Thin surface films quartz crystal microbalance

Such approximation is valid when the thickness of the polymeric layer is small compared to die thickness of die crystal, and the measured frequency change is small with respect to the resonant frequency of the unloaded crystal. Mass changes up to 0.05% of die crystal mass commonly meet this approximation. In die absence of molecular specificity, EQCM cannot be used for molecular-level characterization of surfaces. Electrochemical quartz crystal microbalance devices also hold promise for the task of affinity-based chemical sensing, as they allow simultaneous measurements of both tile mass and die current. The principles and capabilities of EQCM have been reviewed (67,68). The combination of EQCM widi scanning electrochemical microscopy has also been reported recently for studying die dissolution and etching of various thin films (69). The recent development of a multichannel quartz crystal microbalance (70), based on arrays of resonators, should further enhance die scope and power of EQCM. 

We first experimented with the Quartz Crystal Microbalance (QCM) in order to measure the ablation rate in 1987 (12). The only technique used before was the stylus profilometer which revealed enough accuracy for etch rate of the order of 0.1 pm, but was unable to probe the region of the ablation threshold where the etch rate is expressed in a few A/pulse. Polymer surfaces are easily damaged by the probe tip and the meaning of these measurements are often questionable. Scanning electron microscopy (21) and more recently interferometry (22) were also used. The principle of the QCM was demonstrated in 1957 by Sauerbrey (22) and the technique was developed in thin film chemistiy. analytical and physical chemistry (24). The equipment used in this work is described in previous publications (25). When connected to an appropriate oscillating circuit, the basic vibration frequency (FQ) of the crystal is 5 MHz. When a film covers one of the electrodes, a negative shift <5F, proportional to its mass, is induced ... 

Piacham T, Josell A, Arwin H, Prachayasittikul V, Ye L. Molecularly imprinted polymer thin films on quartz crystal microbalance using a surface bound photo-radical initiator. Anal Chim Acta 2005 536 191-196. 

Another tool used to study friction on the molecular scale is the quartz crystal microbalance (QCM) introduced in Section 9.4.1. The QCM has been used to monitor the adsorption of thin films on surfaces via the induced frequency shift [385], In the years since 1986, Krim and coworkers could show that the slippage of adsorbed layers on the QCM leads to a damping of the oscillator [472], This damping is reflected as a decrease in the quality factor Q of the oscillator. From the change in Q, a characteristic time constant rs, the so-called slip-time, can be derived. This corresponds to the time for the moving object s speed to fall to 1 /e, i.e. 

The strong dependence of the layer structure on the nature of the contacting electrolyte has been further investigated by using the electrochemical quartz crystal microbalance (EQCM). As discussed above in Chapter 3, this technique is based on the measurement of the frequency with which a coated quartz crystal vibrates, and this frequency can then be related to the mass of this crystal provided that the material attached to the surface is rigid. In this way, the changes that occur in thin films as a result of redox processes can be monitored. 

Through the combination of SPR with a - poten-tiostat, SPR can be measured in-situ during an electrochemical experiment (electrochemical surface plasmon resonace, ESPR). Respective setups are nowadays commercially available. Voltammetric methods, coupled to SPR, are advantageously utilized for investigations of - conducting polymers, thin film formation under influence of electric fields or potential variation, as well as - electropolymerization, or for development of -> biosensors and - modified electrodes. Further in-situ techniques, successfully used with SPR, include electrochemical - impedance measurements and -+ electrochemical quartz crystal microbalance. 

Pei YX, Yu H, Pei ZC, Theurer M, Ammer C, Andre S, Gabius HJ, Yan MD, Ramstrom O (2007) Photoderivatized polymer thin films at quartz crystal microbalance surfaces sensors for carbohydrate-protein interactions. Anal Chem 79 6897-6902... 

Marx, K.A. (2003). Quartz crystal microbalance A useful tool for studying thin polymer films and complex biomolecular systems at the solution-surface interface. Biomacromolecules, 4, 1099-1120. 

Quartz crystal microbalance is operated in typical resonant frequencies ranging from 1 to 10 MHz, with most of them operating in 5-10 MHz. A typical QCM is a disk in the size of 10-16 mm in diameter with a thickness of approximately 0.15 mm. A thin metal film, gold, aluminum, or others, is deposited onto the surface of the quartz serving as electrodes. The metal... 

In the gravimetric method, the adsorbent (usually in the form of powder) is placed into a bulb, which is mounted on a sensitive balance and the bulb is then evacuated. Next, the weight increase of the adsorbent solid as a function of the absorptive gas pressure is monitored at constant temperature. More recently, the quartz crystal microbalance (QCM) technique has been applied this is very sensitive to mass increases. Quartz is a piezoelectric material and the thin crystal can be excited to oscillate in a traverse shear mode at its resonance frequency when a.c. voltage is applied across the metal (usually gold) electrodes, which are layered on two faces of the crystal. When the mass on the crystal increases upon adsorption, its resonance frequency decreases. The increase in the mass is calculated from the reduction in resonance frequency. On the other hand, adsorption on single flat surfaces can also be measured by ellipsometry, which measures the film thickness of transparent films optically using the difference between light reflection from bare and adsorbed surfaces. 

Compact chemical sensors can be broadly classified as being based on electronic or optical readout mechanisms [28]. The electronic sensor types would include resistive, capacitive, surface acoustic wave (SAW), electrochemical, and mass (e.g., quartz crystal microbalance (QCM) and microelectromechanical systems (MEMSs)). Chemical specificity of most sensors relies critically on the materials designed either as part of the sensor readout itself (e.g., semiconducting metal oxides, nanoparticle films, or polymers in resistive sensors) or on a chemically sensitive coating (e.g., polymers used in MEMS, QCM, and SAW sensors). This review will focus on the mechanism of sensing in conductivity based chemical sensors that contain a semiconducting thin film of a phthalocyanine or metal phthalocyanine sensing layer. 

Abstract In this chapter we focus on the application of the piezoelectric-based quartz crystal microbalance (QCM) technique to create and study thin polymeric films. The electrochemical variant of the quartz crystal microbalance technique (EQCM) allows one to study changes in the interfacial mass and physical properties associated with electron transfer processes occurring at the electrode surface, such as those accompanying... 

It has been shown that the TEA process leads to high-quality films [43—45]. The mechanism involving the CBD of CdS thin films from the ammonia-thiourea system have been studied in situ by means of the quartz crystal microbalance technique (QCM) [25]. The formation of CdS was assumed to result from the decomposition of adsorbed thiourea molecules via the formation of an intermediate surface complex with cadmium hydroxide. This mechanism is different from the dissociation mechanism involving the formation of free sulfide ions in solution, and which had previously been reported [46-49]. Thus, the influence of growth parameters such as bath temperature, deposition rate, bath composition, etc., on various film properties has been studied [37, 39, 41, 50, 51], and the main parameters which determine the quality of the films were deduced. The chemical deposition of CdS thin films generally consisted of the decomposition of thiourea in an alkaline solution containing a cadmium salt The deposition process was based on the slow release of Cd and S ions in solution which then condensed on an ion-by-ion basis on the substrate. The reaction process for the formation of CdS may be described by the following steps [25, 35, 36, 43, 52-54]. 

The first subdiscipline of chemistry in which the QCM was widely applied was electrochemistry. In 1992 Buttry and Ward published a review entitled Measurement of interfacial processes at electrode surfaces with the electrochemical quartz crystal microbalance , with 133 references [8]. This is the most widely cited paper on quartz crystal microbalances. After presenting the basic principles of AT-cut quartz resonators, the authors discuss the experimental aspects and relation of electrochemical parameters to QCM frequency changes. In their review of the investigation of thin films, they discuss electrodeposition of metals, dissolution of metal films, electrovalency measurements of anion adsorption, hydrogen absorption in metal films, bubble formation, and self-assembled monolayers. The review concludes with a brief section on redox and conducting polymer films. 

Almost any metal electrode may be applied. One must take care not to operate too close to the limits of the electrochemical window of the used combination of electrode and electrolyte solution in order to avoid catalytic or undesired side effects such as gas evolution reactions. When using thin film electrodes, such as in combined quartz crystal microbalance (QCMB) studies, extreme care must be taken not to scratch the metal surface, usually gold, in order to maintain an electronically conductive path within the electrode. Examples of such experiments are given in the literature [4-7]. Also, when using metal electrodes in aqueous solutions, the background voltammogram should be examined very closely as the formation of surface oxides or the like may be mistaken for signals of the solid under study. 

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