Quartz Crystal Microbalance Method Research Articles

Measurement of Pt consumption from Pt electrodes during water electrolysis using the quartz crystal microbalance (QCM) method: Effect of the water electrolysis method and the concentration of chloride ions in the aqueous solution

The consumption of the Pt electrocatalyst, which occurs when aqueous solution with neutral pH is electrolyzed with a Pt electrode to produce hydrogen or oxygen, was measured from the change in resonance frequency using the QCM method. First, it was found that the Pt consumption from the electrode during water electrolysis while applying a steady positive potential was very small, but it was almost proportional to the time the current was applied. Second, when electrolysis was performed by polarity reversal electrolysis of the anode and cathode periodically during electrolysis, the amount of Pt consumed increased in proportion to the number of polarity reversal was exchanged. The Pt consumption obtained by the QCM method was in close agreement with the value obtained by EDX method, proving the validity of the measurement method. The QCM measurement method was also proven to be a reliable method of measurement.

Quartz crystal microbalance analysis of effects of surfactants on dissolution kinetics of poly(4-hydroxystyrene) partially protected with t-butoxycarbonyl group

Abstract Surfactants comprise water-repellent and water-attracting moieties and have been used to improve the lithographic performance of resist materials. However, the effects of surfactants on the dissolution kinetics of these materials are still unclear. In this study, the effects of surfactants on the dissolution kinetics of partially-protected poly(4-hydroxystyrene) (PHS) in 0.26 N tetramethylammonium hydroxide aqueous solution was investigated using a quartz crystal microbalance method. Anionic (sodium n-octanonate, sodium 1-hexanesulfonate, n-dodecylbenzenesulfonic acid, and sodium n-dodecyl sulfate), cationic (methylamine hydrochloride, dodecyltrimethylammonium chloride, and 30% ammonium lauryl sulfate solution), nonionic (sorbitan monooleate, polyoxyethylene(23)lauryl ether, and polyoxyethylene(10)hydrogenated castor oil), and amphoteric (35% lauryl dimethylaminoacetic acid solution) surfactants were examined. The surfactant significantly affected the dissolution kinetics of the PHS films. The surfactant effects were significantly reduced by protecting the hydroxyl groups of PHS. The effect of the surfactant on the dissolution kinetics depended on the surfactant rather than on the surfactant type.

Reversible storage of tetraethyl ammonium cation in CFx-based cathode

Carbon fluorides (CFx) are considered as the potential cation storage materials in alkali metal-based battery systems because of the high theoretical specific capacity (865 mAh g-1 when x = 1). However, the reversibility of cathode reaction is seriously disturbed by the strong metal-fluorine interactions among the electrode products (e.g., LiF). By contrast, the relatively weak N-F bond makes the CFx-based battery system using quaternary ammonium cation (QAA+) a promising alternate, but the electrode mechanism between CFx and QAA+is little understood yet. In this work, tetraethylammonium cation (TEA+) is employed as the charge carrier using the electrolyte solution of sulfolane (SL) for CFx cathode. The CF0.56 electrode exports 710 mAh g-1 during the initial TEA+-CF reaction, and the electrode product (TEAF) can be decomposed under elevated potential that yields amorphous carbon fluoride and a reversible capacity of ∼300 mAh g-1 can be reached in the subsequent galvanostatic charge-discharge cycles. The TEAF product is non-crystallizable that exists in a sticky form on the surface of electrode, which contributes to an improved electrode structural stability while also leads to an unsatisfactory performance of the amorphous carbon fluoride with large number of superficial active sites. The electrode mechanism and the mechanical property of electrode interface are discussed in depth by in-situ Raman and electrochemical quartz crystal microbalance (EQCM) methods.

Evaluation of reflective fiber-optic surface plasmon resonance sensor for monitoring scale deposition.

A reflective surface plasmon resonance (SPR) sensor was evaluated for real-time monitoring of scale deposition. The sensor consists of an optical fiber, only 5mm at the gold-coated tip of the sensing area. The effect of silica growth on the sensor response was evaluated using a Na2SiO3 solution. The sensitivity of the sensor to silica was 1.6 ± 0.3nm per one immersion in the solution of 1000mg/L (as SiO2) at 85°Cand subsequnt air drying, as indicated by theSPR peak shift. The amount of silica deposited on the gold surface was measured by the quartz crystal microbalancemethod, and the SPR sensitivity of 0.089nm/ng to silica mass was obtained. The detection limit (3σ) of the SPR sensor was 17ng, correspondingto a thickness of 2.5nm for amorphous silica. The SPR sensor wastested in geothermal brine sampled at the Sumikawa Geothermal Power Plant, where a clear SPR shift was observed, suggesting the effectiveness of the SPR sensor for scale monitoring.

Electrochemical quartz crystal microbalance study of underpotential deposition of mercury on iridium metal and iridium oxide

AbstractTo evaluate the properties of an Ir‐based catalyst (IrOx), which is the anode in polymer electrolyte membrane‐type water electrolysis, a new method for estimating the electrochemical surface area (ECSA) is required. ECSA evaluation using the underpotential deposition of mercury (Hg‐UPD) can be applied to metals and oxides. However, research regarding Hg‐UPD is needed because several Hg(II)/Hg(I) redox reactions occur simultaneously, and direct evidence of Hg‐UPD on IrOx has not been reported. We previously confirmed the Hg‐UPD phenomenon on Ir polycrystalline films using the electrochemical quartz crystal microbalance (EQCM) method. However, measurements on IrOx electrodes were not performed. In this study, Ir and IrOx electrodes are prepared by the sputtering method, and their Hg deposition behavior observed by EQCM. We quantitatively confirm Hg‐UPD on Ir metal surfaces and provide new evidence of Hg‐UPD on the IrOx surface. These results contribute to establishing the ECSA evaluation of various Ir‐based catalysts.

Stratified polymer dissolution model based on impedance data from quartz crystal microbalance method

Abstract In lithography, the development process is essential for achieving high fidelity. The quartz crystal microbalance (QCM) method is a primary tool for analyzing the dissolution kinetics of resist polymers by measuring their frequency and impedance. However, impedance charts are underutilized. We propose a stratified polymer dissolution model (SPDM) to simulate polymer dissolution in developers and analyze QCM charts. Using SPDM, we accurately reproduced both the frequency and impedance charts. The feature values describing the dissolution kinetics were successfully extracted from the QCM charts, enabling the investigation of the effects of developers on dissolution kinetics.

Effects of acid generator anions on radiation-induced decomposition and dissolution kinetics of chemically amplified resists

Chemically amplified resists (CARs) are widely used in lithography for manufacturing semiconductor devices. To reduce the occurrence of stochastic defects in CARs, increased acid generator concentration is required. In this study, we investigated the effects of acid generator anions on the radiation-induced decomposition of acid generators using electron pulse radiolysis and γ-radiolysis methods. Their effects on the dissolution dynamics of poly(4-hydroxystyrene) (PHS) films were also investigated using contact angle measurement and quartz crystal microbalance methods. Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-1-butanesulfonate, triphenylsulfonium 4-toluenesulfonate, and triphenylsulfonium salicylate, were used as acid generators or photodecomposable quenchers. The anions showed minimal effect on the decomposition of the acid generators and photodecomposable quenchers; however, they influenced the surface free energy, dissolution kinetics of the PHS films, and water penetration into the PHS films. In particular, the effect of salicylate on the dissolution kinetics of PHS films is significant.

Dissolution dynamics of partially protected poly(4-hydroxystyrene) in organic developers investigated by a quartz crystal microbalance (QCM) method

Poly(4-hydroxystyrene) (PHS) molecules in solid films are connected to each other through polar and nonpolar molecular interaction and hydrogen bonds. Although the dissociation of phenolic hydroxyl groups plays a major role in the dissolution of PHS films in tetramethylammonium hydroxide (TMAH) aqueous developer, it is important to clarify the effects of other interactions. In this study, we investigated the dissolution dynamics of partially protected PHS in organic developer by a quartz crystal microbalance method to deepen the fundamental understanding of the dissolution dynamics of chemically amplified resists. The dissolution dynamics in the solvents, in which the phenolic hydroxyl groups are hardly dissociated, was measured. In a 50 vol% methanol aqueous developer, a large swelling was observed. By decreasing the polarity of the developer, the dissolution dynamics was significantly changed. In the hexyl acetate, the dissolution kinetics of PHS films became similar to that in TMAH aqueous developer although the dissolution mechanism is different.

Dissolution dynamics of poly(4-hydroxystyrene) partially protected with t-butoxycarbonyl group in alkyltrimethylammonium hydroxide aqueous developers

Novel developers with low biotoxicity have attracted considerable attention with respect to ensuring environmental sustainability. In this study, the dissolution dynamics of poly(4-hydroxylstyrene) (PHS) partially protected with a t-butoxycarbonyl (t-Boc) group in alkyltrimethylammonium hydroxide and tetraethylammonium hydroxide aqueous solutions (0.26 N) were investigated by the quartz crystal microbalance method. One of the methyl groups of tetramethylammonium hydroxide (TMAH) was substituted by ethyl, propyl, and butyl groups. Depending on the developer used, the dissolution dynamics of PHS and t-Boc-protected PHS (t-Boc PHS) films showed different tendencies. The dissolution rate of PHS was higher in the TMAH developer than in the butyltrimethylammonium hydroxide (B-TMAH) developer, whereas that of the t-Boc PHS (30 mol%-protected) film was higher in the B-TMAH developer than in the TMAH developer. The elongation of one of the alkyl chains is beneficial for the penetration of the developer and the separation of nonpolar molecular interactions among t-Boc PHS molecules.

Exploring tear viscosity with quartz crystal microbalance technology.

Tear viscosity is a critical property affecting tear distribution and ocular surface stability. While not widely established as a primary diagnostic marker, deviations from normal viscosity can impact ocular health, potentially contributing to conditions such as dry eye syndrome. Despite their importance, traditional viscometers require sample volumes that are not feasible to use with tear volume. This research introduces a novel Quartz Crystal Microbalance (QCM)-based method for tear viscosity measurement, offering a viscometer prototype that operates with minimal sample volumes. Human tear samples, solutions used in artificial eye drops, and various commercial eye drop brands were evaluated. Results show that the QCM method aligns with established viscosity ranges. The average viscosity of healthy human tears was found to be 1.73 ± 0.61 cP, aligning with the typical range of 1-10 cP. Variability in the viscositiesof eye drop can be attributed to differences in their chemical compositions. The QCM method offers benefits such as reduced sample consumption and rapid results, enhancing understanding of tear dynamics for ocular health. Further research with larger sample sizes is needed to establish normative viscosity values in healthy individuals and those with dry eye syndrome, which is crucial for validating the device's clinical efficacy.

Optimization of Electrospray Deposition Conditions of ZnO Thin Films for Ammonia Sensing.

This study focuses on the influence of electrospray deposition parameters on the morphology, topography, optical and sensing properties of ZnO films deposited on gold electrodes of quartz crystal resonators. The substrate temperature, precursor feed rate and emitter's voltage were varied. Zinc acetate dehydrate dissolved in a mixture of deionized water, ethanol and acetic acid was used as a precursor. The surface morphology and average roughness of the films were studied by scanning electron microscopy (SEM) and 3D optical profilometry, respectively, while the optical properties were investigated by diffuse reflectance and photoluminescence measurements. The sensing response toward ammonia was tested and verified by the quartz crystal microbalance (QCM) method. The studies demonstrated that electrospray deposition parameters strongly influence the surface morphology, roughness and gas sensing properties of the films. The deposition parameters were optimized in order for the highest sensitivity toward ammonia to be achieved. The successful implementation of the electrospray method as a simple, versatile and low-cost method for deposition of ammonia-sensitive and selective ZnO films used as a sensing medium in QCM sensors was demonstrated and discussed.

Effect of asphaltene flocculation size on deposition using a modified quartz crystal microbalance in-house setup and microscopic image analysis: Model oil, inhibitory and nanoparticle solutions case studies

Asphaltene deposition phenomenon is a challenging event that may occur during the oil production process, causing difficulties such as formation damage and wettability alteration. To overcome these challenges, inhibitors and nanoparticles are commonly used as treatments. The size of asphaltene flocculation is a critical factor in the deposition process. In this study, we investigated the effect of asphaltene flocculation size on deposition using the quartz crystal microbalance (QCM) method in both model oil and inhibitory solutions containing Linear alkylbenzene (LABs), Sodium laureth sulfate (SLES), and 4-Dodecylbenzenesulfonic (DBSA), as well as solutions with nanoparticles such as TiO2 and SiO2. A novel in-house setup was designed to overcome experimental challenges and microscopic images were used as a visual approach for better interpretation of results. Our findings showed that TiO2 and SLES had the greatest performance in postponing flocculation points among nanoparticles and inhibitory solutions, respectively. We also observed that inhibitors were more effective in delaying the flocculation point as the concentration of heptane in the model oil decreased, with a weakened effect at higher heptane concentrations. Based on the interaction of forces, we obtained an average surface area of 17.5 square micrometres as the required value for aggregate deposition. Furthermore, inhibitory solutions showed a much lower growth rate and smaller aggregates compared to normal solutions.

Dissolution dynamics of zirconia nanocluster resist

The metal oxide resists are promising materials for the high numerical aperture EUV lithography. In the metal oxide resists, the bridging ligands are generated upon exposure to radiations, which results in the formation of a pattern insoluble in developers. In this study, the dissolution dynamics of zirconia nanocluster resist was investigated using a quartz crystal microbalance method. The ligand was methacrylate. The developers used were ethyl, butyl, amyl, hexyl, 2-methylbutyl, and 3-methylbutyl acetates. The zirconia nanocluster resist showed characteristic dissolution dynamics. After the immersion into developers, the frequency slowly decreased with approximately constant impedance (no viscosity change of the film) for a while and then rapidly dissolved with the softening of resist film. The dependences of dissolution dynamics on the molecular structures of acetates and post exposure baking were clarified. The effect of branched structure at the third position of butyl was, in particular, remarkable.

Screening Peptide Drug Candidates To Neutralize Whole Viral Agents: A Case Study with Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2).

The COVID-19 pandemic revealed the need for therapeutic and pharmaceutical molecule development in a short time with different approaches. Although boosting immunological memory by vaccination was the quickest and robust strategy, still medication is required for the immediate treatment of a patient. A popular approach is the mining of new therapeutic molecules. Peptide-based drug candidates are also becoming a popular avenue. To target whole pathogenic viral agents, peptide libraries can be employed. With this motivation, we have used the 12mer M13 phage display library for selecting SARS-CoV-2 targeting peptides as potential neutralizing molecules to prevent viral infections. Panning was applied with four iterative cycles to select SARS-CoV-2 targeting phage particles displaying 12-amino acid-long peptides. Randomly selected peptide sequences were synthesized by a solid-state peptide synthesis method. Later, selected peptides were analyzed by the quartz crystal microbalance method to characterize their molecular interaction with SARS-CoV-2's S protein. Finally, the neutralization activity of the selected peptides was probed with an in-house enzyme-linked immunosorbent assay. The results showed that scpep3, scpep8, and scpep10 peptides have both binding and neutralizing capacity for S1 protein as a candidate for therapeutic molecule. The results of this study have a translational potential with future in vivo and human studies.

Dissolution dynamics of poly(4-hydroxystyrene) in potassium hydroxide (KOH) and sodium hydroxide (NaOH) aqueous solutions investigated by quartz crystal microbalance (QCM) method

Abstract The molecular size of alkaline cation has been reported to affect the dissolution of resist film in alkaline aqueous solution. However, the details are still unclear. In this study, the dissolution dynamics of poly(4-hydroxystyrene) (PHS) in potassium hydroxide (KOH) and sodium hydroxide (NaOH) aqueous solutions was investigated to clarify the effects of small alkaline cations on the dissolution dynamics of typical backbone polymer for chemically amplified resists by a quartz crystal microbalance (QCM) method. The temporal changes in the frequency and impedance of QCM substrates during development were measured. The maximum impedance reachable during development significantly exceeded that of the developer saturated with PHS unlike the case of tetramethylammonium and tetraethylammonium cations. This means that the PHS matrix near surface was swollen by decreasing the size of alkaline cation. By either increasing or decreasing the size of alkaline cation from tetramethylammonium and tetraethylammonium cations, the transient swelling layer became thick.

The Interaction between Anesthetic Isoflurane and Model-Biomembrane Monolayer Using Simultaneous Quartz Crystal Microbalance (QCM) and Quartz Crystal Impedance (QCI) Methods.

The interaction between anesthetic Isoflurane (Iso) and model-biomembrane on the water surface has been investigated using quartz crystal microbalance (QCM) and quartz crystal impedance (QCI) methods. The model-biomembranes used were dipalmitoyl phosphatidyl choline (DPPC), DPPC-palmitic acid (PA) mixture (DPPC:PA = 8:2), DPPC-Alamethicin (Al) mixture (DPPC:Al = 39:1), and DPPC-β-Lactoglobulin (βLG) mixture (DPPC:βLG = 139:1) monolayers, respectively. The quartz crystal oscillator (QCO) was attached horizontally to each monolayer, and QCM and QCI measurements were performed simultaneously. It was found that Iso hydrate physisorbed on each monolayer/water interface from QCM and changed those interfacial viscosities from QCI. With an increase in Iso concentration, pure DPPC, DPPC-PA mixed, and DPPC-Al mixed monolayers showed a two-step process of Iso hydrate on both physisorption and viscosity, whereas it was a one-step for the DPPC-βLG mixed monolayer. The viscosity change in the DPPC-βLG mixed monolayer with the physisorption of Iso hydrate was much larger than that of other monolayers, in spite of the one-step process. From these results, the action mechanism of anesthetics and their relevance to the expression of anesthesia were discussed, based on the "release of interfacial hydrated water" hypothesis on the membrane/water interface.

Dissolution dynamics of poly(4-hydroxystyrene-co-methacrylic acid) in tetraalkylammonium hydroxide aqueous solutions

Resist materials and their lithography processes are essential for achieving further miniaturization in semiconductor microfabrication. In the sub-20 nm half-pitch region, the development process becomes particularly important due to the occurrence of stochastic defects (pinching and bridging). However, the details of dissolution dynamics are still unclear. In this study, we investigated the dissolution dynamics of poly(4-hydroxystyrene-co-methacrylic acid) (PHSMA) films in tetraalkylammonium hydroxide (TAAH) aqueous solutions using a quartz crystal microbalance method. PHSMA is a typical backbone polymer used in extreme UV lithography. For poly(4-hydroxystyrene) films, it has been reported that the dissolution mode changed when the alkyl chain length of TAAH increased. However, the mode change was not observed for PHSMA films. This difference is considered to be caused by the formation of thick transient swelling layers of PHSMA films owing to the fast water intake and the molecular interaction of the hydroxyl groups of hydroxystyrene units.

Classification of binding property of amyloid β to lipid membranes: Membranomic research using quartz crystal microbalance combined with the immobilization of lipid planar membranes

A biomembrane-related fibrillogenesis of Amyloid β from Alzheimer’ disease (Aβ) is closely related to its accumulation behavior. A binding property of Aβ peptides from Alzheimer’ disease to lipid membranes was then classified by a quartz crystal microbalance (QCM) method combined with an immobilization technique using thiol self-assembled membrane. The accumulated amounts of Aβ, Δfmax, was determined from the measurement of the maximal frequency reduction using QCM. The plots of Δfmax to Aβ concentration gave the slope and saturated value of Δfmax, (Δfmax)sat that are the parameters for binding property of Aβ to lipid membranes. Therefore, the Aβ-binding property on lipid membranes was classified by the slope and (Δfmax)sat. The plural lipid system was described as X + Y where X = L1, L1/L2, and L1/L2/L3. The slope and (Δfmax)sat values plotted as a function of mixing ratio of Y to X was classified on a basis of the lever principle (LP). The LP violation observed in both parameters resulted from the formation of the crevice or pothole, as Aβ-specific binding site, generated at the boundary between ld and lo phases. The LP violation observed only in the slope resulted from glycolipid-rich domain acting as Aβ-specific binding site. Furthermore, lipid planar membranes indicating strong LP violation favored strong fibrillogenesis. Especially, lipid planar membranes indicating the LP violation only in the slope induced lateral aggregated and spherulitic fibrillar aggregates. Thus, the classification of Aβ binding property on lipid membranes appeared to be related to the fibrillogenesis with a certain morphology.

Magnetically Modulated Differential Quartz Crystal Microbalances for Rapid, Ultrasensitive, and Direct Probing of Prostate-Specific Antigens Conjugated with Magnetic Beads.

The occurrence and development of diseases are closely related to overexpression of specific biomarkers in the serum of patients. Rapid and sensitive biomarker detection is beneficial for early diagnosis and treatment. However, the current laboratory processes and assays for biomarker detection are expensive and time-consuming, and their operation also requires a large number of professionals. We developed a magnetically modulated differential quartz crystal microbalance (MMD-QCM) method combined with magnetic bead (MB) labels for rapid and highly sensitive quantitative detection of prostate-specific antigen (PSA). Because MBs exhibit magnetized rotation motion under an applied AC magnetic field, a pair of QCMs are utilized to measure the difference between the magnetic motion intensities of the MBs and the MB-PSA immune complex to determine the PSA concentration. Experimental results demonstrate that the proposed method can be adopted to determine the PSA concentration in a wide range of 0.01-1000 ng/mL as well as exhibit a low detection limit of 0.065 ng/mL. In addition, the proposed scheme enables fast detection and low sample consumption. The single detection process takes less than 4 h and requires only 113 μL of sample solution. The proposed detection strategy is superior to the existing detection method and can be effectively used in early screening and prognostic diagnosis of cancer and other related diseases owing to its simplicity, low cost, and high speed.

Nanocomposites Based on Multi-Walled Carbon Nanotubes, Magnetite Nanoparticles, and Core–Shell Molecularly Imprinted Polymers in Piezoelectric Sensors for the Determination of Macrolide Antibiotics

A piezoelectric sensor with a recognition layer based on magnetic carbon nanocomposites, including multi-walled carbon nanotubes, magnetic Fe3O4 nanoparticles, and polymer nanospheres with molecular imprints of erythromycin and azithromycin, obtained by the “core–shell” method, is developed. Silicon dioxide particles are used as cores, on the surface of which a shell molecularly imprinted with macrolides is synthesized by free radical polymerization or the sol–gel method. SiO2 particles are obtained by the Stober method by varying the ratio of reagents during the synthesis. The size of the cores and nanoparticles of molecularly imprinted polymers (MIP) is determined by atomic force microscopy, and the density and uniformity of the layer on the surface of magnetic carbon nanocomposites (MCNC) are determined by the piezoelectric quartz crystal microbalance method. The optimal ratio of the reagents (template : functional monomer : cross-monomer) is established by a spectrophotometric method during the synthesis of “core–shell” nanostructures by free radical polymerization. A thin shell of SiO2 with imprints of an antibiotic based on organosilicon compounds used in the synthesis of the core is formed by the sol–gel method on the surface of the silicon dioxide core. The sensor recognition layer is formed under the action of an external magnetic field. The dependence of the analytical signal of the sensor based on MIP@SiO2/MCNC on concentration is linear in the range 5–160 µg/mL for azithromycin and 10–160 µg/mL for erythromycin, and with a recognition layer based on SiO2@SiO2/MCNC, in the concentration range 20–400 µg/mL for erythromycin.