Quartz Crystal Microbalance Method Research Articles

Differential sputtering yield measurement of ion grid materials by novel arch array system

In this experimental study the differential sputtering yield and total sputtering yield of ion thruster grid materials (Mo and C/C composite) under low-energy ion bombardment has been investigated. A novel combinable aluminum arch array is developed to determine the spatial distributions of sputtered atoms in different azimuthal angles. The quartz crystal microbalance (QCM) method is used to validate the typical distribution profile of sputtered atoms at the 180° azimuthal angle. The distribution characteristics of sputtered atoms as well as the specific regions of maximum differential sputtering yield under different incident energies, incident angles and ion species (Xe, Kr, Ar) have been discussed. The sputtering resistance performance of C/C composite materials have been compared with Mo metal by measuring the total sputtering yield. The spatial distributions of C/C differential sputtering yield are found highly anisotropic even under normal incidence, a multi-region discontinuous distribution characteristic of maximum differential sputtering yield have been observed in C/C composite material. The experimental results about the spatial distribution of sputtered atoms are of great importance for establishing the sputter-redeposition models of grid apertures to accurately predict the evolution of grid morphology and lifetime of ion thruster.

Influence of deposition temperature and time on structural and gas sensing properties of electrochemically deposited ZrO2 layers

This research is focused on the influence of deposition temperature and time on structural and gas sensing properties of electrochemically deposited ZrO2 layers. ZrO2 layers were deposited on gold electrodes of quartz resonators by electrochemical process using a three-electrode electrochemical system. The deposition was carried out in an aqueous solution containing ZrOCl2 (5 mM) and KCl (0.1 M). The surface morphology, structure and average roughness of the layers were determined by Scanning Electron Microscopy (SEM) and 3D optical profilometry. Studies demonstrated that deposition temperature strongly influences the surface morphology of the films, especially at higher temperatures whereas weaker dependence on deposition time was observed. The layers sensitivity to volatile organic compound (VOC) vapors was determined by the quartz crystal microbalance method (QCM) method. The measurements of sensitivity were performed in an airtight box at different concentrations.

Beyond Stereoisomeric Effects: Exploring the Importance of Intermolecular Electron Spin Interactions in Biorecognition.

This work shows that electron spin polarization and stereoisomeric effects make comparable contributions to the enantioselective binding of amino acids. Magneto-electrochemical quartz crystal microbalance methods are used to study the adsorption of chiral amino acids onto a monolayer film of chiral molecules that are spin polarized by an underlying ferromagnetic substrate. The direction of the electron spin polarization affects both the kinetics and thermodynamics of the enantiospecific adsorption of the amino acids. Comparison of these data with the circular dichroism (CD) spectra of the amino acid adsorbates shows that the CD spectrum of the interacting group provides a good figure-of-merit for predicting the contributions of electron spin to the intermolecular interaction. These findings demonstrate the importance of electron spin in enantioselective intermolecular interactions between chiral amino acids and represent a paradigm shift for how selectivity should be viewed in biorecognition.

Spin-Based Chiral Separations and the Importance of Molecule-Solvent Interactions.

This work uses magneto-electrochemical quartz crystal microbalance methods to study the enantiospecific adsorption of chiral molecules onto a ferromagnetic substrate. The effects of solution conditions, pH, and solvent isotope composition indicate that the kinetics of the enantiomeric adsorption depend strongly on the charge state and geometry of the adsorbate, whereas no thermodynamic contributions to enantiospecificity are found. Density functional theory calculations reveal that an interplay between the adsorbate and solvent molecules is important for defining the observed enantiospecific preference with an applied magnetic field; however, it remains unclear if intermolecular vibrational couplings contribute to the phenomenon.

Classification of dissolution modes of partially protected poly(4-hydroxystyrene) in tetraalkylammonium hydroxide aqueous solutions

The development of high-numerical aperture exposure tools for EUV lithography is in progress. The development process (the dissolution of resist films) is the key to fine patterning. The dissolution dynamics of acidic polymers (the backbone polymers of chemically amplified resists) depend on various parameters related to molecular structures. In this study, the dissolution dynamics in tetraalkylammonium hydroxide (TAAH) aqueous solutions were classified into six classes on the basis of the frequency and impedance changes observed during the development process by a quartz crystal microbalance method. The relationship between class and physical parameters of materials was analyzed by decision tree and support vector machine methods. The feature values used were the alkyl chain length, molecular weight, and concentration of TAAH; the viscosity of the developer; and the protection ratio, molecular weight, contact angle, surface free energies of polymers, and film thickness. The classification accuracy was 0.80 for the validation data.

In Situ Gravimetric Probing of Copper Sulfide Formation on the Counter Electrode for Quantum Dot Sensitized Solar Cells

Copper sulfide is a classical counter electrode (CE) catalytic material for the high catalytic activity of polysulfide in quantum dot-sensitized solar cells (QDSSCs). Actually, copper sulfide is a complicated compound. Different preparation methods will lead to the difference in the morphology and structure of copper sulfide, which has a profound impact on its catalytic activity. However, the formation mechanism and electrochemical properties of copper sulfide are rarely reported in the field of QDSSCs. Herein, we report an approach to obtain a high-stability counter electrode material by the electrochemical synthesis in sodium sulfide solution. The in situ electrochemical quartz crystal microbalance (EQCM) method was also employed to reveal the detailed transformation mechanism of copper vulcanized into copper sulfide during cyclic voltammetry in sodium sulfide solution. According to the calculation results of mpe theory, the formation of copper sulfide is accompanied by side reactions such as the conversion of polysulfide ions and water oxidation. Copper sulfide was proven to be a copper-rich phase by X-ray photoelectron spectroscopy (XPS) and other characterization methods. The photoconversion and stability of QDSSCs were studied using CdSe QD as the sensitizing material. The results show that the performance of copper sulfide prepared by this working method is better than the CE prepared by chemical bath deposition (CBD), and the replicability of photoelectric conversion efficiency (PCE) is better than CBD-CE. This work has theoretical significance to reveal the complex formation mechanism, electrochemical process mechanism, and working mechanism of copper sulfide in QDSSCs.

Quartz Crystal Microbalance Method to Measure Nanoparticle-Receptor Interactions and Evaluate Nanoparticle Design Efficiency.

Conjugation of biomolecules on the surface of nanoparticles (NPs) to achieve active targeting is widely investigated within the scientific community. However, while a basic framework of the physicochemical processes underpinning bionanoparticle recognition is now emerging, the precise evaluation of the interactions between engineered NPs and biological targets remains underdeveloped. Here, we show how the adaptation of a method currently used to evaluate molecular ligand-receptor interactions by quartz crystal microbalance (QCM) can be used to obtain concrete insights into interactions between different NP architectures and assemblies of receptors. Using a model bionanoparticle grafted with oriented apolipoprotein E (ApoE) fragments, we examine key aspects of bionanoparticle engineering for effective interactions with target receptors. We show that the QCM technique can be used to rapidly measure construct-receptor interactions across biologically relevant exchange times. We contrast random adsorption of the ligand at the surface of the NPs, resulting in no measurable interaction with target receptors, to grafted oriented constructs, which are strongly recognized even at lower graft densities. The effects of other basic parameters impacting the interaction such as ligand graft density, receptor immobilization density, and linker length were also efficiently evaluated with this technique. Dramatic changes in interaction outcomes with subtle alterations in these parameters highlight the general importance of measuring the interactions between engineered NPs and target receptors ex situ early on in the construct development process for the rational design of bionanoparticles.

Recent advances in assembly strategies of new advanced materials-based analytical methods for the detection of cardiac biomarkers as a diagnosis tool

Acute myocardial infarction (AMI) is a type of cardiac disease which is one of the main reasons for mortality worldwide. The fabrication of reliable diagnosis methods to predict heart attacks is difficult due to the low-level concentration of responsible biomarkers and limited time between the first symptoms and the heart attack. However, new advanced nanomaterials have led to the fabrication of new nanoplatforms for the detection and therapy of AMI. These nanomaterials have been utilized to fabricate different types of nanobiosensors for early-stage detection of cardiac biomarkers. In this review, the influence of new advanced materials on the fabricated sensing platforms for cardiac biomarkers has been reviewed. Key points of the developed analytical methods have been addressed regarding their advantages, limitations, and also their potential to be as a commercial device in near future. Various analytical methods have utilized for the fabrication of the sensing probes including optical (fluorescence, molecular absorbance, surface Plasmon resonance, and surface-enhanced Raman spectroscopy), electrochemical (electrochemical impedance spectroscopy, electrochemiluminescence, etc.), and quartz crystal microbalance methods. In conclusion, this review may provide a direction for future researches by introducing the most promising materials and analytical methods for AMI detection.

Spin Selectivity Damage Dependence of Adsorption of dsDNA on Ferromagnets.

The adsorption of oxidatively damaged DNA onto ferromagnetic substrates was investigated. Both confocal fluorescence microscopy and quartz crystal microbalance methods show that the adsorption rate and the coverage depend on the magnetization direction of the substrate and the position of the damage site on the DNA relative to the substrate. SQUID magnetometry measurements show that the subsequent magnetic susceptibility of the DNA-coated ferromagnetic film depends on the direction of the magnetic field that was applied to the ferromagnetic film as the molecules were adsorbed. This study reveals that (i) the spin and charge polarization in DNA molecules is changed significantly by oxidative damage in the G bases and (ii) the rate of adsorption on a ferromagnet, as a function of the direction of the magnetic dipole of the surface, can be used as an assay to detect oxidative damage in the DNA.

Effects of photoacid generator decomposition on dissolution kinetics of poly(4-hydroxystyrene) in tetraalkylammonium hydroxide aqueous solutions

For the advancement of lithography, the resist materials and processes are the most critical factors. In particular, the process of developing resist materials is important in reducing the line width roughness and stochastic defects. In this study, a quartz crystal microbalance method was used to investigate the dissolution dynamics of poly(4-hydroxystyrene) (PHS) films containing triphenylsulfonium nonaflate (TPS-nf) in tetraalkylammonium hydroxide (TAAH) aqueous solutions. The time required for dissolution increased with the alkyl chain length of TAAH. The dissolution rate of PHS films increased with UV irradiation dose for tetramethylammonium hydroxide and tetraethylammonium hydroxide developers, whereas the dissolution time increased for the tetrabutylammonium hydroxide developer. For the tetrapropylammonium hydroxide developer, the dissolution time of PHS films without postexposure baking (PEB) slightly decreased with UV irradiation, whereas that with PEB increased. Both the surface free energy of PHS films and the molecular size of TAAH are considered to affect dissolution kinetics.

Dissolution dynamics of partially protected poly(4-hydroxystyrene) in tetraalkylammonium hydroxide aqueous solution

A 0.26 M tetramethylammonium hydroxide (TMAH) aqueous solution has been used as a standard developer for manufacturing semiconductor devices. Alternative developers have recently attracted much attention because the 0.26 M TMAH developer may be approaching its performance limit. In this study, we measured the dissolution and swelling behavior of resist polymers in tetraalkylammonium hydroxide (TAAH) aqueous solutions using a quartz crystal microbalance method to clarify the effects of the alkyl chain length of TAAH. The resist polymer was poly(4-hydroxystyrene), whose hydroxyl groups were partially protected with t-butoxycarbonyl groups. When the alkyl chain length of TAAH was increased from two (ethyl) to three (propyl), the dissolution mode markedly changed. The dissolution mode did not depend on the polymer polarity. The change in the dissolution mode is probably caused by the size effect of TAAH, considering the independence of polymer polarity and the discrete change in the dissolution mode.

Biased quartz crystal microbalance method for studies of chemical vapor deposition surface chemistry induced by plasma electrons.

A recently presented chemical vapor deposition (CVD) method involves using plasma electrons as reducing agents for deposition of metals. The plasma electrons are attracted to the substrate surface by a positive substrate bias. Here, we present how a standard quartz crystal microbalance (QCM) system can be modified to allow applying a DC bias to the QCM sensor to attract plasma electrons to it and thereby also enable in situ growth monitoring during the electron-assisted CVD method. We show initial results from mass gain evolution over time during deposition of iron films using the biased QCM and how the biased QCM can be used for process development and provide insight into the surface chemistry by time-resolving the CVD method. Post-deposition analyses of the QCM crystals by cross-section electron microscopy and high-resolution x-ray photoelectron spectroscopy show that the QCM crystals are coated by an iron-containing film and thus function as substrates in the CVD process. A comparison of the areal mass density given by the QCM crystal and the areal mass density from elastic recoil detection analysis and Rutherford backscattering spectrometry was done to verify the function of the QCM setup. Time-resolved CVD experiments show that this biased QCM method holds great promise as one of the tools for understanding the surface chemistry of the newly developed CVD method.

Molecular Liquids versus Ionic Liquids: The Interplay between Inter-Molecular and Intra-Molecular Hydrogen Bonding as Seen by Vaporisation Thermodynamics.

In this study, we determined the enthalpies of vaporisation for a suitable set of molecular and ionic liquids using modern techniques for vapour pressure measurements, such as the quartz crystal microbalance, thermogravimetric analysis (TGA), and gas chromatographic methods. This enabled us to measure reasonable vapour pressures, avoiding the problem of the decomposition of the ionic liquids at high temperatures. The enthalpies of vaporisation could be further analysed by applying the well-known "group contribution" methods for molecular liquids and the "centerpiece" method for ionic liquids. This combined approach allowed for the dissection of the enthalpies of vaporisation into different types of molecular interaction, including hydrogen bonding and the dispersion interaction in the liquid phase, without knowing the existing species in both the liquid and gas phases.

Dependence of Dissolution Kinetics of Main-Chain Scission Type Resists on Molecular Weight

The dissolution kinetics and molecular weight in main-chain scission type resists such as poly(methyl methacrylate) (PMMA) and ZEP520A were investigated using a quartz crystal microbalance (QCM) method and a Gel Permeation Chromatography (GPC) to clarify the effects of the molecular weight after polymer degradation on the dissolution kinetics. G-values of main chain scissions in PMMA and ZEP520A are estimated using GPC measurement. The G-value of ZEP520A showed higher G-values than that of PMMA. There are three molecular weight regions in PMMA, whereas there are only two molecular weight regions in ZEP 520A. The dissolution behavior depends on molecular weight after polymer degradation in both PMMA and ZEP 520A. These results indicate that ZEP520A is better to be better lithographic performance.

Investigation of Early Corrosion Behavior of Canister Candidate Materials in Oxic Groundwater by the EQCM Method

This study investigated the corrosion mass changes of canister candidate materials (Cu, Ni, Ti, SS304) in an oxic groundwater solution using the electrochemical quartz crystal microbalance method in order to estimate corrosion thickness. The materials were immersed in naturally aerated groundwater with and without the addition of chloride ions to observe the mass changes as well as the open-circuit potential (corrosion potential). In the oxic groundwater solution, Ni, Ti, and SS304 exhibited negligible mass changes, indicating their insusceptibility to general corrosion. In contrast, the Cu electrode exhibited a relatively significant mass change (63.8 ng/cm2 for 60 h), and the maximum corrosion thickness was estimated to be approximately 0.1 μm/yr. In the presence of chloride ions, the Ni and Ti electrodes did not reveal demonstrate any significant changes, whereas the SS304 electrode was slightly increased compared to an absence of chloride ions. A lower mass change occurred when the Cu electrode was immersed in the chloride-containing groundwater solution compared with the absence of chlorides because the dissolution of Cu as CuCl 2 − was involved in Cu2O formation.

Enhanced hydrogen adsorption properties of mesoporous nano-TiO2@SnO2

Today, hydrogen as being one of the most advantageous energy supplies for various applications and specifically not with carbon emissions, alluring strategies are made possible for its production and storage. Since the metal oxides (MOs) semiconductors give rise to the development of new technologies related to renewable energy and environmental issues, this work is envisioned to study the hydrogen adsorption properties of TiO2@SnO2 catalyst synthesized via novel approach by integrating sol–gel and thermal decomposition methods. The synthesized TiO2 and its composite have been analyzed by sophisticated instruments to reveal the drastic enhancement of hydrogen adsorption. In this work, hydrogen measurements were accomplished by quartz crystal (QC) microbalance method. The Raman scattering experiment of the composite revealed the lower peak intensity compared with pure TiO2, which demonstrated the surface defects that created oxygen vacancies with reduced oxidation states of the metal centers. Meanwhile, the mesoporous nanostructure of TiO2@SnO2 could be confirmed via High resolution transmission electron (HR-TEM) microscopic analysis. Besides, the intermediate states of the composite were analyzed through Photoluminescence (PL) spectra which demonstrated the delay in recombining charges. The Barrett-Joyner- Halenda (BJH) method illustrated the larger pore size and pore volume with decreased surface area of the composite. The addition of SnO2 into TiO2 has reported 4 times greater the adsorption of pristine TiO2 particles, because of the capacity of SnO2 to hinder pores. Moreover, the titania oxidation states play a predominant role in the procurement of larger H2 adsorption. Also, the Ti4+ and Sn4+ reveal fragile Kubas type of adsorption that facilitated the hydrogen storage.

Evaluation of Green-Synthesized Cuprospinel Nanoparticles as a Nanosensor for Detection of Low-Concentration Cd(II) Ion in the Aqueous Solutions by the Quartz Crystal Microbalance Method.

Cd(II) heavy metal is an extremely dangerous hazardous material for both humans and the environment. Its high toxicity is the reason behind the examination of new techniques for detecting very small concentrations of Cd(II). Recently, Quartz Crystal Microbalance (QCM) has been one of the techniques that have been widely used to detect trace heavy metal ions in solutions. It is a simple, inexpensive, portable, and sensitive gravimetric sensor due to its quality sensitivity lowest to nanograms. In this work, Cuprospinel nanoparticles were synthesized through the green synthesis approach using Psidium guajava L. leaf extract as a reducing agent, which is the first scientific description to report the preparation of these nanoparticles by this method. Subsequently, the synthesized nanoparticles were subjected to the characterization of their crystallinity, structure, and morphology by the XRD, N2 adsorption–desorption, zeta potential, DLS, AFM, SEM, and TEM analyzers. The prepared Cuprospinel nanoparticles were evaluated as a nanosensor for the detection of the very low concentration of Cd(II) ions in aqueous solutions using the QCM technique. The results of the characterization proved that the Cuprospinel nanoparticles have formed in the nanoscale with sub-spherical shapes and particles size ranging from 20 to 80 nm. The BET surface area and pore size analysis revealed that the synthesized Cuprospinel nanoparticles possess a surface area of 47.3 m2/g, an average pore size of 1.5 nm, and a micropore volume of 0.064 cc/g. The QCM results demonstrated the success of the Cuprospinel nanoparticles sensor in detecting the tiny amounts of Cd(II) ions in the aqueous solutions with concentrations reaching about 3.6 ng/L.

Electrostatic effect on the dissolution kinetics of poly(4-hydroxystyrene) in alkaline aqueous solution

The effects of pH and ionic strength on the dissolution behavior of poly(4-hydroxystyrene) (PHS) in an alkaline solution were studied to gain a fundamental understanding of the dissolution of chemically amplified resists (CARs). Tetramethylammonium hydroxide, which is a standard developer in recent lithography, and its corresponding salts were used. Dynamic light scattering (DLS) and quartz crystal microbalance (QCM) methods were used to study the state of PHS chains in solution and the dissolution behavior of PHS films, respectively. In DLS, a higher pH and ionic strength caused PHS chains to become more dispersed owing to an increase in the number of dissociated acidic groups and the resulting increase in repulsive force. The results of the QCM method showed that the diffusion of the polymer into the liquid phase from the film corresponds to an increase in the number of dissociated acidic groups, but did not correspond to the magnitude of transient swelling.

A quartz crystal microbalance method to quantify the size of hyaluronan and other glycosaminoglycans on surfaces

Hyaluronan (HA) is a major component of peri- and extra-cellular matrices and plays important roles in many biological processes such as cell adhesion, proliferation and migration. The abundance, size distribution and presentation of HA dictate its biological effects and are also useful indicators of pathologies and disease progression. Methods to assess the molecular mass of free-floating HA and other glycosaminoglycans (GAGs) are well established. In many biological and technological settings, however, GAGs are displayed on surfaces, and methods to obtain the size of surface-attached GAGs are lacking. Here, we present a method to size HA that is end-attached to surfaces. The method is based on the quartz crystal microbalance with dissipation monitoring (QCM-D) and exploits that the softness and thickness of films of grafted HA increase with HA size. These two quantities are sensitively reflected by the ratio of the dissipation shift (ΔD) and the negative frequency shift (− Δf) measured by QCM-D upon the formation of HA films. Using a series of size-defined HA preparations, ranging in size from ~ 2 kDa tetrasaccharides to ~ 1 MDa polysaccharides, we establish a monotonic yet non-linear standard curve of the ΔD/ − Δf ratio as a function of HA size, which reflects the distinct conformations adopted by grafted HA chains depending on their size and surface coverage. We demonstrate that the standard curve can be used to determine the mean size of HA, as well as other GAGs, such as chondroitin sulfate and heparan sulfate, of preparations of previously unknown size in the range from 1 to 500 kDa, with a resolution of better than 10%. For polydisperse samples, our analysis shows that the process of surface-grafting preferentially selects smaller GAG chains, and thus reduces the average size of GAGs that are immobilised on surfaces comparative to the original solution sample. Our results establish a quantitative method to size HA and other GAGs grafted on surfaces, and also highlight the importance of sizing GAGs directly on surfaces. The method should be useful for the development and quality control of GAG-based surface coatings in a wide range of research areas, from molecular interaction analysis to biomaterials coatings.

Swelling and dissolution kinetics of poly(4-hydroxystyrene) in tetrabutylammonium hydroxide (TBAH) aqueous solutions studied by quartz crystal microbalance (QCM) method—in comparison with tetramethylammonium hydroxide (TMAH) aqueous solutions

The dissolution (including the formation of a transient swelling layer) of a resist polymer is key to realizing ultrafine patterning. However, the details of the dissolution of resist polymers remain unclarified. In this study, the swelling and dissolution kinetics of poly(4-hydroxystyrene) (PHS) films in tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH) aqueous solutions were investigated by a quartz crystal microbalance method. PHS is a typical backbone polymer (a dissolution agent) of chemically amplified resists. The swelling and dissolution kinetics of PHS were observed by changing the protection ratio of the hydroxyl groups of PHS and the alkaline concentration in developers. Not only the dissolution rate but also the mode of dissolution depended on the molecular structure of tetraalkylammonium cations. For polymer matrices with strong hydrogen bond networks such as PHS, the penetration of tetrabutylammonium cations is considered to be strongly suppressed by their long alkyl chains.