Mid-infrared tunable absorber based on an Ag/SiO2/VO2/Ag/VO2 multilayer structure and its molecular sensing capability.

We present a design of middle-infrared modulation absorbers based on vanadium dioxide (VO2). By using the electron beam evaporation technique, the Ag/SiO2/VO2/Ag/VO2 multilayer structure can achieve double band strong absorption in the mid-infrared, and dynamically adjust the absorption performance through VO2. The simulation results demonstrate a remarkable absorption rate of 91.8% and 98.9% at 9.09 µm and 10.25 µm, respectively. The high absorption is elucidated by analyzing the field strength distribution in each layer. Meanwhile, based on the phase change characteristics of VO2, the absorber has exceptional thermal regulation, with a remarkable 78% heat regulation range in the mid-infrared band. The size altering of the absorbing layer is effective in enhancing and optimizing the structure's absorption performance. The structure is used to characterize probe molecules of CV and R6 G by mid-infrared spectroscopy, which illustrates an impressive limit of detection (LOD) of 10-7 M for both substances. These results provide valuable insights for designing future high-performance tunable optical devices.

Porous rod-shaped Fe2O3/Ag/BP: a novel substrate for highly sensitive SERS detection of persistent organic pollutants.

A surface enhanced Raman scattering (SERS) substrate of porous rod-shaped ferric oxide (Fe2O3) combined with silver nanoparticles (Ag NPs) and black phosphorus (Fe2O3/Ag/BP) was fabricated to detect the persistent organic pollutants (POPs) at low concentration. The organic pollutant Rhodamine 6G (R6G) was used as the probe molecule to study the performances of Fe2O3/Ag/BP, and 4-chlorobiphenyl (PCB-3) was the target of detection. The limit of detection (LOD) of R6G based on this novel SERS substrate Fe2O3/Ag/BP was as low as 1.0 × 10-15M, which was five orders of magnitude lower than that of Fe2O3/Ag (10-10M). The enhancement factor (EF) of Fe2O3/Ag/BP was 6.44 × 108, which was 3.1 times higher than that of porous rod-shaped Fe2O3/Ag (2.08 × 108). The Raman signal of R6G based on Fe2O3/Ag/BP had a good homogeneity, and the relative standard deviation (RSD) of Raman signal intensities of R6G at 1643 cm-1was only 5.97%. Furthermore, the Fe2O3/Ag/BP substrate exhibited a recyclability through the photocatalytic degradation of R6G. The LOD of PCB-3 based on Fe2O3/Ag/BP was 10-9M. Besides, Fe2O3/Ag/BP had a high SERS activity even it was kept in a centrifuge tube without requiring complicated treatment. These results highlight the potential application of Fe2O3/Ag/BP for ultra-trace detection of POPs in the environment.

Highly sensitive AuNSs@AgNR SERS substrates for rapid determination of aromatic amines.

The leakage of aromatic amines will pose a great threat to human health and the ecological environment. Therefore, there is an urgent need to achieve rapid and high-sensitivity detection of such substances. In this study, a simple surface-enhanced Raman scattering (SERS) method based on gold nanostars-modified silver nanorods (AuNSs@AgNRs) was established for the detection of benzidine and 4-aminobiphenyl (4-ABP). The enhancement factors of the substrate towards rhodamine 6G (R6G) and crystal violet (CV) were 4.67 × 108 and 1.11 × 108, respectively. Combined with density functional theory (DFT), the AuNSs@AgNR substrate achieved the rapid detection of benzidine and 4-ABP and obtained low detection limits (LODbenzidine = 7.09 × 10-9 M; LOD4-ABP = 1.20 × 10-9 M). Furthermore, the AuNSs@AgNR substrate can realize the high-sensitivity detection of benzidine and 4-ABP in the spiked river water samples within 3 min, which means that the AuNSs@AgNR-based SERS method can be used as a portable platform to realize the on-site rapid detection of environmental pollutants.

Fabrication of multifunctional g-C3N4-modified Au/Ag NRs arrays for ultrasensitive and recyclable SERS detection of bisphenol A residues.

Monolayer g-C3N4-modified Au/Ag nanorods (g-C3N4/Au/Ag NRs) array is fabricated as a dual-function platform with high surface-enhanced Raman scattering (SERS) response and excellent photocatalytic degradation ability for bisphenol A (BPA) residues. FDTD simulation results of Au/Ag NRs proves that the electromagnetic field intensity is significantly enhanced at the gap of Ag NRs and Au NPs and the protrusion of Au NPs, which endows the arrays with excellent SERS activity. The arrays exhibit high sensitivity for rhodamine 6G (R6G) (LOD = 1.1 × 10-11 mol/L) and high SERS enhancement (EF = 9.2 × 107). In addition, the g-C3N4/Au/Ag NRs could degrade ˃90% of BPA adsorbed on the substrate surface within 140 min under visible light irradiation, and maintains its SERS activity after repeated use for 4 times. The dual-function platform with high SERS response and excellent recycling capability is proved to be reliable and is very promising for monitoring of BPA residues in food.

Visible transparent mid-infrared broadband absorbers based on gradient refractive indexes and multi-size cavity resonances.

We proposed a multi-layered nanorod structure with the same tilt angle and different diameters, which has high visible transmittance and strong 3-5 µm absorption based on the principles of the gradient of the refractive index and the multi-size cavity resonances. The indium tin oxide (ITO) was selected as the target material to fabricate the structure by using a glancing angle deposition method. The experimental results show that when the deposition angle θ is 80°, swing deposition is successively done with the rotation angle φ of ±8°, ± 5°, ± 3°, and 0° on the surface of the substrate, and the quartz crystal microbalance thicknesses of ITO nanorods are 220 nm for each deposition, the average transmittance is 80.5% in the range of 400-800 nm and the integrated absorption is 86% in the 3-5 µm band. Such a simple, low-cost, and easy-to-fabricate device has potential applications in window stealth materials and other related fields.

3-5 µm mid-infrared broadband absorbers composed of layered ITO nanorod arrays with high visible light transmittance.

A mid-infrared broadband absorber with high visible light transmittance is proposed in this paper. The absorber is composed of layered ITO nanorod arrays with increasing angles fabricated by oblique angle deposition technique. The experimental results show that the average transmittance of the absorber reaches 80% in the 400-800 nm band and the integrated absorption reaches 82.9% in the 3-5 µm band, when the QCM thickness of the first layer of film is 100 nm and the deposition angle θ is 10°, the QCM heights of the second to fifth layers of nanorods are all 330 nm, and their deposition angles are 55°, 68°, 80°, and 87°, respectively. The high transmittance in the visible band is attributed to the gradient of the refractive index. The broadband absorption in the mid-infrared band results from different resonances in the empty cavities with different sizes. Such a simple and large-area absorber has potential applications in window materials and infrared cloaking.

ITO/Si/ITO semi-cone-shell chiral complexes on silicon nanocones with broadband circular dichroism in the mid-infrared wavelength.

This paper proposed ITO/Si/ITO semi-cone-shell chiral complexes on silicon nanocones with broadband CD in the mid-infrared band. The experimental results show that when the deposition angle θ = 45°, the first ITO deposition of ta = 100 nm, the second Si deposition of tb = 200 nm with the azimuth angle unchanged, and the third ITO deposition of tc = 200 nm after rotating the azimuth angle of 60°, the prepared chiral structure has a broadband CD response in the mid-infrared band of 2.5-4 µm. The broadband CD effect is produced by the internal resonance of the three-dimensional open cavity. The cone structure can be regarded as a plurality of planar open resonant rings with different diameters, and these rings resonate at different wavelengths. The experimental results also show that the proposed chiral ITO structure exhibits a better broadband CD response than that of the structure composed of traditional metal Ag. Such a chiral structure provides a new method for the design of CD devices in the mid-infrared band.

Molecular-substrate interaction on dynamic SERS detection of butylated hydroxyanisole on a silver nano-tripod substrate.

Surface-enhanced Raman spectroscopy (SERS) relies heavily on a substrate for highly sensitive detection, which may have poor performance due to weak adsorption of molecules on the surface. The substrate-molecule interaction is a crucial factor in the SERS detection of weakly adsorbed molecules. Herein, we performed a dynamic SERS detection of butylated hydroxyanisole (BHA) on a silver nano-tripod (AgNT) substrate and reported the instability detection process of BHA. The interaction of BHA molecules with the AgNT substrate was analyzed by the detected phenomena combined with molecular electrostatic potential (MEP) and SERS surface selection rules, and a dynamic adsorption model of BHA molecules was developed. The model postulates that the conversion of solution state for molecular adsorption orientation is the key to dynamic SERS detection. The signal acquisition time of BHA was extended from 1 min to 3 min by adjusting the detection solvent, which improved the practicality and operability of SERS detection. Combining surface adsorption analysis with the SERS process may provide a reference for the detection and analysis of other weakly adsorbed molecules.

Highly sensitive gold nanoparticles-modified silver nanorod arrays for determination of methyl viologen.

Gold nanoparticles-modified silver nanorod (AuNPs@AgNR) arrays were fabricated as surface-enhanced Raman spectroscopy (SERS) substrates. The coffee ring effect of the AuNPs@AgNR was explored as a preconcentration method for enriching the target analytes and increasing the "hot spots." Furthermore, methyl viologen (MV) as a toxic herbicide used in agricultural production was successfully determined to investigate the application of the coffee ring effect on AuNPs@AgNR arrays and density functional theory (DFT) was employed to calculate its vibrational modes of corresponding characteristic peaks. Good linearity was obtained in the range 0.10-100 mg/L, and the limit of detection (LOD) of MV was estimated to be 0.01 mg/L, which was lower than the US maximum residue limits (MRLs). This method was also applied to practical detection of MV in river water and apple peel with LODs of 0.10 mg/L and 0.05 mg/L, respectively. SERS results suggest that the coffee ring on AuNPs@AgNR arrays provides a promising way for monitoring environmental pollution and food safety caused by pesticides.

Preparation of a silver nano-tripod structure by a tilting angle deposition technique and its SERS application.

A silver nano-tripod (AgNT) structure with a high-density "hot spots" distribution was fabricated by a tilting angle deposition technique. The electric field simulation distribution showed that the electric field enhancement of the AgNT structures is optimal when the tilting angle is 72°. Such AgNT substrates were successfully obtained experimentally when the included angle between the silver vapor and the normal of the sample platform was set to 86°. R6G and CV were used as probe molecules to investigate the SERS activity of AgNT, which revealed that the detection limits of AgNT for R6G and CV were 2.24×10-8 M and 4.01×10-8 M, the relative standard deviations (RSDs) were 4.26% and 4.44%, and the enhancement factors (EFs) were 9.58×106 and 1.16×107, respectively. The AgNT substrates with simple preparation and high distribution density of "hot spots" illustrate a good application prospect in environmental monitoring.

Large-area mid-infrared broadband absorbers based on spiral ITO resulting from the combination of two different broadening absorption methods.

A large-area mid-infrared broadband absorber is proposed in this paper. The absorber is a spiral ITO structure grown on a hexagonal lattice arrangement of silicon nanopillars by using a glancing angle deposition method. The experimental results show that when the heights of the silicon nanopillars are 1.7 µm and the number of rotation depositions is n = 5, that is, the rotation angle is 150 degrees, the absorber absorbs more than 81% of electromagnetic waves in the 2.5-6 µm spectral range. In the atmospheric window of 3-5 µm, the integral absorption reaches 96%. The experimental results also show that the absorbing ability of the ITO structure in the mid-infrared atmospheric window is significantly stronger than that of the structure composed of silver under the same preparation conditions. The main reasons for the broadband absorption are that the spiral ITO structure has resonant absorption of electromagnetic waves with different wavelengths in the empty cavity regions with different sizes, and ITO has longer penetration depths than noble metals in the mid-infrared band, which brings about stronger broadband absorption. The combination of the two leads to a broadening of the total absorption spectrum. The higher heights of the silicon nanopillars enhance absorption further. Additionally, the loose spiral ITO distributions indicate lower mean plasma concentration and then increase penetration depths further, resulting in stronger light absorption. Such a large-area mid-infrared absorption structure with a simple preparation method has potential applications in mid-infrared cloaking and sensing.

Two-dimensional MXene modified AgNRs as a surface-enhanced Raman scattering substrate for sensitive determination of polychlorinated biphenyls.

Ultrathin two-dimensional MXene nanosheets were decorated on the surface of silver nanorods (AgNRs) through a facile modification strategy to prepare highly sensitive and reproducible SERS substrates (AgNR/MXene substrate). The MXene nanosheets could suppress the oxidation of the silver nanorods, which endows the substrate with good stability and reproducibility. Due to the strong interaction between AgNR/MXene and the analytes, the substrate also exhibited high SERS performance with the limit of detection (LOD) of crystal violet (CV) as low as 2.48 × 10-11 M. In particular, the AgNR/MXene substrate enabled on-site determination of 3,3',4,4'-tetrachlorobiphenyl (PCB-77) and 4-chlorobiphenyl (PCB-3) and the LODs were low at 2.43 × 10-10 and 2.14 × 10-9 M, respectively. In addition, the AgNR/MXene substrate could be used for the detection of single-component and multi-component PCBs in real soil samples with good recovery percentages (90.3% and 91.6% for PCB-3 and PCB-77 in single-component format, 108.1% and 106.5% for PCB-3 and PCB-77 in multi-component format). The AgNR/MXene substrate combines the synergistic properties of both AgNRs and MXene, showing great potential in simultaneous SERS detection of multiple pollutants at the point of need.

Fabrication of paper-based SERS substrates by spraying silver and gold nanoparticles for SERS determination of malachite green, methylene blue, and crystal violet in fish.

A disposable surface-enhanced Raman scattering (SERS) substrate was prepared by successively spraying silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) onto commercial filter paper using an inexpensive consumer sprayer. The strong surface enhancement of AgNPs and chemical stability of AuNPs can be advantageously combined. The substrate exhibited excellent SERS activity for malachite green (MG), methylene blue (MB), and crystal violet (CV) under 785-nm excitation, with limits of detection (LODs) of 4.3 × 10-9, 2.0 × 10-8, and 8.1 × 10-8 M, respectively. The substrate exhibited long-term stability, and it can be stored under ambient conditions for 4 weeks with a relative standard deviation of less than 3% among peak intensities. The substrate also showed good reproducibility with a relative standard deviation of 7.1% among different substrate peak intensities. The substrates enable on-site determination of residual fishery drugs and distinguish MG, MB, and CV mixtures in spiked fish within 5 min, and the average recoveries in fish scales and fish meat were better 90.1% and 76.9%, respectively. The method exhibited rapidity, simplicity, and high sensitivity and is expected to be used for the screening of additives in food.

L-shaped ITO structures fabricated by oblique angle deposition technique for mid-infrared circular dichroism.

This paper proposes a mid-infrared chiral structure, which consists of L-shaped indium tin oxide (ITO) films formed on self-assembled monolayer polystyrene microspheres in two orthogonal directions by oblique angle deposition technique. Experimental results demonstrate that the structure exhibit circular dichroism (CD) responses in the range of 2.5 - 4 µm. As the thickness difference of the ITO films in the two orthogonal directions increases, the CD response enhances. The reason is that the ITO films produce cross dipoles and their bigger differences in thickness bring to bigger phase differences in optical chirality. The experimental results also demonstrate that the CD signals are evidently stronger than those of the structure consisting of silver in the mid-infrared band. This work provides a new idea for the fabrication of mid-infrared chiral structures, which have potential applications in the polarization state control of mid-infrared lasers.

Non-homogeneous composite GMR structure to realize increased filtering range.

A non-homogeneous composite guided-mode resonant (GMR) filter structure is proposed that avoids the multi-mode resonance effect and increases resonant wavelength tuning range. The composite filter structure is engineered using a combination of a varied-line-spacing (VLS) grating layer with a wedge-shaped waveguide layer. The grating is fabricated by holographic interference lithography (IL), while the wedge-shaped layer is fabricated using masked ion beam etching (MIBE) technology. The resonant wavelength has been observed to vary as a function of the spatial position on the structure. In the fabricated structure, over a length of 30 mm, the grating period increment is measured to be 149.2 nm, whereas the increment of the waveguide film thickness is approximately 100 nm. Experimental results show that a primary reflectance peak is achieved spanning a wavelength range of 805.8-1119.0 nm. The device is designed using the rigorous coupled-wave analysis (RCWA) method, and the proposed device is toward the practical application of GMR filters.

Large-area broadband optical absorber fabricated by shadowing sphere lithography.

We report a large-area broadband optical absorber consisting of Ag/SiO2 stacked plasmonic layers fabricated on a self-assembly polystyrene sphere monolayer using the glancing angle deposition. Such an absorber can absorb more than 90% of light in the spectral range of 350 - 850 nm when the polystyrene spheres have a diameter of 750 nm. The broadband absorption is due to the overlap of localized plasmonic resonance wavelengths resulting from different patchy sizes and shapes of Ag coating on polystyrene spheres. Such a simple, flexible and large-area absorber has potential applications in light cloaking and energy conversion.

Growth and optical properties of Ag-Ti composite nanorods based on oblique angle co-deposition technique.

Ag-Ti composite nanorod structures with various Ag compositions were fabricated by the oblique angle co-deposition technique, and their optical transmission spectra are tuned by composition ratios of Ag and Ti, polarization directions, and deposition angles. Such tunable optical properties have potential applications in optoelectronics. Specially, for the Ag80 composite nanorod structures, there exists a wavelength, where it is isotropic. We also show that the transmission spectra of the Ag80 composite nanorod structure for the deposition angle of 87.5° are greater than 90%, while the transmission spectra for the 75° deposition angle are lower than 20%. Utilizing such a property, high or low transmission lenses can be designed.

Switchable reflection/transmission utilizing polarization on a plasmonic structure consisting of self-assembly polystyrene spheres with silver patches.

We report a plasmonic structure for switchable reflection and transmission by polarization. The structure is composed of a hexagonal-packed polystyrene sphere array with silver patches on them. Simulations and experiments demonstrated that the conversions between reflected beams and transmitted ones can be performed when the polarization directions of incident beams vary from 0° to 90°. A switchable reflection and transmission at a given wavelength can be obtained, as long as sizes of PS spheres and azimuthal angles are properly chosen. Such a patchy plasmonic structure serving as a switch between reflection and transmission have potential applications in photoelectric control devices.

In vitro investigation of the mechanics of fixed red blood cells based on optical trap micromanipulation and image analysis.

Erythrocyte deformability correlates with various diseases. Single-cell measurements via optical tweezers (OTs) enable quantitative exploration but may encounter inaccuracies due to erythrocyte life cycle mixing. We present a three-step methodology to address these challenges. Firstly, density gradient centrifugation minimizes erythrocyte variations. Secondly, OTs measure membrane shear force across layers. Thirdly, MATLAB analyzes dynamic cell areas. Results combined with membrane shear force data reveal erythrocyte deformational capacity. To further characterize the deformability of diseased erythrocytes, the experiments used glutaraldehyde-fixed erythrocytes to simulate diseased cells. OTs detect increased shear modulus, while image recognition indicates decreased deformation. The integration of OTs and image recognition presents a comprehensive approach to deformation analysis, introducing novel ideas and methodologies for investigating erythrocytic lesions.

Thin layer chromatography coupled with surface enhanced Raman scattering for rapid separation and on-site detection of multi-components.

The separation and detection of multi-component mixtures has always been a challenging task. Traditional detection methods often suffer from complex operation, high cost, and low sensitivity. Surface enhanced Raman scattering (SERS) technique is a high sensitivity, powerful and rapid detection tool, which can realize the specific detection of single substance components, but it must solve the problem that multi-component mixtures cannot be accurately determined. Thin layer chromatography (TLC) technology, as a high-throughput separation technology, uses chromatographic plate as the stationary phase, and could select different developing phases for separation experiments. The advantages of TLC technology in short distance and rapid separation are widely used in protein, dye and biomedical fields. However, TLC technology has limitations in detection ability and difficulty in obtaining ideal signal intensity. The combination of TLC technology and SERS technology made the operation procedure simple and the sample size small, which can achieve rapid on-site separation and quantitative detection of mixtures. Due to the rapid development of TLC-SERS technology, it has been widely used in the investigation of various complex systems. This paper reviews the application of TLC-SERS technology in food science, environmental pollution and biomedicine.