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Communication
Giant enhancement of second-order nonlinearity of
epsilon-near-zero-medium by a plasmonic metasurface
Junhong Deng, Yutao Tang, Shumei Chen, Kingfai Li, Anatoly V Zayats, and Guixin Li
Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.0c01810 • Publication Date (Web): 04 Jun 2020
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Page 1 of 20 Nano Letters

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 Nano Letters Page 2 of 20

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6 Giant enhancement of second-order nonlinearity of
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8 epsilon-near-zero-medium by a plasmonic
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10 metasurface
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13 Junhong Deng,⊥ Yutao Tang,⊥ Shumei Chen, Kingfai Li, Anatoly V. Zayats,* and Guixin Li*
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16 KEYWORDS: Plasmonics, Nonlinear Metasurfaces, Second-harmonic Generation, Epsilon
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19 Near Zero materials.
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22 ABSTRACT: Nonlinear frequency conversion at the nanoscale is important for many applications
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24 in free-space and integrated photonics. In epsilon-near-zero (ENZ) materials, second-harmonic
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26 generation (SHG) is significantly enhanced but the oblique incidence is required to address
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nonlinearity. To circumvent this constraint, we design a hybrid metasurface consisting of
29 plasmonic nanostructures on an ENZ nanofilm generating strongly enhanced SHG at normal
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31 incidence in transmission. We shown that the Au meta-atoms on an indium-tin-oxide (ITO) layer
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33 provide an approximately 104-fold experimentally measured SHG enhancement at normal
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incidence at the fundamental wavelength near the ENZ condition of ITO.This giant enhancement
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36 stems from reshaping the vectorial properties of the incident light near the Au nanostructures and
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38 its increased coupling to the ENZ film. The proposed hybrid ENZ metasurface offers a promising
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40 platform for developing ultracompact and efficient nonlinear optical sources at the nanoscale.
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Page 3 of 20 Nano Letters

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3 Nonlinear nanophotonic devices have been attracting much attention in the last two decades. The
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6 strong localization of light at the nanoscale can greatly reduce the size of nonlinear frequency
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8 converters and also improve the speed of nonlinear optical switching and modulation1–2. However,
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10 the lack of sufficient propagation length and the absence of traditional phase matching conditions
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in nonlinear nanophotonic devices inevitably results in low efficiency of nonlinear optical
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15 conversion. To circumvent this constraint, various approaches have been proposed to engineer
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17 optical modes using novel artificial nanostructures, such as photonic crystals, plasmonic
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nanoantennas, metamaterials and metasurfaces3–7. Among these nanostructures, photonic
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22 metasurfaces have recently emerged as a versatile platform for manipulating various degrees of
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24 freedom of light beams7, 8. Compared to other artificial media such as photonic crystals and
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26 metamaterials, 2D metasurfaces are much easier to fabricate and integrate in optoelectronic
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29 technologies. In the linear optical regime, metasurfaces provide control over the phase and
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31 amplitude of light, and metasurface holography and flat metalenses with various optical
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33 functionalities have been extensively studied9–13. In the nonlinear optical regime, metasurface-
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based devices have shown excellent performance for manipulating second 14–21 and third harmonic
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38 generation (SHG and THG)22, 23.
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40 Epsilon-near-zero (ENZ) materials represent a new kind of promising nonlinear optical
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media. ENZ behaviour is observed at the onset of a plasmonic response in metals or highly doped
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45 semiconductors, such as indium-tin oxide (ITO) and aluminium-doped zinc oxide (AZO), and can
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47 be engineered in metamaterial composites24–30. In ENZ media, the need for phase matching
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49 condition in nonlinear processes is greatly reduced30. Interesting nonlinear optical properties of
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52 ENZ materials have been experimentally demonstrated, such as modulation of the plasma
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54 frequency of ITO and indium-doped cadmium oxide by controlling the wavelength and power of
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 Nano Letters Page 4 of 20

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3 pumping light29, 30, 32. The extremely large third-order nonlinearity from ITO and AZO has been
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6 experimentally observed under ENZ conditions29, 30. By placing the plasmonic nanoantennas onto
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8 a thin ITO thin film, extremely large intensity-dependent refractive index has been achieved31.
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10 In the ENZ conditions, ITO thin films have been shown to radiate strong SHG and THG
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signals under the oblique incidence of the fundamental light26. This strong nonlinear frequency
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15 conversion at oblique incidence can be explained by the anisotropy of the nonlinear response of
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17 ITO and the enhancement of the fundamental field in the ENZ medium due to the continuity of
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the electric field components normal to the interface33–35. At the same time, the electric field
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22 components parallel to the interface poorly penetrate the ENZ medium and weakly participate in
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24 the nonlinear processes. Therefore, at normal incidence, the nonlinear conversion is extremely
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26 weak.
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29 Here, we realize a strategy to greatly enhance the SHG from ENZ materials at normal
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31 incidence by placing plasmonic (Au) meta-atoms on the interface to facilitate the fundamental
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33 field coupling to the ENZ layer where SHG is generated (Figure 1). The plasmonic nanostructures
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generate strong electric field components in the near-field normal to the ENZ substrate, resulting
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38 in the enhanced SHG. The symmetry of plasmonic meta-atoms additionally allows controlling
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40 polarization of the generated light. We demonstrate experimentally and theoretically the role of
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coupling of the near-field scattering to the ENZ layer, which results in an experimentally observed
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45 almost 104-fold SHG enhancement and conversion efficiency approximately 7.8 × 10-8 W-1 in a
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47 15-nm-thick ITO layer at normal incidence. The theoretical simulations predict at the fundamental
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49 wavelength (FW) near the ENZ condition, more than 108-fold SH intensity enhancement from the
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52 hybrid Au-ITO metasurface at normal incidence compared to a bare ITO film at oblique incidence.
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Page 5 of 20 Nano Letters

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3 Results
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6 Plasmonic-ENZ Metasurfaces
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Plasmonic-ENZ metasurfaces were designed and fabricated as described in SI in two different
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11 configurations (Figure 2a and 2b). The 30 nm thick plasmonic (Au) meta-atoms were chosen to
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13 have three-fold (C3) rotational symmetry. The meta-atoms are arranged in a hexagonal lattice of
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15 550 nm period, so that the interaction between the meta-atoms is negligible. The overall size of
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18 the metasurface is around 300 × 300 μm2. Two metasurfaces were experimentally studied in order
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20 to elucidate the interaction between the meta-atoms and the ENZ layer: hybrid plasmonic-ENZ
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22 C3-ITO metasurface with 30 nm Au/15 nm ITO/SiO2 substrate and a C3-SiO2-ITO metasurface
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25 with 30 nm Au/100 nm SiO2/15 nm ITO/SiO2 substrate, with a dielectric layer between plasmonic
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27 meta-atoms and an ENZ film. The ITO has an ENZ wavelength of approximately 1160 nm (Figure
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29 S1(a)). A bare ITO film has the featureless transmission spectrum (Figure S1(b)). The transmission
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spectrum of the C3-ITO metasurface exhibits two broad features, each with two resonances in both
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34 the FW range at approximately 1115 nm and 1445 nm and in the SHG range around 630 nm and
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36 720 nm (Figures 2c and S3(a, c)). These resonances correspond to the different localized surface
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38 plasmon (LSP) modes of the Au meta-atoms. The resonance at a wavelength of 1115 nm is situated
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41 close to the ENZ wavelength where the absorption of the scattered Ez field would take place in
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43 ITO and gives rise to the transmission minimum. The transmission spectra of the C3-SiO2-ITO
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45 metasurface show the LSPs in the FW and SHG ranges at approximately 1120 nm and 630 nm,
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48 respectively (Figures 2d and S3(b, d)). Simulations using the measured optical properties of ITO
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50 reproduce the transmission spectra (Figures S3c and S3d). For both metasurfaces, the resonances
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52 in the FW range are situated at around the ENZ wavelength of ITO.
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 Nano Letters Page 6 of 20

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3 Strongly enhanced SHG at the fundamental wavelength of approximately 1240 nm, close
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6 to the ENZ wavelength is observed from the hybrid C3-ITO metasurface even at normal incidence,
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8 whereas a bare ITO film exhibits 4 orders of magnitude smaller SHG intensity (Figures 3a and
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10 S4). At the same time, for the metasurface with the SiO2 layer between the plasmonic meta-atoms
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and the ENZ layer, the enhancement is more than 200 times smaller, due to the reduced interaction
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15 between plasmonic meta-atoms and the ENZ layer.
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17 Nonlinear Optical Measurements
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Since the gold meta-atoms have three-fold rotational symmetry, from the symmetry
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22 selection rules in harmonic generation, the polarization of SHG wave is determined by that of the
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24 fundamental wave (FW). If the C3 meta-atom is excited by circularly polarized FW, it will radiate
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26 SHG wave with opposite circular polarization to that of FW3, 7, 22. Polarization resolved spectra of
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29 SHG waves show significant intensity differences of SHG between different polarization
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31 configurations (Figures 3 and S4a). This confirms the symmetry selection rules for the SHG
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33 polarization, even in the case of an ENZ media where the SHG is driven primarily by the field
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components normal to the nonlinear substrate, but the symmetry of the fundamental field and thus,
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38 the induced nonlinear polarization in ITO, is determined by the symmetry of the plasmonic meta-
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40 atoms and not their shape (the latter may influence the field enhancement).
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SHG intensities as a function of the fundamental power are characterized by the slope
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45 values of approximately 1.95 and 1.93 for the FW with LCP and RCP polarization states (Figure
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47 S4b); these slopes agree well with the theoretical value of 2 for the second-order nonlinear optical
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49 processes. The second-harmonic conversion efficiencies for the Au-ITO metasurface and a bare
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52 ITO layer at normal incidence, defined as   P2 P2 , can be estimated to be approximately 7.8 ×
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Page 7 of 20 Nano Letters

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3 10-8 W-1 and 10-11 W-1, respectively. The latter is probably determined by the crystallite structure
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6 of the ITO film.
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8 Discussion
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10 In a phenomenological model, the SHG from an ITO layer can be described by the
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13 dominant second-order nonlinear susceptibility component  zzz 27. Therefore, SHG from a bare
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15 ITO film cannot be generated at normal incidence. For the studied metasurfaces, SHG is generated
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18 even at normal incidence due to the electric field components normal to the interface generated in
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20 the near-field by the plasmonic resonances of the meta-atoms. The modelling of the SHG process
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is performed as follows. Firstly, the nonlinear polarization P 2 (r )   0  (2) E (r )  E (r ) is calculated
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25 by using both the complex field E (r ) and the nonlinear optical susceptibility  (2) of the gold and
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28 ITO at a given position r. By illuminating a metasurface with a plane wave at a SHG wavelength,
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30 a factor G (r ) , which describes the radiation of the SHG waves, can be obtained based on the
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33 reciprocal optical processes from near field to far field or vice versa. Finally, the electric field of
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35 the far-field SHG at position R can be simulated from the nonlinear polarisation at each local
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position 𝑟 in the gold and ITO layers through the equation ESHG ( R)   G ( R, r )  PSHG (r )d r , with
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40 the values of refractive index and the effective second-order susceptibility of gold36, 37 and ITO27,
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42 31.
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45 The simulated spectra qualitatively agree with the experimental ones (cf. Figures 3a and
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47 3b). For both of the C3-ITO and C3-SiO2-ITO metasurfaces, the calculated SHG signals follow
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the polarization selection rules. In order to validate the source of the SHG signal, the simulations
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52 of the SHG with and without taking into account the nonlinear susceptibility of ITO were carried
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54 out, which reveal the practical absence of the SHG if only the nonlinear response of Au meta-
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 Nano Letters Page 8 of 20

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3 atoms is considered without the contribution from ITO (Figure S6b). With the introduction of the
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6 silica layer between the plasmonic meta-atoms and the ITO layer in the simulations, the SHG
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8 signal drops dramatically, accompanied by a blue-shift of the resonance (Figures S7 and S8). This
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10 dependence originates from the reduction of coupling between the meta-atom resonances and the
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ITO layer resulting in the lower fundamental electric field polarized perpendicularly to the ITO
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15 interface penetrating the ENZ layer. The slight deviations in the resonance positions and shape of
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17 the simulated and experimental SHG spectra might be due to the dispersion of the nonlinear
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susceptibility of ITO, which is not considered in the simulations.
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22 For a normally incident fundamental wave, the SHG from an ITO film cannot be generated,
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24 however, the excitation of plasmonic meta-atoms generate, even under normal illumination, the
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26 electric field components normal to the ITO interface. To understand this behavior and the origin
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29 of the near-field coupling of the fundamental light, the spatial distributions of nonlinear
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31 polarizations on the two metasurfaces with and without the silica layer were simulated (Figure 4).
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33 At a FW of 1300 nm, which corresponds to the SHG resonance of the C3-ITO metasurface, the
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distribution of the fundamental electric field induced by the illumination with circularly polarized
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38 light at normal incidence show significant presence of z-component of the near-field under the
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40 meta-atoms in the ITO layer (Figures 4e and 4f). At the same time, the x-y components are
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primarily present on the Au meta-atoms (Figures 4a and 4b). Thus, z-polarised electric field is
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45 efficiently generated and funnelled into the nonlinear ITO layer where it generates SHG. The
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47 nonlinear polarization P SHG induced in the ITO layer follows the symmetry of the meta-atoms
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50 (Figures 4i and 4j) and, therefore, the generated SHG obeys the polarization selection rules
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52 determined by this symmetry. At a FW of 1180 nm corresponding to the plasmonic resonance of
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the C3-SiO2-ITO metasurface, the strong field enhancement and excitation of the z-component of
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Page 9 of 20 Nano Letters

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3 the fundamental near-field takes place near the meta-atoms, however, this z-component of the
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6 near-field does not funnel into the nonlinear ITO film because the silica layer, being dielectric,
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8 does not support longitudinal waves, and the field exponentially decays before reaching ITO
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10 (Figures 4c, 4d, 4g and 4h). The ratio of the norm of the z-field components in the ITO in the case
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of C3-ITO and C3-SiO2-ITO metasurfaces is approximately 15, which translates in the lower
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15 nonlinear polarisation induced in the latter metasurface (Figures 4k and 4l).
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17 The angular dependence of the SHG enhancement from the hybrid metasurface is
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completely different from the one from a bare ITO film (Figure S9). In the latter case, the SHG is
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22 practically zero under normal illumination due to the anisotropic nonlinearity of ITO requiring the
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24 fundamental field component normal to the surface and increases with the angle of incidence26,27.
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26 In the case of the plasmonic-ITO metasurface, the SHG intensity is highest at normal incidence of
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29 the fundamental light and slowly drops for larger angles. Despite this drop, the SHG from the Au-
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31 ITO metasurface is still many orders of magnitude higher than from a bare ITO, exhibiting more
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33 than 108-fold SHG enhancement at the normal incidence excitation compared to a bare ITO film
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at the most favorable oblique angle of incidence.
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38 Conclusion
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41 We demonstrated strong enhancement of the transmitted SHG from the hybrid plasmonic-ENZ
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43 metasurfaces at normal incidence, facilitated by the excitation of z-components of the fundamental
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45 field by the plasmonic meta-atoms and coupling this field to the ENZ layer. A ~ 104-fold
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enhancement of SHG is experimentally observed near the ENZ wavelength of an ultrathin ITO
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50 film, while maintaining the circular polarization states of the SHG waves. The theoretical
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52 simulations predict more than 108-fold enhancement of the SHG from the hybrid metasureface
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under the excitation at normal incidence compared to a bare ITO film at oblique incidence. A
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 Nano Letters Page 10 of 20

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3 phenomenological model was developed to elucidate the mechanism of this giant SHG
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6 enhancement in the hybrid plasmonic-ENZ metasurface. The intensity of SHG can be controlled
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8 by a dielectric spacer layer between the plasmonic metasurface and ENZ medium, which affects
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10 coupling of the fundamental light to ENZ layer. The proposed strategy for manipulating the field
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enhancement in the ENZ material can be applicable to other plasmonic-ENZ systems and
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15 nonlinearities and may open new routes for designing compact and polarization selective nonlinear
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Methods
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22 Fabrication of the Hybrid Plasmonic Metasurfaces. C3-ITO and C3-SiO2-ITO metasurfaces
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are fabricated by using electron beam lithography (EBL) and electron-beam evaporation technique.
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27 For C3-ITO metasurface, a thin positive electron resist layer (2.5% PMMA, ALLRESIST) with
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29 the thickness of about 120 nm is spin-coated onto the ITO glass substrate covered with a 15 nm
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thick ITO film. The substrate is baked at temperature of 180 oC for 3 min. The metasurface patterns
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34 are then transferred onto the positive photoresist layer using electron beam lithography and the
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36 resist is developed. Afterwards, a 30-nm-thick gold thin film is deposited onto the photoresist by
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38 e-beam evaporation (AUTO500, HHV) with the deposition rate of 0.086 nm/s followed by a lift-
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41 off process. For the C3-SiO2-ITO metasurface, before spin-coating the positive photoresist, a SiO2
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43 spacer layer with thickness of 100 nm is deposited onto the ITO glass substrate using electron
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45 beam evaporation method. Subsequently, the gold plasmonic metasurfaces are fabricated using
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EBL and metal lift off processes.
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50 SHG Measurements. The second harmonic generation intensity was measured using an optical
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52 parametric oscillator pumped by Ti: Sapphire laser with repetition frequency of 80 MHz and pulse
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duration of ~ 250 fs. The wavelength was tuned across the spectral range of the ENZ of the ITO
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Page 11 of 20 Nano Letters

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3 from 1140 to 1500 nm. The fundamental light was incident perpendicularly to the metasurface and
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6 the spot size on the surface was approximately 20 µm in diameter after passing through a 4 x
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8 objective lens (NA= 0.1). The SHG signal from metasurfaces was collected in transmission
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10 through the substrate by an infinity-corrected objective lens (10x, NA = 0.1). After filtering the
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fundamental light using a shortpass filter, the SHG signal was spectrally analyzed with an Andor
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Figure 1. Schematic illustration of second harmonic generation from hybrid plasmonic-ENZ
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20 metasurfaces. (a) C3-ITO metasurface and (b) C3-SiO2-ITO metasurface. The Au plasmonic meta-
21 atoms with three-fold rotational symmetry (C3) are arranged in a hexagonal lattice. The symmetry
22 selection rules are manifested by the opposite handedness of the fundamental and the SHG waves.
23 SHG intensity from the C3-SiO2-ITO metasurface is weaker than that from the C3-ITO
24 metasurface, this is because the coupling between gold meta-atoms and the ITO layer is weaken
25 by inserting a silica layer between them.
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27 Figure 2. Hybrid plasmonic-ENZ metasurfaces and their optical properties. (a) and (b) Scanning
28 electron microscopy images of the fabricated C3-ITO (a) and C3-SiO2-ITO (b) metasurfaces (scale
29 bar: 500 nm): 30 nm-thick Au meta-atoms are arranged in hexagonal lattice of a 550 nm period.
30 The width of the arms of the meta-atoms is 80 nm. The lengths of the arms of 195 nm (a) and 150
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nm (b) are chosen to keep the resonance near the ENZ wavelength for both metasurfaces. The ITO
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film is 15 nm thick. In (b), a silica layer is 100 nm thick. (c) and (d) Transmission spectra of the
34 metasurfaces measured for horizontally (H) and vertically (V) polarized light (the orientation is
35 shown in the insert in (a) and (b)) in the spectral range of the fundamental wave. The transmission
36 of the ITO film and the metasurfaces in the SHG spectral range is shown in Figure S1b. The
37 simulated transmission spectra of the metasurfaces are shown in Figure S3.
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34 Figure 3. Measured and simulated polarization dependent SHG spectra of C3-ITO (a, c) and C3-
35 SiO2-ITO (b, d) metasurfaces. The metasurfaces are excited with circularly polarized FW and both
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left and right circularly polarized (LCPSHG and RCPSHG) components of SHG signals are measured.
38 The fundamental wave propagates at normal incidence from the metasurface to the substrate
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Figure 4. The distribution of the total fundamental electric field at the Au-ITO interfaces. (a, b):
41 C3-ITO (z=45 nm) and (c, d): C3-SiO2-ITO metasurfaces (z=145 nm). The metasurfaces are
42 illuminated by the normally incident circularly polarized light of different handedness at the
43 resonant wavelengths of the enhanced SHG. (e-h) The distribution of the z-component of the
44 fundamental field, |Ez|, in the x-z plane (the position of the cross-section are indicated in (a-d) by
45 dashed lines in (a, b) y = 70 nm and in (c, d) y = 40 nm, where maximum of the field enhancement
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47 is observed). (i-l) The spatial distribution of the nonlinear polarization P SHG integrated over the
48 ITO film thickness in (i, j) C3-ITO and (k, l) C3-SiO2-ITO metasurfaces in the x-y plane for
49 different polarization configurations.
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3 ASSOCIATED CONTENT
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7 Supporting information.
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9 The supporting information is available free of charge via the internet at http://pubs.acs.org.
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12 The supporting information includes ITO thin film properties; Transmissions Spectra of the
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Metasurfaces; SHG Measurements; SHG Simulations.
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16 AUTHOR INFORMATION
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18 Corresponding Authors
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20 Anatoly V. Zayats
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22 Department of Physics and London Centre for Nanotechnology, King’s College London, Strand,
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London, WC2R 2LS, UK
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25
Email: a.zayats@kcl.ac.uk
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27
Guixin Li
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29
Department of Materials Science and Engineering, Shenzhen Institute for Quantum Science and
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31 Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
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33
Email: ligx@sustech.edu.cn
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35
Authors
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37 Junhong Deng − Department of Materials Science and Engineering, Shenzhen Institute for
38 Quantum Science and Engineering, Southern University of Science and Technology, Shenzhen,
39 518055, China.
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41 Yutao Tang −Department of Materials Science and Engineering, Shenzhen Institute for Quantum
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43
Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055,
44 China.
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46 Shumei Chen −School of Science, Harbin Institute of Technology (Shenzhen), 518055, China
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48 Kingfai Li − Department of Materials Science and Engineering, Shenzhen Institute for Quantum
49 Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055,
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China.
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Author Contributions
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Page 17 of 20 Nano Letters

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3 ⊥These authors contribute equally to this work. G. L. proposed the idea and supervised the project.
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6 J. D. fabricated the metsasurface, J. D., Y. T., and K. L. conducted the optical measurements. G.
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8 L. and A. Z. wrote the manuscript with the input from all auhtors.
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ACKNOWLEDGMENTS
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13 G. L. acknowledges the support from National Natural Science Foundation of China (91950114,
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15 11774145), Guangdong Provincial Innovation and Entrepreneurship Project (2017ZT07C071). A.
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17
Z. acknowledge the support from EPSRC (UK) and the ERC iCOMM project (789340). A. Z. and
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20 G. L. thank the support from the Royal Society International Exchanges Project (IES\R2\170121).
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22 All the data supporting this research are presented in the article and in the Supporting Information.
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