. All spectra showed an absorption peak at around λ = 520 nm (marked by dashed arrow and “PS” in Fig. 3b), which signifies the first diffracted order of 2D close-packed monolayer arrays.29 The unpolarized absorption of CPNs showed no distinct handedness-dependent feature, as indicated in Fig. 3b. A broad peak appeared at λ = 620 nm, and this peak corresponds to the localized surface plasmon resonance (LSPR) of the Ag film. The CPNs showed a distinct chiroptical response at around λ = 550 nm. The L-CPNs exhibited positive rotation in the visible range from 500–700 nm, which implies that the absorption of LCP light was stronger than that of RCP light. The maximum amplitude of +0.434 deg was reached at λ = 560 nm. The R-CPNs, as expected, showed an opposite trend of rotation and reached the maximum amplitude of −0.541 deg at λ = 565 nm. The chiroptical response of CPNs did not result from the chiral templates nor from induced chiral current in the Ag film by chiral templates as verified in Supporting Information Sections S3 and S4. Moreover, a series of experiments was conducted to demonstrate that the optical properties of linear dichroism and linear birefringence are negligible (see Supporting Information Section S5). This is reasonable for hexagonal close-packed CPNs on the PS nanosphere are isotropic at the macro-scale, even if they have different orientations at the micro-scale. To show how the deposition thickness of Ag influences the CD signal, the CD spectra with increasing T3 are presented in Fig. 4b. With T3 increasing from 10 nm to 15 nm, the magnitude of the CD peak significantly increased from +0.434 deg and −0.541 deg to +0.814 deg and −0.839


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deg for L-CPNs and R-CPNs, respectively. Furthermore, the CD peak red-shifted to a wavelength of around λ = 610 nm. The same trend was displayed when T3 was further increased, and the position of the CD peak reached its peak at λ = 625 when T3 = 20 nm. The CD peak remained at λ = 625 nm when T3 = 25 nm (Fig. S6). Dissymmetry factor g is a parameter to evaluate the chirality of a chiral structure and is a dimensionless quantity factor. The g factor is defined as g = ∆A/A, where ∆A = CD (deg)/33 is the differential absorption between LCP and RCP light and A is the unpolarized absorption. For the CPNs, the g factor was also calculated, as shown in Fig. 4c. The magnitude of the g factor is higher than 0.03 around the peak and is comparable with those in recent studies.23 Quantitative analysis of CD spectra with increasing T3 is shown in Fig. 5. The position of the CD peak red-shifted with increasing T3 and reached its peak when T3 = 25 nm, as shown in Fig. 5a. However, the value of the CD peak displayed trends different from that of position. Figure 5b clearly shows that the values of the CD peaks increased with increasing T3, even when T3 = 25 nm. Enlargement and red-shifting of the LSPR mode of Ag occurred with increasing T3, as marked by solid arrow in Fig. 5c. These phenomena are related to the enlargement and redshifting of the chiroptical response. Moreover, given the use of chiral templates, the plasmonic material only required normal incident evaporation. The effect of the surface diffusion of the incident material can be eliminated,30 so a wide choice of materials can be used to fabricate CPNs (Supporting Information Section S7). Three models were simulated with the finite element method (FEM) to interpret the experimental results (see Supporting Information Section S8 for further details). The simulated geometric models are based on SEM and TEM images, which are shown in Fig. 6a. The thickness of the chiral templates of the SiO2 layer was estimated to be 30 nm (see Supporting


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Information Section S3). CPNs were assumed as L-shaped structures on L-shaped SiO2 when T3 = 10 nm, and the influence of the Ag island on the nanosphere was ignored (Fig. 6a). The size distribution of Ag islands was shown in Supporting Information Section S8 along with the absorption spectrum of the Ag islands with average size. The absorption peak is located at λ = 485 nm. Therefore, the Ag islands did not contribute to the chiroptical response. The thickness of the L-shaped structure was t1 = 10 nm. As T3 approached 15 nm, the influence of the Ag film on the nanosphere was considered and simplified as a disk that connects to the L-shaped structure on the inner side but splits on the outer side of the L-shaped structure. The thickness and radius of the disk were t2 = 10 nm and r = 150 nm, respectively. When T3 = 20 nm, the parameters were set as t1 = t2 = 12 nm and r = 180 nm. The CD spectra were defined similarly as the experimental one (∆A = ALCP − ARCP) in the simulation. The L-shaped structure showed a CD peak with a maximum of ∆A = 0.059 at λ = 570 nm, which means that ALCP is larger than ARCP (Fig. 6b). When the L-shaped structure was connected with the disk with r = 150 nm, the CD peak remarkably increased to ∆A = 0.122, and the position of the CD peak red-shifted to λ = 577 nm. When r = 180 nm together with t1 = t2 = 12 nm, the CD signal enlarged to ∆A = 0.163, namely, 2.8 times that of the L-shaped structure with thickness t1 = 10 nm, and red-shifting occurred from λ = 570 nm to λ = 585 nm. The simulation results presented similar trends of enlargement and red-shifting as the experimental results. To determine the chiroptical mechanism of CPNs with different thicknesses, Fig. 7 shows the calculation absorption spectra for LCP and RCP light excitation as well as the ∆A spectra. Figures 7c and 7d show the near-field charge distributions of the L-shaped structure at λ = 570 nm for both excitation polarization. The equivalent current is marked with black-dashed arrows. It can be clearly observed that the near-field charge is mainly distributed on the surface of the


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CPNs. Only the magnetic dipole mode was excited for the L-shaped structure under the excitation of LCP and RCP light. Under LCP light excitation, the magnetic dipole was around the entire L-shaped structure (Fig. 7c). However, under RCP light excitation, the magnetic dipole mainly resided in one arm of the L-shaped structure (Fig. 7d). The chiroptical mode was distinctly altered from that of the L-shaped structure when the L-shaped structure was connected with the disk. The equivalent current in the L-shaped structure coupled with that in the disk and formed a magnetic dipole moment, and an electric dipole appeared on the other side of the disk (Figs. 7g and 7h). Equivalent magnetic and electric dipole moments are marked by black solid arrows and translated to the bottom part of Figs. 7g and 7h. The angle between the electric and magnetic dipole moments is less than 90° for both LCP and RCP excitations (Figs. 7g and 7h). The enlargement and red-shifting of the chiroptical response when T3 increased can be attributed to two facts. First, only magnetic dipole can be excited when T3 is small, and the CD response is weak. Both magnetic and electric dipoles are excited when T3 is increased; they couple with each other and result in the enlargement of the CD response. Second, the L-shaped structure connects with the Ag film on the nanosphere, the dimension of which increases with increasing T3. Thus, the electric resonance length of the electric dipole moment increases and causes the red-shift. The simulation enlargement is larger than that of the experimental one because of the cancellation effect caused by the random orientation of the PS array in the experiment.24 The limitation of the red-shift in the spectra is due to the CPNs reaching the dimension limitation, which is the dimension of the nanosphere. Moreover, the red-shift in the simulation results is weaker than that in the experimental one because the electric resonance length in the experiment is on the curved Ag shell, which is larger than the disk in the simulation.


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4. CONCLUSION Large-scale CPNs were fabricated with homemade chiral templates. Both experimental and simulation results showed a tunable chiroptical response in the visible to near-IR regions. The simulation results revealed that the use of chiral templates caused the CPNs to possess a tunable chiroptical mode by tuning the deposition thickness of Ag. Only the magnetic dipole was excited when deposition thickness of Ag was small. Increasing the deposition thickness resulted in both electric and magnetic dipoles being excited and coupling with each other, thus causing the CD response become stronger. This result provides a concise method to fabricate CPNs with a tunable chiroptical response mode. Moreover, CPNs can be fabricated with a wide choice of materials because of the versatility of chiral templates. The chiral electric field is mainly on the surface of CPNs, which could be used in the application of sensors to amplify the CD signal of chiral molecules. The versatility of chiral templates and the tunable chiroptical mode make the application of CPNs in diverse areas very promising.

ASSOCIATED CONTENT Supporting Information Available: This material is available free of charge on the ACS Publications website http://pubs.acs.org. Experimental and simulation details, TEM and SEM images and additional CD spectra.

Corresponding Author Zhongyue Zhang


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School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 China, E-mail: [email protected], Phone: 86-029-81530764.

Conflict of interest: The authors declare no competing financial interest.

Acknowledgements This work was supported by National Nature science Foundation of China (NSFC) (Grant No.61575117). Fundamental Research Funds for the Central Universities of Ministry of Education of China (Grant No. GK201601008). Innovation Fund for graduate students of Shaanxi Normal University (Grant No. 2016CSZ013) and Foundation for Excellent PhD Dissertation of Shaanxi Normal University (Grant No. X2014YB08).

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FIGURES

Figure 1. Schematics of the fabrication process (a) shadow growth of first SiO2 layer; (b) shadow growth of second SiO2 layer to form left-handed chiral templates (bottom is top view of left handed chital template); (c) normal deposition of Ag layer to form left handed CPNs (bottom shows L-CPNs viewed from different angle ).

Figure 2. SEM image and TEM image of CPNs. SEM images showing L-CPNs with fixed parameters of T1 = T2 = 60 nm and different T3: (a) T3 = 10 nm, (b) T3 = 15 nm and (c) T3 = 20 nm. All scale bars in (a), (b) and (c) represent 200 nm. TEM image of single L-CPN on nanosphere with parameter of T1 = T2 = 60 nm and T3 =20 nm.


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Figure 3. Optical properties of CPNs with T3 = 10 nm. (a) Schematic of CD measurements; (b) absorption spectrum and (c) CD spectrum.

Figure 4. Optical activities of CPNs with different deposition thickness of silver. (a) Top-view SEM images show various silver thickness of CPNs on PS nanosphere. All scale bars represent 200 nm; (b) CD and (c) g-factor spectra for L-CPNs and R-CPNs are shown with same order of silver thickness as SEM images.


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Figure 5. Quantitative analysis of CD response as function of deposition thickness of silver. (a) The plots of position of CDmax versus deposition thickness; (b) The plots of CDmax versus deposition thickness. (c) Absorption spectra with different deposition thickness of silver.

Figure 6. FEM simulation of the chiroptical of CPNs. (a) Schematics evolution of geometric models based on SEM and TEM images, as shown in insets the white areas and the blue areas represent the silver and SiO2, respectively; (b) Calculated CD spectrum of L-shaped chiral structure with t1 = 10 nm, (c) CPNs with t1 = 10 nm, t2 = 10 nm and r = 150 nm and (d) CPNs with t1 = 12 nm, t2 = 12 nm and r = 180 nm, insets show the calculation structure relate to the CD spectra.


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Figure 7. Circular polarized absorption spectra of (a) left-handed L-shaped chiral structure and (e) L-CPNs; CD spectra of (b) left-handed L-shaped structure and (f) L-CPNs. Near-field charge density distributions of L-shaped structure (c) and (d), as well as L-CPNs (g) and (h) under LCP and RCP excitation at resonant wavelength. The parameter of L-shaped structure is t1 = 10 nm; the parameters of CPNs are t1 = 10 nm, t2 = 10 nm, and r = 150 nm. Equivalent magnetic dipole moment and electric dipole moment are marked by green arrows.


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Figure1. Schematics of the fabrication process (a) shadow growth of first SiO2 layer; (b) shadow growth of second SiO2 layer to form left-handed chiral templates (bottom is top view of left handed chital template); (c) normal deposition of Ag layer to form left handed CPNs (bottom shows L-CPNs viewed from different angle ).


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Figure2. SEM image and TEM image of CPNs. SEM images showing L-CPNs with fixed parameters of T1 = T2 = 60 nm and different T3: (a) T3 = 10 nm, (b) T3 = 15 nm and (c) T3 = 20 nm. All scale bars in (a), (b) and (c) represent 200 nm. TEM image of single L-CPN on nanosphere with parameter of T1 = T2 = 60 nm and T3 =20 nm.


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Figure3. Optical properties of CPNs with T3 = 10 nm. (a) Schematic of CD measurements; (b) absorption spectrum and (c) CD spectrum.


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Figure4. Optical activities of CPNs with different deposition thickness of silver. (a) Top-view SEM images show various silver thickness of CPNs on PS nanosphere. All scale bars represent 200 nm; (b) CD and (c) g-factor spectra for L-CPNs and R-CPNs are shown with same order of silver thickness as SEM images.


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Figure5. Quantitative analysis of CD response as function of deposition thickness of silver. (a) The plots of position of CDmax versus deposition thickness; (b) The plots of CDmax versus deposition thickness. (c) Absorption spectra with different deposition thickness of silver.


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Figure6. FEM simulation of the chiroptical of CPNs. (a) Schematics evolution of geometric models based on SEM and TEM images, as shown in insets the white areas and the blue areas represent the silver and SiO2, respectively; (b) Calculated CD spectrum of L-shaped chiral structure with t1 = 10 nm, (c) CPNs with t1 = 10 nm, t2 = 10 nm and r = 150 nm and (d) CPNs with t1 = 12 nm, t2 = 12 nm and r = 180 nm, insets show the calculation structure relate to the CD spectra.


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Figure7. Circular polarized absorption spectra of (a) left-handed L-shaped chiral structure and (e) L-CPNs; CD spectra of (b) left-handed L-shaped structure and (f) L-CPNs. Near-field charge density distributions of L-shaped structure (c) and (d), as well as L-CPNs (g) and (h) under LCP and RCP excitation at resonant wavelength. The parameter of L-shaped structure is t1 = 10 nm; the parameters of CPNs are t1 = 10 nm, t2 = 10 nm, and r = 150 nm. Equivalent magnetic dipole moment and electric dipole moment are marked by green arrows.


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Tunable Chiroptical Response of Chiral Plasmonic Nanostructures

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