QCM WITH ELECTRODE CONFIGURATION BASED ON DISTRIBUTION OF AREA FOR IMPROVING MASS SENSITIVITY (DAIS)
20230296564 · 2023-09-21
Inventors
Cpc classification
G01N29/022
PHYSICS
International classification
Abstract
In a preferred embodiment, there is provided a quartz crystal microbalance comprising a pair of electrodes and a quartz crystal disposed therebetween, one said electrode operable as a sensing electrode for interacting with an analyte, wherein said sensing electrode comprises an array of sensing electrode members positioned within a sensing electrode surface portion on the quartz crystal.
Claims
1. A quartz crystal microbalance comprising a pair of electrodes and a quartz crystal disposed therebetween, one said electrode operable as a sensing electrode for interacting with an analyte, wherein said sensing electrode comprises an array of sensing electrode members arranged on the quartz crystal.
2. The quartz crystal microbalance of claim 1, wherein the electrodes comprise the sensing electrode and a reference electrode, and the quartz crystal has a generally planar shape having opposed first and second surfaces respectively for contacting the sensing and reference electrodes, the sensing and reference electrodes being generally aligned in a direction along a depth of the quartz crystal.
3. The quartz crystal microbalance of claim 2, wherein the array of sensing electrode members is arranged on an area on the quartz crystal smaller than the reference electrode.
4. The quartz crystal microbalance of claim 1, wherein each said sensing electrode member independently of each other has a general shape selected from the group consisting of circle, square, triangle, rectangle, pentagon, triangle, ellipse, hexagon, heptagon, octagon, nonagon and decagon.
5. The quartz crystal microbalance of claim 1, wherein the sensing electrode members comprise a central sensing electrode member and one or more peripheral sensing electrode members for placement around the central sensing electrode member, optionally wherein one or more said peripheral sensing electrode members contact or at least partially overlap with the central sensing electrode member, and optionally wherein the central sensing electrode member is sized about equal or larger than the peripheral sensing electrode members.
6. The quartz crystal microbalance of claim 5, wherein the central and peripheral sensing electrode members are generally circular in shape, and the peripheral sensing electrode members are for placement along a periphery of the central sensing electrode member.
7. The quartz crystal microbalance of claim 5, wherein a plurality of said peripheral sensing electrode members are arranged along one or more enclosing lines around the central sensing electrode member.
8. The quartz crystal microbalance of claim 7, wherein the peripheral sensing electrode members are arranged along at least first and second said enclosing lines around the central sensing electrode member, the first enclosing line being interposed between the central sensing electrode member and the second enclosing line.
9. The quartz crystal microbalance of claim 8, wherein the central and peripheral sensing electrode members are generally circular in shape, and the peripheral sensing electrode members arranged along the first enclosing line are for placement along a periphery of the central sensing electrode member and interposed between the central sensing electrode member and the peripheral sensing electrode members arranged along the second enclosing line.
10. The quartz crystal microbalance of claim 8, wherein one or more said peripheral sensing electrode members arranged along the first enclosing line contact or at least partially overlap with the central sensing electrode member, and one or more said peripheral sensing electrode members arranged along the second enclosing line contact or at least partially overlap with one or more said peripheral sensing electrode members arranged along the first enclosing line.
11. The quartz crystal microbalance of claim 1, wherein the electrodes comprise gold, or wherein the quartz crystal microbalance is for operation with a harmonic overtone.
12. A quartz crystal microbalance comprising sensing and reference electrodes and a generally planar quartz crystal having opposed first and second surfaces respectively for contacting the sensing and reference electrodes, the sensing electrode being for interacting with an analyte, and the sensing and reference electrodes being generally aligned in a direction along a depth of the quartz crystal, wherein the sensing electrode comprises an array of sensing electrode members arranged on the quartz crystal, and wherein the sensing electrode members comprise a central sensing electrode member and one or more peripheral sensing electrode members for placement around the central sensing electrode member.
13. The quartz crystal microbalance of claim 12, wherein the quartz crystal has a generally discoid shape, and the sensing and reference electrodes are located at or proximal to a center of the quartz crystal.
14. The quartz crystal microbalance of claim 12, wherein the reference electrode and each said sensing electrode member independently of each other has a shape selected from the group consisting of circle, square, triangle, rectangle, pentagon, triangle, ellipse, hexagon, heptagon, octagon, nonagon and decagon.
15. The quartz crystal microbalance of claim 12, wherein the array of sensing electrode members is arranged on an area on the quartz crystal smaller than the reference electrode.
16. The quartz crystal microbalance of claim 12, wherein one or more said peripheral sensing electrode members contact or at least partially overlap with the central sensing electrode member, or wherein the central sensing electrode member is sized about equal or larger than the peripheral sensing electrode members.
17. The quartz crystal microbalance of claim 12, wherein the central and peripheral sensing electrode members are generally circular in shape, and the peripheral sensing electrode members are for placement along a periphery of the central sensing electrode member.
18. The quartz crystal microbalance of claim 12, wherein a plurality of said peripheral sensing electrode members are arranged along one or more enclosing lines around the central sensing electrode member.
19. The quartz crystal microbalance of claim 18, wherein the peripheral sensing electrode members are arranged along at least first and second said enclosing lines around the central sensing electrode member, the first enclosing line being interposed between the central sensing electrode member and the second enclosing line.
20. The quartz crystal microbalance of claim 19, wherein the central and peripheral sensing electrode members are generally circular in shape, and the peripheral sensing electrode members arranged along the first enclosing line are for placement along a periphery of the central sensing electrode member and interposed between the central sensing electrode member and the peripheral sensing electrode members arranged along the second enclosing line.
21. The quartz crystal microbalance of claim 19, wherein one or more said peripheral sensing electrode members arranged along the first enclosing line contact or at least partially overlap with the central sensing electrode member, and one or more said peripheral sensing electrode members arranged along the second enclosing line contact or at least partially overlap with one or more said peripheral sensing electrode members arranged along the first enclosing line.
22. The quartz crystal microbalance of claim 12, wherein the electrodes comprise gold, or wherein the quartz crystal microbalance is for operation with a harmonic overtone.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Reference may now be had to the following detailed description taken together with the accompanying drawings in which:
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0060] It has been observed with the uniformity distribution of a QCM with conventional circular electrode that the amplitude of vibration increases at the center of the electrode (R=0) and reduces in a Gaussian pattern moving towards the edges of the active electrode area (R.sub.n), as seen in
Mass Sensitivity Analysis of a QCM with Conventional Circular Electrode Configuration
[0061] COMSOL Multiphysics simulation software, version 5.5, was used to build the conventional QCM geometry as illustrated in
[0062] The QCM geometry was built using the parameters mentioned in Table 1 below. The geometry includes quartz crystal, top electrode and bottom electrode which are represented by the software as domains. The material properties used in the COMSOL simulations are listed in Table 2 below.
TABLE-US-00001 TABLE 1 Dimensional parameters of a 5 MHz conventional QCM for mesh dependency analysis Parameter Value Quartz radius 10 [mm] Quartz thickness 333 [μm] Electrode radius 4.25 [mm] Electrode thickness 300 [nm] Voltage 10 [V]
TABLE-US-00002 TABLE 2 Material properties utilized in COMSOL simulations Shear (μ)/ Young's (Y) No. Material Domain Density Modulus Permittivity 1. Quartz 1 2.468 g/cm.sup.3 μ = 2.947 × 10.sup.11 1 g/cm/s.sup.2 2. Gold 2, 3 19.3 g/cm.sup.3 Y = 70 GPa 1
[0063] To investigate the mass sensitivity and the uniformity distribution across the circular electrode, the resonant frequency of a 5 MHz QCM was simulated, as seen in
[0064] The fundamental resonant frequency of the QCM with conventional circular electrode was found to be 4.425 MHz. The resonant frequency of the QCM for an added mass per unit area of 20 μg/mm.sup.2 was determined as 4.341 MHz. The resonant frequency shift for the added mass was calculated as 84 kHz and the corresponding mass sensitivity was evaluated from equation (3) to be 74 Hz/μg mm.sup.2. The unequal distribution of uniformity across the circular electrode diminishes the sensing performance of the device near the electrode edges, due to the energy trapping present in the center. Hence, the energy trapping effect was further investigated by analyzing the mass loading area present on the QCM electrode.
Analysis of Effect of Mass Loading Area on Mass Sensitivity
[0065] Commercial QCM sensors consist of a sensing layer present on the sensing electrode which is responsible for analyte interaction in the form of mass loading. A change in the resonant frequency of the QCM is observed due to this mass loading effect and the corresponding area is known as the mass loading area, as seen in
[0066] In this analysis, the mass loading area was considered as a boundary layer of zero thickness present on the top electrode with an adsorption capability of 20 μg/mm.sup.2. The mass loading area of the QCM was varied for values of 0.425 mm, 0.85 mm, 1.275 mm, 1.7 mm, 2.125 mm, 2.55 mm, 2.975 mm, 3.4 mm, 3.825 mm, and 4.25 mm, which corresponds to 10% to 100% coverage of the entire top electrode. The resonant frequency shift for an added mass per unit area of 20 μg/mm.sup.2 was estimated to determine the mass sensitivity.
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[0068] In the following analysis, the influence of mass loading area on mass sensitivity was investigated for a 5 MHZ QCM with different electrode radii values, as seen in
[0069] A 5 MHz QCM with electrode radii values of 1 mm, 1.5 mm, 2.5 mm, 4.25 mm and 5.5 mm was built using the design parameters mentioned in Table 1 to determine the influence of mass loading area on the mass sensitivity. Here, the mass loading area was considered as a boundary layer of zero thickness present on the top electrode with an adsorption capability of 20 μg/mm.sup.2. The mass loading area of the QCM was varied for values corresponding between 10% and 100% coverage of the entire top electrode.
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[0072] It has been appreciated that collectively utilizing smaller electrodes in the place of a larger conventional electrode may facilitate an approach to improve mass sensitivity of the device by capitalizing the areas of opportunity on the QCM surface, while also ensuring a higher mass sensitivity. Employing this concept, electrode configurations of the QCM were developed based on distribution of the mass loading area to improve mass sensitivity.
[0073] The outcome of the investigation on mass loading area involving a 5 MHz QCM with an electrode radius of 5.5 mm and 1 mm was considered. As seen in
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[0075] Table 3 below identifies the parameters utilized to design the 5 MHz QCM used in this analysis. The resonant frequency and frequency shift were determined for an added mass per unit area of 20 μg/mm.sup.2 to evaluate the mass sensitivity.
TABLE-US-00003 TABLE 3 Design Parameters of a QCM with novel DAIS electrode configuration Parameter Value Quartz radius 10 [mm] Quartz thickness 333 [μm] Top outer electrode and 2.96 [mm] bottom electrode radius Electrode thickness 300 [nm] voltage 10 [V]
[0076] Table 4 below presents comparison of the resonant frequency shift and the mass sensitivities of the QCM with DAIS electrode and circular electrode configurations. The circular electrode configuration attained a higher frequency shift of 83.5 kHz and a mass sensitivity of 151 Hz/μg mm.sup.2. The DAIS electrode configuration achieved a comparable frequency shift of 82.5 kHz and exhibited a higher mass sensitivity of 185 Hz/μg mm.sup.2 while possessing a noticeably lesser mass loading area.
TABLE-US-00004 TABLE 4 Comparison of resonant frequency shift and mass sensitivity of the DAIS electrode configuration and the conventional circular electrode configuration. Conventional Circular DAIS electrode - design 1 Electrode Mass loading 22.21 mm.sup.2 27.52 mm.sup.2 area Frequency F.sub.1 = 4.4565 MHz F.sub.1 = 4.4445 MHz shift F.sub.2 = 4.374 MHz F.sub.2 = 4.361 Δf = 82.5 kHz MHzΔf = 83.5 kHz Mass 182 Hz/μg mm.sup.2 151 Hz/μg mm.sup.2 Sensitivity
[0077] The central electrode area of the DAIS—design 1 consisting of 7 circular electrodes of radius 0.76 mm was replaced by a single circular electrode of radius 1.75 mm in the DAIS—design 2, as seen in
TABLE-US-00005 TABLE 5 Comparison of resonant frequency shift and mass sensitivity of the DAIS electrode configurations design 1 and design 2 DAIS electrode - design 1 DAIS electrode - design 2 Mass loading 22.21 mm.sup.2 22.26 mm.sup.2 area Frequency F.sub.1 = 4.4565 MHz F.sub.1 = 4.455 MHz shift F.sub.2 = 4.374 MHz F.sub.2 = 4.3725 MHz Δf = 82.5 kHz Δf = 82.5 kHz Mass 182 Hz/μg mm.sup.2 185 Hz/μg mm.sup.2 Sensitivity
[0078] The DAIS electrode—design 1 and design 2 attained similar frequency shift and comparable mass sensitivity values. This indicates that the central overlapping electrodes in the DAIS configuration can be replaced by a singular electrode of equivalent mass loading area, which corroborates the presence of the inherent energy trapping.
[0079] To investigate the effect of surrounding electrodes, the DAIS—design 3 was designed, which utilized smaller surrounding electrodes of radius 0.62 mm, while the central electrode radius was fixed at 1.75 mm, and the design parameters remain unchanged as per Table 3. For comparison, a 5 MHz QCM with a ring-dot electrode configuration of similar mass loading area and equal outer electrode radius was built for comparison. The radius of the central circular electrodes of the ring-dot electrode configuration and the DAIS electrode configuration were kept approximately equal to 1.75 mm. The area of the ring electrode in the ring-dot configuration and the total area of the surrounding circular electrodes of the DAIS—2 configuration were approximately equal to 12 mm.sup.2 (±3% difference). The gap length between the ring and dot electrodes in the ring-dot electrode configuration was equal to the overlap length between the central circular electrode and the smaller surrounding electrodes in the DAIS configuration approximately equal to 0.4 mm.
[0080] Different electrode configurations shown in
TABLE-US-00006 TABLE 6 Comparison of mass sensitivity and area under the uniformity curve for a 5 MHz QCM with circular electrode, ring-dot electrode configuration and the novel DAIS electrode configuration Circular Ring-Dot Electrode Electrode DAIS - design 2 DAIS - design 3 Mass loading 27.52 mm.sup.2 21.8 mm.sup.2 22.26 mm.sup.2 21.533 mm.sup.2 area Mass Sensitivity 151 Hz/μg mm.sup.2 180 Hz/μg mm.sup.2 185 Hz/μg mm.sup.2 190 Hz/μg mm.sup.2 Area under curve 96 mm.sup.2 80 mm.sup.2 91 mm.sup.2 82 mm.sup.2 (uniformity area)
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[0082] The ring-dot electrode configuration exhibited a poor uniformity distribution, despite comprising a distributed electrode setup. This is due to the large dot electrode and a comparatively smaller ring electrode area which diminishes the uniformity distribution. The displacement amplitude at the center was found to be nearly 21 nm, which was seen to reduce to the range of 5-10 nm near the electrode edges, thereby resulting in a narrower uniformity distribution. The uniformity area of the ring-dot electrode configuration was evaluated as 80 mm.sup.2.
[0083] The uniformity distribution of the DAIS—design 2 was found to be similar to the conventional circular electrode configuration, while possessing lesser mass loading area. It attained a displacement amplitude of approximately 23 nm at the center, which was observed to decrease radially to the range of 10-15 nm near the electrode edges. The uniformity area of the DAIS—design 2 was estimated as 91 mm.sup.2. Hence, for a 19% lesser mass loading area, there was only a 5% decrease in the uniformity distribution of the DAIS—design 2 in comparison with the conventional circular electrode. Table 6 shows that the DAIS—design 2 also attained a comparable frequency shift, and a higher mass sensitivity of 185 Hz/μg mm.sup.2 compared to the conventional circular electrode configuration.
[0084] The uniformity area of the DAIS—design 3 was estimated as 82 mm.sup.2. Hence, for a 22% lesser mass loading area, there was only a 14% decrease in the uniformity distribution of the DAIS—design 3, in comparison with the conventional circular electrode. The DAIS—design 3 also attained a comparable frequency shift, and a higher mass sensitivity of 190 Hz/μg mm.sup.2 in contrast with the conventional circular electrode configuration.
[0085] The analysis results suggests that QCM electrodes designed using DAIS approach provided a competent sensing performance by capitalizing on the inherent energy tapping effect. Their ability to attain a higher mass sensitivity and retain the uniformity, while utilizing lesser mass loading area may serve as a proof of principle for sensing applications. Investigating the DAIS approach to build a plausibly optimized QCM electrode configuration could further improve the mass sensitivity of the device for a lesser mass loading area, thereby enabling DAIS approach for fabricating potential candidates for sensing in environments with low analyte concentration.
[0086] In yet another experimental study, another 5 MHz quartz crystal microbalance was considered with the electrode configuration seen in
TABLE-US-00007 Parameter Value Oscillator radius 10 [mm] Oscillator thickness 333 [μm] Top outer electrode and 2.5 [mm] bottom electrode radius Electrode thickness 300 [nm] Alternating voltage 10 [V]
[0087] The resonance frequency shift for an added mass was determined to be as provided below:
TABLE-US-00008 2.5 mm Conventional Circular DAIS - design 0 Electrode QCM Mass loading area 16.1 mm.sup.2 19.634 mm.sup.2 Electrode radius 1 mm × 6 2.5 mm outer radius = 2.5 mm Frequency shift F.sub.1 = 4.4625 MHz F.sub.1 = 4.455 MHz (Δf) F.sub.2 = 4.373 MHz F.sub.2 = 4.372 MHz Δf = 89.5 kHz Δf = 83 kHz
[0088] The above suggested that the quartz crystal microbalance attained a higher resonant frequency shift and thus mass sensitivity for the same added mass compared to conventional circular electrode configuration, and the uniformity distribution achieved by the microbalance was comparable to conventional design, as may be illustrated by
[0089] It has been recognized that a modification to the conventional circular electrode configuration, or the n-m electrode configuration, may permit studies on the radial dependence and effect of unequal electrode radii on the QCM mass sensitivity. The QCM with n-m electrode configuration illustrated as seen in
[0090] Analogous to the above, the DAIS may involve localizing the energy trapping effect by identifying the regions on the QCM electrode which provides a higher resonant frequency shift due to mass loading. Positioning the mass loading area on these regions may provide a means to capture the energy trapping effect and consequently enhance the mass sensitivity of the QCM while utilizing lesser mass loading area. Hence, an analysis was conducted to infer the effect of unequal radius of the novel DAIS electrode configuration and bottom circular electrode configuration to investigate the uniformity distribution and the mass sensitivity of the QCM. Provided below is a table showing dimensional parameters of 5 MHz DAIS electrode QCM for mass sensitivity analysis:
TABLE-US-00009 Parameter Value Quartz radius 10 mm Quartz thickness 333 μm Top DAIS electrode radius 2.96 mm Bottom electrode radius 2.96, 5.92, 8.88 mm Electrode thickness 300 nm
In this analysis, as seen in
[0091] It has been appreciated that the fundamental resonant frequency of the QCM may be enhanced by operating in higher harmonic overtones to attain enhanced mass sensitivity without altering the quartz thickness. In this overtone mode, the Sauerbrey's equation is modified as:
where ‘n’ represents the overtone number (n=1, 3, 5, 7 . . . ). When operated at higher resonant frequencies, the frequency shift measured and observed is higher, thereby depicting a potentially higher mass sensitivity in comparison with the fundamental mode. However, while operating at higher frequencies, the stability of the quartz crystal was found to deteriorate due to introduction of noise and vibrational instability which in turn affects the quality factor. Furthermore, the radial mass sensitivity across the conventional QCM is found to converge closer to the centre in higher harmonic overtones, thereby reducing the uniformity area. This in turn results in an unequal and diminished sensing performance across the QCM electrode and near to the electrode edges.
[0092] By localizing the energy trapping effect across the quartz surface, the DAIS electrode configuration was found to possibly permit enhanced mass sensitivity while retaining the radial mass sensitivity distribution, thereby not diminishing the uniformity area. Hence, in an analysis, the QCM with DAIS electrode configuration with an outer electrode radius of 2.96 mm was excited at harmonic overtones of n=1,3,5 to investigate the influence on mass sensitivity and the radial mass sensitivity distribution. Furthermore, the analysis results were contrasted with a QCM with conventional circular electrode configuration operating in similar overtone modes.
[0093] To fabricate the QCM with novel DAIS electrode configuration, blank polished AT-cut quartz crystals with an operating frequency of 5 MHz may be used with fabrication steps involving microfabrication techniques for developing conventional QCM sensors, such as using a shadow mask to form the electrode pattern, followed by electrode deposition using gold as the material. As seen in
[0094] While the invention has been described with reference to preferred embodiments, the invention is not or intended by the applicant to be so limited. A person skilled in the art would readily recognize and incorporate various modifications, additional elements and/or different combinations of the described components consistent with the scope of the invention as described herein.