Design of Dual-resonant Metasurface
As the first step, we designed metasurface that introduces dual-resonance. Analysis about the origin of superb colorimetric performance in dual-resonance spectrum with particular specifications will be dictated in the next section. We adopted double bar structure as a unit-cell of metasurface as described in Fig. 2 (a). Since the corresponding structure has been shown to introduce multiple resonant modes within a narrow wavelength range in the previous research, it can be noted to be prospective candidate for exciting dual-resonance27. We put 40 nm-thick silicon nitride layer on top of the double bar structured silicon layer. The dielectric constants of silicon and silicon nitride are taken from Palik and Philipp, respectively28,29. Stacked silicon nitride layer exhibiting refractive index value similar to the geometric mean of silicon and surrounding environment acts as an index matching layer suppressing high-order mode due to Fabry-Perot like resonance in short wavelengths14. Accordingly, as shown in Fig. 2 (b), it is possible to attenuate background noise at short wavelengths, increasing similarity with the target spectrum and achieving more pronounced double peak spectrum overview. In the unit-cell structure, period (P), height (H), length (L), and width (W) were selected as variable parameters to be modulated. The center of the both bars are located at a distance of P/4 from the center of lattice. Fig. 2 (c) represents simulated representative dual-resonance spectrum in the visible region for x-polarized normal illumination when P=290 nm, H=160 nm, L=210 nm, and W=50 nm, respectively. Numerical simulations are conducted by finite-difference time-domain (FDTD) approach implemented in the Lumerical software package. To gain insight into the nature of each resonance, EM field distributions are numerically analyzed. Inset figure in Fig. 2 (c) shows electric and magnetic field distribution at each resonance. At the resonance around the wavelength of 600 nm (bottom part of the inset), displacement current loop is formed with strong magnetic fields in the core of the resonator that corresponds to magnetic dipole (MD) mode. In addition, since this magnetic field formed by MD mode penetrates two parallel bars, interaction with their surroundings can occur more actively. These field distributions can assist the enhancement of spectroscopic sensitivity for bio-molecular detection. In the case of wavelength of 470 nm, electric near-field is strongly concentrated not only inside the resonator, but also on top of the substrate and between adjacent unit-cells (top part of the inset). It can be inferred that these field distributions arise from Mie lattice resonance30,31. Lattice resonance is collective resonance which occurs in periodic nano-array stemming from the radiative coupling of resonances of individual nano-resonator. It is enhanced near specific wavelength where diffraction order occurs, called Rayleigh anomaly (RA)32,33. At wavelength slightly higher than the RA, lattice resonance can occur and be reinforced as the coupling effect arises. In the proposed structure, corresponding RA wavelength is calculated by multiplying refractive index of substrate and period; λ = nP = 423.4 nm. Therefore, at the wavelength about 470 nm, by the radiative coupling around the RA wavelength, distinct reflection peak appears as the resonant mode introduced by hybridization of electric quadrupole and electric dipole moment is strengthened. Mode profile penetrating the top of the substrate serves to further strengthen coupling effect between adjacent unit-cells. Multipole decomposition results and detailed EM field distributions in each resonance are included in supplementary information S1. Meanwhile, in order to train DNN for an inverse design process, we constructed training sets from enough full-wave simulation results obtained by changing four structural variables (P, H, L, and W). Entire simulated reflectance spectra are shown as two-dimensional color map in Fig. 2 (d). Ranging from 245 to 400 nm for P, from 70 to 190 nm for H, from 170 to 290 nm for L, and from 40 to 150 nm for W, a total of 2,637 spectra were obtained. From the reflectance color map, we confirmed that dual-resonance can occur and be modulated within the design space of the proposed structure.
Finding Double-peak Lorentzian Spectrum for Maximized Color Difference
The next step is to find an optimized reflectance spectrum in the visible to maximize the color difference per refractive index unit (RIU) of the proposed dual-resonance metasurface colorimetric sensor. Prior to the spectrum finding process, we firstly needed to define a figure of merit (FoM) for colorimetric sensing. Previous studies about colorimetric sensing adopted the change in chromaticity per RIU as FoM caused by resonance shift19,22. However, as this metric does not reflect changes in saturation and brightness of color, it does not accurately correspond to color changes people perceive with naked eyes in reality. Therefore, we utilized CIEDE2000 (ΔE00) for quantitative and practical analysis of color difference, which has been developed in the field of color science. In order to resolve extant perceptual non-uniformity issue in CIELAB color space, ΔE00 is the latest color distance metric defined by refining CIE76 (ΔE) value which is a Euclidean distance between two colors in CIELAB space34. A detailed description for the CIELAB color space and the definition of ΔE00 are included in supplementary information S2.
To derive reflectance spectrum optimized for color difference detection, we used sum of multiple Lorentzian functions, one of the ideal symmetric spectral lineshape functions, which are most frequently observed ones in phenomena related to light radiation. In the case of asymmetric spectra such as Fano lineshape, which is frequently utilized in previous research to enhance sensitivity of nanophotonic sensor by reinforcing local field near the nanostructure, due to influence of the continuum state existent in entire region of spectrum, inevitable background noise exists from the perspective of colorimetry18,35,36. On the other hand, Lorentzian lineshape is more advantageous to enhance color purity and colorimetric sensing performance (Fig. S2 (a)) because of lower background reflection. The Lorentzian function can similarly fit the dual-resonant reflectance spectrum appearing on the proposed metasurface. Therefore, the nth arbitrary spectrum for the target spectra to enter input of DNN is expressed by the following Lorentzian function.
In the above equation, Ai,n , Wi,n and Xci,n represent amplitude, linewidth, and wavelength of each resonance of the nth arbitrary spectrum, respectively. Using (1), random values of A, W, Xc are iteratively generated. Then, for each candidate spectrum, we calculated the CIELAB coordinate value (L*,a*,b*) under the standard illuminant condition. From the calculated (L*,a*,b*) , ΔE00/nm is calculated for slight spectral shift and only the candidates above a certain figure of ΔE00/nm were picked out. These random sampling processes are sufficiently repeated until a specific tendency was found in the selected lineshapes. Detailed procedures can be found in supplementary information S3.
Figures 3(a) and 3(b) exhibit the finally selected seven target spectra and the corresponding ΔE00/nm values obtained from abovementioned processes after considering the optical loss in the visible area of silicon material. From Fig. S2 (c) in supplementary information S3, it is apparent that these dual-resonance type target spectra show color difference that exceeds that of single resonance with extremely sharp line-width. In Fig. 2 (c), we selected the three of the target spectra with the highest ΔE00/nm, and each calculated reflected color shifting these spectra by 5 nm in each step (i.e ΔXcn=5nm ) is shown on two-dimensional section of the CIELAB coordinates to analyze principles of the massive color difference in these dual-resonance spectra. In all instances, it is discernible that the calculated colors are commonly located in neutral region where both a* and b* are close to zero, and L* indicating lightness has a value of about 50. The reason why massive colorimetric performance is presented in these specific areas on CIELAB could be found out by introducing the concept of discrimination threshold ellipse37. Discrimination threshold ellipse is defined as an area in which the human eye cannot differentiate colors inside the same ellipse even if they are different. In other words, the smaller the ellipse size is, the easier it is to recognize even trivial color variations. According to the previous color perception experiments38,39, the region with the smallest ellipse locates is in the vicinity of the origin at the (a*,b*) coordinate and L* between 40 and 60. These values correspond exactly to the area in which the calculated color of the target spectra is located as shown in Fig. 3 (c), thus verifying the cause of the exceptional color difference generated by dual-resonance spectrum. Additionally, further analysis can be made from the spectral lineshape itself of the target spectra. Examining the target spectra, firstly in the resonance occurring at longer wavelengths, since the peak point is commonly located between 650 and 700 nm, when the analyte is adsorbed on sensor causing spectral red-shifts, parts of the resonance deviate outside the visible region. Therefore, the ratio of red constituting the structural color decreases rapidly, inducing dramatic color variations. In the case of resonance at shorter wavelengths, the resonance wavelength is located in the blue-green area (i.e λ=460~510nm)
in order to place the constituted color on coordinates of CIELAB where the abovementioned ellipse has the smallest size when combined with the first resonance. As a result, in the target spectra with high FoM, the resonance wavelengths of both resonances are commonly located at particular spots.
Bidirectional Deep Neural Network: Characterization and Evaluation
We conducted multi-parameter optimization of the unit-cell of the proposed metasurface by training the DNN with thousands of full wave simulation data enabling more exquisite and time-efficient design process. We set up bidirectional network which cascaded inverse network at the input terminal of the pre-trained forward network. It is because the spectrum-geometry pairs have difficulty in constructing one-to-one-mapping (i.e. non-uniqueness problem) when establishing DNN architecture with general inverse network (direct prediction of geometric parameters from spectra)23,40,41. Architecture of the bidirectional network is shown in Fig. 4 (a). We put in the simulated reflectance for 117 wavelength points in the visible range between 360 nm and 830 nm (abbreviated by RTN) as an input to the inverse network. Inverse network predicts geometric parameters from RT, and the predicted reflectance RP from these value by ensuing forward network becomes the output of the entire bidirectional network. Mean squared error (MSE) between RP and RT was set as loss function of the network, and normalized geometric parameters of the unit-cell can be found by extracting weight of the intermediate layer. As described in the first sub-section, a total of 2,637 spectrum-geometry pairs were obtained through EM simulations by setting (P, H, L, W) shown in Fig. 2 (a) as geometric variables. These pairs were divided into 1,680 training sets and 945 validation and test sets. On the other hand, instead of dense layer, we utilized one-dimensional-convolutional layer (Conv-1D) to make DNN robust against overfitting, and improve regression accuracy42. As a result of trial-and-error for various hyperparameter conditions and the number of layers, optimized forward DNN architecture consists of 4-neuron input layer, 4 Conv-1D layers, followed by 256-neuron fully connected layer and 117-neuron output layer. Inverse network maintained equal architecture with the forward network but only changed order of input and output shape. The number of filters of each Conv-1D layer is 128 and kernel size is 3. A rectified linear unit (ReLU) activation function was applied to every end of layers. As a result of updating all of weights through Adam optimizer with learning rate of 0.001 and batch size of 16, highly accurate spectrum prediction capability could be obtained in the test set (MSE=5.69×10-4) For the bidirectional network which is constructed by connecting inverse network with pre-trained forward network, the same hyperparameter condition was substituted and trained over 5,000 epochs. Consequently, in the validation and test set, the losses were 1.2×10-3 , and 2.1×10-3 , respectively, implying that the network is well-converged. Figure 4 (b) shows that the bidirectional network can almost accurately predict various reflected spectral shapes (RP) arising from the proposed metasurface obtained by FDTD simulations (RT). These results suggest that the designed bidirectional DNN can also serve as immensely time-efficient simulator in designing desired metasurface.
Colorimetric Sensing Performance for Optimized Metasurface
Table 1
Geometric parameters predicted by designed DNN and corresponding mean squared error.
Target
|
P
|
H
|
L
|
W
|
MSE
|
|
363.61
|
129.52
|
190.19
|
107.64
|
0.0316
|
|
354.49
|
152.17
|
234.30
|
60.94
|
0.0103
|
|
339.25
|
141.42
|
210.83
|
85.14
|
0.0042
|
|
328.06
|
140.54
|
219.44
|
100.98
|
0.0150
|
|
371.50
|
107.55
|
214.06
|
64.38
|
0.0244
|
|
359.08
|
148.38
|
214.59
|
84.30
|
0.0290
|
|
337.99
|
137.76
|
208.34
|
97.67
|
0.0064
|
Deploying abovementioned bidirectional DNN, we performed the inverse design of metasurface for 7 target spectra. Table 1 shows the geometric parameters the DNN predicted and the corresponding loss value. Among them, for the two spectra showing the lowest MSE (T3 and T7), we compared reflectance between target spectral lineshapes, FDTD simulation results obtained by substituting predicted geometric parameters, and DNN predictions as indicated in Fig. 5 (a). Although there is a slight discrepancy compared to the target due to the constraints of the design space of the proposed metasurface structure, thanks to the sufficient fidelity of the DNN, we could obtain predicted reflectance that is almost consistent with the FDTD simulation results. Afterward, in order to evaluate colorimetric sensing performance for these two most adequate cases, we displayed the change in structural color reflected from the designed metasurface according to environmental change. We selected glucose solution as target detection analyte that can well express the conditions for minute change in peripheral refractive index. The refractive index per concentration of the glucose solution was calculated using the following equation43.
where nw is the refractive index of water which is set to 1.33, and C is a concentration of glucose in g/100ml. Figure 5 (b) indicates the reflected structural color according to the variation of glucose level by 5g/100ml. Each step corresponds to change in refractive index (Δn) of about 0.0072. Anyone can easily observe with naked eye that designed colorimetric sensor indicates notable sensitivity in color variation even with very little environmental changes. In Fig. 5 (c), the aforementioned results are expressed as a quantitative graph through ΔE00 with respect to the glucose level. From almost linearly proportional correlations between ΔE00 and concentrations, calculated ΔE00/RIU, FoM of the proposed colorimetric sensor, reaches about 190.23 for T3 and 165.58 for T7. According to the color recognition experiments conducted in Ref. 44, the minimum ΔE00 for noticeable color difference is specified as 1.5, and appreciable difference can be felt in 3.0 and above. That is, in agreement with calculated ΔE00 in each glucose level, the concentration over 15g/100ml (Δn=0.0215) can be detected clearly through the proposed colorimetric sensor for both cases (ΔE00 is 4.09 for T3, and 3.56 for T7). Furthermore, we can estimate that resolution limit of the sensor is about 6g/100ml of glucose level (Δn=0.0086) in the case of T3 by calculating minimum concentration in which ΔE00 exceeds 1.5 (ΔE00 = 1.58).