MATERIALS AND METHODS USED WITH PLASMON RESONANCE DETECTION TECHNIQUES
20220229318 · 2022-07-21
Inventors
Cpc classification
G01N15/1436
PHYSICS
G01N21/554
PHYSICS
International classification
Abstract
Improved multilayered magneto-optic-plasmonic (“MOP”) films that are used in connection with surface plasmon detection that have a first layer comprising titanium, a second layer selected from a group consisting of gold and silver, a third layer comprising cobalt, and a fourth layer comprising gold are disclosed. In an embodiment, the film has a first titanium layer with a thickness of approximately 2 nm, a second gold layer with a thickness of 35 nm, a layer of cobalt having a thickness of approximately 8 nm and a fourth gold base layer having a thickness of approximately 10 nm.
Claims
1. An improved multilayered magneto-optic-plasmonic (“MOP”) film used in connection with surface plasmon detection, said film comprising: a first layer comprising titanium, a second layer selected from a group consisting of gold and silver, a third layer comprising cobalt, and a fourth layer comprising gold.
2. The improved MOP film of claim 1 wherein said first titanium layer has a thickness of approximately 2 nm, said second layer is comprised of gold and has a thickness of 35 nm, said third cobalt layer has a thickness of approximately 4 nm and said forth gold base layer has a thickness of approximately 8 nm.
3. The improved MOP film of claim 1 wherein said first titanium layer has a thickness of approximately 2 nm, said second layer is comprised of silver and has a thickness of 35 nm, said third cobalt layer has a thickness of approximately 4 nm, and said forth gold base layer has a thickness of approximately 8 nm.
4. The improved MOP film as recited in claim 1 wherein said first titanium layer has a thickness of approximately 2 nm, said second layer comprise silver and has a thickness of 35 nm, said third layer comprises cobalt and has as thickness of approximately 2 nm and said fourth layer is gold and has a thickness of approximately 4 nm.
5. The improved MOP film as recited in claim 1 wherein said first titanium layer has a thickness of approximately 2 nm, said second layer comprise silver and has a thickness of 35 nm, said third layer comprises cobalt and has as thickness of approximately 2 nm and said fourth layer is gold and has a thickness of approximately 10 nm.
6. The improved MOP of claim 1 wherein the further layer, said fifth lawyer adjacent to said forth Au layer is comprised of polycarbonate having a thickness of between 2 and 15 nm.
7. A system for the measurement of an analyte using surface plasmon resonance, said system comprising; a flow cell for transporting a fluid analyte said flow cell having an inlet port, a chamber comprising walls and an exit port and said flow cell further comprising a multilayered magneto-optic-plasmonic (“MOP”) film said film having a first surface in defining a wall of said chamber, said multilayer film further comprising a first layer comprising titanium having a thickness of approximately 2 nm, a second layer comprising a material selected from a group consisting of gold and silver, said material having a thickness of approximately 35 nm, a third layer comprising cobalt having a thickness of between 2 nm and 4 nm, and a fourth layer comprising gold having a thickness of approximately 10 nm; said system further comprising; a light source, a photodetector, and a processor, wherein said light source is directed at said multilayered MOP film surface and incident angle and light reflected from said film surface is directed to a detector, and said detector creates a signal, and said signal is transmitted to said processor, and said processor compares said signal to a baseline signal and provides an output.
8. The system of claim 7 wherein said fluid comprises a liquid analyte.
9. The system of claim 8 further comprising a pump wherein said pump moves said liquid analyte through said flow cell.
10. The system of claim 7 wherein said light source comprises a prism and the wavelength directed to said film surface can be varied.
11. The system of claim 7 wherein the incident angle that light is directed to said MOP film surface is variable.
12. The system of claim 7 further comprising means to variably apply a magnetic field to said MOP film.
13. A method of measuring for a target agent present in an analyte, said method comprising, preparing a first surface of a MOP film with receptors that can bind with said target agent, wherein said MOP film comprises, a first layer comprising titanium having a thickness of approximately 2 nm , a second layer selected from a group consisting of gold and silver and having a thickness of approximately 35 nm, a third layer comprising cobalt having a thickness of between 2 and 4 nm, and a fourth layer comprising gold having a thickness of approximately 10 nm , and preparing a first standard fluid as a baseline, preparing an analyte comprising said target agent, preparing said forth base layer with an agent selected to bind with said target analyte, incorporating said MOP film to a flow cell adapted to receive said analyte, directing a light source at an opposite surface of said MOP film, introducing said standard fluid to said flow cell, measuring the light reflected from said film to create a first signal, introducing said analyte comprising said target agent to said flow cell, measuring the light reflected from said film when or after said target analyte has passed through said flow cell to create a second signal.
14. The method of claim 13 wherein said light from said light source has a wavelength of 780 nm.
15. The method of claim 13 wherein said light from said light source has a wavelength of 780-785 nm.
16. The method of claim 13 further comprising the application of a magnetic field to said MOP film.
17. The method of claim 13 wherein said probing sample is in liquid.
18. The method of claim 13 wherein said probing sample is helium.
19. The method of claim 13 wherein said probing sample is air.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
DETAILED DESCRIPTION
[0029] Referring now to
[0030] In the system disclosed, a right-angled prism is used for the excitation of the surface plasmons. The circle with a cross symbol 117 is the notation showing the direction of the applied magnetic field H on the MOP film. Both air and Helium were used as the probing samples.
[0031] The configurations disclosed here include the effect created by the adhesion layer, which although may introduces losses, it is often necessary for reliable fabrication, and they are composed of thin plasmonic layers on the side of the sensing surface, which is opposite to a typical or conventional arrangement.
[0032] The complex optical constants of all the materials were obtained from Johnson, P.; Christy, R. Optical constants of transition metals: Ti, V, Cr, Mn, Fe, Co, Ni, and Pd. Physical 206 review B 1974, 9, 5056. See also Rizal, C.; Belotelov, V. I. Sensitivity comparison of surface plasmon resonance (SPR) and magneto-optic 185 SPR biosensors. Eur. Phys. J. Plus 2019; Rizal, C.; Pisana, S.; Hrvoic, I. Improved magnetooptic surface plasmon resonance biosensors. Photonics 187 2018. The optical constants are refined using the experimental results by fitting the data to the model.
[0033] The outer or base 8 nm Au layer also works as a capping layer for both the configurations (Configurations A and B). The total thickness of the multilayer was chosen/optimized to match the thickness of a single Au layer that gives the best result.
[0034] Now referring to
[0035] The multilayered configurations were fabricated using a deposit technique using electron beam (“e-beam”) evaporation on BK7 glass using four crucibles. In the embodiments disclosed, the films were deposited in a single deposition run without breaking vacuum. A characterization performed at the time of fabrication included the verification of the film thickness using atomic force microscopy. The deposition rates were 1.2, 0.7, 0.5 and 0.7 As-1 for Ti, Au, Ag, and Co, respectively. The e-beam evaporation method used to create the films offered structural and morphological control of the materials. Each metal has different deposition rates and these rates were optimized to obtain appropriate smoothness, crystallinity, and layer thicknesses. The outer base 4 nm Au layer also acts as a capping layer and prevents surface oxidation for the fabricated material. In other embodiments a further layer with 0 to 15 nm thick inert polycarbonate laminate plastic is also provided as protective layer. It has been found that the higher sensitivity and improved performances shown by the MO-based SPR sensors, several technical challenges still prevail such as oxidation of sensor surface leading to degradation of performance, issues with reproducibility of the sensor surface due to the difficulty of removing adsorbed materials, and scratching of sensor surface during cleaning. In addition to the composition and layer thickness, interface roughness between each layer of the sensor configuration also plays critical roles in defining MO effect and sensitivity of the sensor. A protective polycarbonate layer does not significantly compromise the MO enhancement and sensitivity. The magneto-optic plasmonic (MOP) sensor is described using classical electromagnetic theory: reflection, transmission, and absorption of the optical radiation. The configurations shown were optimized using COMSOL Multiphysics software—the finite element method and transfer matrix method. COMSOL is a simulation platform that encompasses all of the steps in the modeling workflow from defining geometries, material properties, and the physics.
[0036] The magneto-optic plasmonic (MOP) sensors disclosed—such as the multilayer configuration shown in
[0037] The wavelength, λ dependent permittivity's, linear (e) and non-linear (magneto-optic (ε.sub.mo)) were used for the simulation. The applied magnetic field (H), is considered transverse direction (parallel to the sensor surface and perpendicular to the plane of incidence) whose dielectric permittivity tensor can be given as
where ε.sub.0 is the permittivity of the multilayer at H=0 and ε.sub.mo is the magneto-optic constant due to the applied H field (H=H). The ϵ.sub.mo is quadratic function of the field.
The constants for the optical parameters at 632.8 nm, BK-7 (2.2940+j00), Ti (−6.866+j20.36), Au (−11.13+j1.327), Co (−12.48+j18.45) and emo (−0.65+j0.0005), He (1.00006977), air (1.0005530), and δn632.8 (0.000483) and at 785 nm, BK-7 (02.28+j00), Ti (−06.51+j24.81), Ag (−29.79+j00.3), Co (−16.43+j23.38), and emo (−0.85+j0.0006), Au (−22.86+j01.43), He (01.00006960), Air (01.00055020), and δn785 (0.000483).
[0038] The optical parameters were further refined using the experiment by fitting the experimental data to the theory/model. The model consisted of six layers as: Prism (BK7), Ti, Ag, Co, Au, and probing samples (air or Helium). The effect of external magnetic, H field and excitation λ on SPR and sensitivity were included in the calculation.
[0039] For the p-polarized incident light input through the triangular prism as illustrated in
where ω is the angular frequency, c is the velocity of light in vacuum, and ϵ.sub.d, μ.sub.d and ϵ.sub.m, μ.sub.m are the dielectric permittivity and magnetic permeability functions, respectively. This is done using a right-angled prism as shown in
[0040] The sensitivity of a biosensor is a critical parameter for its bench marking. However, given the nature of a wide variety of biosensors (e.g., chemical, mechanical, electronic biosensors, humidity sensor, NO.sub.2 sensors, poisonous gas sensors, etc.) currently being studied, and whether or not chemical, biological or physical changes are being recorded and/or the localized or propagating SPR are being studied, there is no unified sensitivity metrics available to quantify and compare the performance of each of these biosensors. The new sensitivity metrics are defined as:
[0041] More importantly, since the sensitivity of SPR sensors has been defined differently than the sensitivity of the MOSPR sensors, using the conventional sensitivity definition, we are not able to accurately compare the performance of these sensors side by side. Realizing this problem, new sensitivity benchmark metrics were used to allow the comparison of the performance of SPR sensors to MOSPR sensors.
[0042] Unlike the SPR signal, which depends on the magnitude of Rp, the magnitude of the MOSPR signal depends not only on the relative change in Rp for the p-polarized incident light, but on the relative change in dRp (between the air and Helium media) as well as the derivative of the dRp curve and absolute |dRp| value. This means that the magnitude of the MOSPR signal relies on the characteristics of the plasmon resonance curve as well as the variation of plasmon dispersion due to the opposing magnetic fields (H±/M±). Note that the sign of the ε.sub.mo is taken as positive for the clockwise rotation of the co-ordinate system when viewed along the z-axis and that the z-axis is directed along the H/M direction. The detection limit, D is also defined differently in literature for example, in atomic absorption spectrometry analysis, a diluted solution is analyzed, and the corresponding absorbance is recorded. Another example would be in chemical sensing, where D is defined as the lowest quantity of a substance that can be distinguished from when no sample is present. In most measurements, D is the smallest concentration of either gas or liquid media that generate signals, which are at least 3× more than the instrumental noise, i.e., the 3× the standard deviation, σ of the recorded absorbance signal. Mathematically, D can be represented as: D=s.sub.0+3×σ, where s.sub.0 is the instrumental noise. However, the problem with the above-mentioned definitions is that D is not unique, and the performance of two different sensors are not comparable. Moreover, D can vary depending on the type of noise contribution taken into account during the measurement, and whether or not the instrument is calibrated prior to it. In the current work, D is defined as: D=σS where, σis the standard deviation of the noise (≈5.0×10.sup.−4) and S is the sensitivity, expressed in %/RIU. Note that D can slightly vary depending on the instruments used and the noise they render during measurements. Although D of the sensor can be improved by modulating λ, amplitude, phase or angle of incidence, in the present case of the MOSPR sensor, it is the H field that is used to modulate and improve D. The size, shape, slope, and intensity of the SPR and MOSPR curves and thus, the detection limits are primarily dependent on these parameters.
[0043] For the reflectance and T-MOKE characterization a laser diode from Thorlabs QL7816S-B-L, Germany, was used to generate a linearly p-polarized light. The laser wavelength was tuned via temperature control of the module with an accuracy of 0.01 K and was controlled using a Horiba HR-320 spectrometer. The optical radiation was then collimated and focused using spherical and cylindrical lenses with f=150 mm and 18 mm, respectively. The reflected radiation was collected using a monochrome CMOS matrix camera, IDS UI-3360CP-M-GL, having 2048×1088 px screen (11.264 mm×5.984 mm screen dimension), yielding a 5.5 μm pixel size. The MOP samples were placed inside an electromagnet (H˜≈30 mT) with the inter-polar gap of 30 mm in transverse Kerr geometry (orthogonal to the plane of incidence), and controlled via LabVIEW program to record the real-time reflectance angular spectra as well as the T-MOKE spectra. Air with 30% humidity was blown at atmospheric pressure and room temperature of 21.6° C.
[0044] The optical radiation is incident on the prism with a roughly 3° diverging beam centered around the resonant surface plasmon excitation angle. For both reflectance and T-MOKE effect, angular interrogation is used with the incident angle varied between 39-43° as collected by the CMOS camera. For the T-MOKE study, the multilayers were magnetized in the transverse direction (as indicated by the direction of H in
[0045] The effect of excitation λ on the sensitivity has been studied here.
[0046] Now referring to
[0047]
[0048]
[0049] Still referring to
[0050] The shape of the reflectance curve (Lorentzian) is determined by the mode propagation constant. The real and imaginary parts of the propagation constant can be determined by the SPR angle and resonance width as Re[β]=k0n sin(θSPR), and Im[β]=0.5 k0n Δθ cos(θSPR), respectively.
[0051] The detection limit, D (determined using the experimentally refined theoretical parameters and experimental noise value) of the SPR and MOSPR sensors are listed in Table 4.
TABLE-US-00004 TABLE 4 DETECTION LIMIT (D) OF THE SPR AND MOSPR SENSORS AT λ = 632.8 AND 785 NM, RESPECTIVELY. NOTE THE THICKNESSES OF TOP A AND MIDDLE CO LAYERS. D.sub.SPR (RIU) D.sub.MOSPR (RIU) Material,
(nm) 632.8 nm 785 nm 632.8 nm 785 nm Au(10)/Co(4)/Ag(35)/
.30 × 1.55 × 1.76 × 1.67 × Ti(2) 10.sup.−5 10.sup.−6 10.sup.−
10.sup.−
14
Au(8)/Co(4)/Au(35)/ 4.30 × 1.05 × 1.26 × 1.51 × Ti(2) 10.sup.−5 10.sup.−6 10.sup.−
10.sup.−
work
Au(4)/Co(2)/Ag(35)/ — — 2.05 × 7.10 × Ti(2) 10.sup.−
10.sup.−
work
indicates data missing or illegible when filed
The D obtained for the optimized sensor configuration is ≈7.10×10−6 RIU. This value is comparable (slightly higher) to D for the MOSPR sensors coupled to a photonic crystal.
[0052] The enhancement of MOSPR effect clearly prevails in Ag-rich structures at both visible and IR excitation wave-lengths and is more prevalent at IR λ=785 nm. The ease of calculating/measuring changes in reflectivity vs. θ, sharp resonance peak, and enhancement in detection limit make MOSPR sensors very promising for early disease detection. The detection limit can be further improved by optimizing the excitation λ, modifying light-matter coupling, improving measurement schemes, and reducing the detection noise of the instruments involved. By further optimizing the Co layer thickness to 2 nm, both the sensitivity and detection limit may be further increased.
[0053] The fact that the Ag layer in the multilayer leads to a narrowing of the resonance in the reflectance curve, as indicated by the lower Δθ and higher Q-factor, is an indication of the lower optical losses (higher conductivity) of Ag. Using Ag for the inner plasmonic layer provides higher Q-factor but cannot be used without an additional capping layer for the external plasmonic layer to avoid oxidation. The outer Au layer is in contact with the probing sample, in this case, air.
[0054] Two types of SPR configurations based on 4 or 8 nm of Co and Au versus Ag layers were presented and obtained the quality factor for two plasmonic sensing schemes (SPR versus T-MOKE). While the ferromagnetic Co introduces some losses for the SPR spectra, the T-MOKE response obtained overrides this loss. Magneto-optical non-reciprocity becomes more significant in these structures leading to an increase in the magnitude of the transverse Kerr effect and thus, the Q-factor. The advantage of the T-MOKE sensor over the existing SPR based sensors is significant.
[0055] As identified by SPR and MOSPR characteristics, the magneto-optic-plasmonic configuration disclosed show improved sensitivity and detection limit (D) at both the visible and near infra-red (IR) wavelengths λ. The sensitivity measured at 785 has higher sensitivity than when measured at 632.8. In addition, the results show that when the top AU layer is reduced, the sensitive and detection limit are even higher. The samples studied were continuously passed through the sensor for about 10 seconds at the same speed and the measurement was recorded. The recorded data in this case is not a function of measurement time. Despite the optical loss incurred by the metals, the magnetic activity significantly enhanced the MOSPR sensitivity and detection limit at both wavelengths and almost 4× higher at IR. These results are considered significant and can form the benchmark for studying the performance of a wide variety of biosensors currently being developed or will be developed in the near future. The calculated D is ≈7.10×10.sup.−6 RIU (refractive-index-unit) at 785 nm, which is also larger than the optimized MOSPR sensors coupled to a photonic crystal.
[0056] The foregoing description of the present invention has been presented for purposes of illustration and description but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention, the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.