Abstract: Electrochemical analysis method and system for monitoring and controlling the quality of electrochemical deposition and/or plating processes. The method uses a fingerprinting analysis method of an output signal to indicate whether the chemistry and/or process is operating in the normally expected range and utilizes one or more substrates as working electrode(s) and a) whereby the potential between the one or more working electrodes and one or more reference electrodes is analyzed to provide an output signal fingerprint which is represented as potential difference as a function of time or b) the input power of a process power supply to provide input energy in the form of current and/or potential between the working electrode(s) and a counter-electrode whereby the method utilizes the potential between the one or more working electrode(s) and at least one of: one or more reference electrodes; or one or more counter-electrodes; to provide an output signal fingerprint.

Abstract: A plating apparatus capable of preventing difference in an electrode potential between the pair of cathodes and a disturbance in a current distribution in Haring cell test and so on is provided. A plating apparatus (1) has an anode (12) and a pair of cathodes (13X) (13Y) which are provided in a plating bathtub (11); a plating power source (14) to supply an electric current between the anode (12) and the pair of cathodes (13X) (13Y); and a feedback circuit (21) to have an electrode potential of a first cathode (13X) equal to an electrode potential of a second cathode (13Y) while a summation of electric currents flowing through the pair of cathodes (13X) (13Y) is kept constant.

Abstract: Apparatus and methodology to measure the amplitude of oscillation of differential reflectivity from an electrode surface in contact with liquid with dissolved ions upon applying an oscillatory potential between the said electrode and the said liquid, where the differential reflectivity is a set of optical properties comprised of a change in intensity and phase of the oscillation of reflected light intensity relative to the incident light and a change in polarization of the reflected light. Analysis of the reflected beam may be used to determine various parameters of the electrochemical processes.

Abstract: The invention relates to an electrochemical analysis method for monitoring and controlling the quality of electrochemical deposition and/or plating processes whereby the electrochemical analysis method uses a fingerprinting analysis method of an output signal to have an indicator of whether the chemistry and/or process is operating in the normally expected range, whereby the method utilizes one or more substrates as working electrode(s) and a) whereby the potential between the one or more working electrodes and one or more reference electrodes being analyzed to provide an output signal fingerprint which is represented as potential difference as a function of time or b) the input power of a process power supply to provide input energy in the form of current and/or potential between the working electrode(s) and a counter-electrode whereby the method utilizes the potential between the one or more working electrode(s) and at least one of: one or more reference electrodes; or one or more counter-electrodes; to pro

Abstract: An electroplating apparatus for filling recessed features on a semiconductor substrate includes a vessel configured to maintain a concentrated electroplating solution at a temperature of at least about 40° C., wherein the solution would have formed a precipitate at 20° C. This vessel is in fluidic communication with an electroplating cell configured for bringing the concentrated electrolyte in contact with the semiconductor substrate at a temperature of at least about 40° C., or the vessel is the electroplating cell. In order to prevent precipitation of metal salts from the electrolyte, the apparatus further includes a controller having program instructions for adding a diluent to the concentrated electroplating solution in the vessel to avoid precipitation of a salt from the concentrated electroplating solution in response to a signal indicating that the electrolyte is at risk of precipitation.

Abstract: The presently claimed invention provides an accurate, fast, and cost effective method for determining the additive concentrations of at least two inhibitors simultaneously in an electroplating bath by using different electrical load conditions. The method of the present invention is able to determine additive concentrations of different inhibitors effectively during on-line feedback control for adjusting the amount of additives in the electroplating bath to maintain the additive concentrations within pre-defined limits during device production.

Abstract: An apparatus and a method for selectively etching an encapsulant forming a package of resinous material around an electronic device includes an electronic device package mountable on the etch head; a conductive electrode in electrical contact with package leads of the electronic device package to apply a first voltage to the package leads of the electronic device; a first pump configured to pump a first quantity of the etchant solution from the source into the etch head where the etchant solution is electrically biased to a second voltage different from the first voltage. An etch cavity is formed on an exterior surface of the electronic device package. When the etchant solution has etched through an exterior surface of the electronic device package, the conductive bond wires of the electronic device is prevented from being etched by the applied first voltage.

Abstract: The embodiments herein relate to methods and apparatus for determining whether a particular test bath is able to successfully fill a feature on a substrate. In various cases, the substrate is a semiconductor substrate and the feature is a through-silicon-via. Generally, two experiments are used: a first experiment simulates the conditions present in a field region of the substrate during the fill process, and the second experiment simulates the conditions present in a feature on the substrate during the fill process. The output from these experiments may be used with various techniques to predict whether the particular bath will result in an adequately filled feature.

Abstract: The present invention describes a method for the measurement of the stabilizer additive concentration in electroless metal and metal alloy plating electrolytes comprising a voltammetric measurement. Said method comprises the steps a. conditioning of the working electrode, b. interaction of intermediates on the working electrode, c. measurement of the Faradaic current and d. determining the Faradaic current.

Abstract: An auxiliary leveler additive that cannot be analyzed by conventional CVS methods for acid copper plating baths is analyzed by cyclic voltammetry at a platinum rotating disk electrode from its effect on the anodic current at very positive potentials.

Abstract: A method for improving the precision of electrochemical measurements made using an electrochemical cell is provided. The method comprises preconditioning a working electrode of the cell by (i) baking the working electrode; and/or (ii) incubating the working electrode; and/or (iii) applying a preconditioning potential across the cell; and/or (iv) treating the working electrode with a UV laser.

Abstract: A method for forming a defect marker on a thin film of a photovoltaic device by plating to detect pinholes and/or electrical shunts during device fabrication is disclosed. Also disclosed is a system for implementing such a method.

Abstract: Methods and systems for monitoring electrolyte bath fluids are provided. The electrolyte bath fluids can be electroplating, electroless plating or etching solutions. The monitoring systems employ microfluidic devices, which have built in microfluidic channels and microfabricated thin-film electrodes. The devices are configured with fluid pumps to control the movement and mixing of test fluids through the microfluidic channels. The microfabricated thin-film electrodes are configured so that the plating or etching bath fluid composition can be characterized by electrochemical measurements. The monitoring methods and system provide faster measurement times, generate minimal waste, and occupy dramatically reduced physical space compared to conventional bath-monitor systems. The monitoring systems and method also provide low-cost system and methods for measuring or monitoring electroless plating bath rates.

Abstract: Provided herein are methods and apparatus for determining leveler concentration in an electroplating solution. The approach allows the concentration of leveler to be detected and measured, even at very low leveler concentrations. According to the various embodiments, the methods involve providing an electrode with a metal surface, exposing the electrode to a pre-acceleration solution with at least one accelerator, allowing the surface of the electrode to become saturated with accelerator, measuring an electrochemical response while plating the electrode in a solution, and determining the concentration of leveler in the solution by comparing the measured electrochemical response to a model relating leveler concentration to known electrochemical responses. According to other embodiments, the apparatus includes an electrode, a measuring apparatus or an electrochemical cell configured to measure an electrochemical response, and a controller designed to carry out the method outlined above.

Abstract: The evaporation of the stripping liquid 6 changes the concentration of the standard electrolyte. This causes the quantification accuracy of the chemical substance to be lowered. In order to solve the above problem, this invention provides a method for quantifying a chemical substance contained in a sample solution, characterized by the following stripping gel. The stripping gel covers the stripping electrode, and contains a standard electrolyte and an ionic liquid; however, the stripping gel contains no water. Furthermore, the ionic liquid is hydrophobic and nonvolatile, and the standard electrolyte is consisted of the anion and a metallic ion.

Abstract: The working electrode in the flow channel of a flow-through electrolytic detection cell is preconditioned by flowing a preconditioning electroplating solution with preconditioner species through the flow channel while applying a negative potential. Flow of liquid through the flow channel is rapidly switched from preconditioning solution to a target solution containing an organic target solute to be measured. The transient response of the system resulting from exposure of the working electrode to organic target solute is detected by measuring current density during an initial transient time period. An unknown concentration of target solute is determined by comparing the transient response with one or more transient responses characteristic of known concentrations. A preferred measuring system is operable to switch flow from preconditioning solution to target solution in about 200 milliseconds or less.

Abstract: An electrochemical sensing method that includes (a) providing an electrochemical cell having a working electrode and a pseudo reference electrode; (b) providing a sample comprising a metal, the sample being in contact with the working electrode and the metal being capable of being oxidized or reduced at the working electrode when the metal is bound to the working electrode; (c) preconditioning the working electrode by (i) applying a time varying preconditioning potential between the working and pseudo reference electrodes; and/or (ii) baking the working electrode; and/or (iii) air-ageing the working electrode; and (d) applying a measuring potential between the working and pseudo reference electrodes and, during application of said measuring potential, measuring the current generated by oxidation/reduction of the metal at the working electrode.

Abstract: A wellbore tool has an electrochemical sensor for measuring the amount of hydrogen sulphide or thiols in a fluid downhole in a wellbore. The sensor comprises a temperature- and pressure-resistant housing containing a flow path for the fluids. The fluids flow over one side of a gas permeable membrane the other side of the membrane being exposed to a chamber containing at least two electrodes and containing a reaction solution which together with the hydrogen sulphide or thiols create a redox reaction resulting in an electrical current dependent upon the amount of hydrogen sulphide or thiols in the fluid. Measurement is made by passing formation fluid along the flow path and repeatedly applying varying potential to one electrode and measuring the peak current flowing between that electrode and a second electrode.

Abstract: There is provided a method for preparation of a transition metal electroplated porous carbon nanofiber composite for hydrogen storage. Specifically, the preparation method of a transition metal electroplated porous carbon nanofiber composite for hydrogen storage according to the present invention comprises electroplating a transition metal with a controlled particle diameter and a surface dispersion ratio on a porous carbon nanofiber with specific surface area from 500 to 3000 m2/g, pore volume from 0.1 to 2.0 cc/g and diameter from 10 to 500 nm. With increased hydrogen storage capacity, the transition metal electroplated porous carbon nanofiber composite provided by the present invention can be utilized as hydrogen storage medium of active material for electrodes of electrochemical devices, such as fuel cell, secondary cell and supercapcitor.

Abstract: Methods for cleaning and regenerating a working electrode in an electrochemical cell; method for measuring the concentration of a metal in a liquid sample in an electrochemical cell having a working electrode, the method including a step for cleaning and/or regenerating the electrode; and an assembly having an ultrasonic device in sonic communication with an electrochemical cell.

Abstract: Disclosed herein are a wafer defect analysis apparatus, an ion extraction device used therein and a wafer defect analysis method using the same, which separate a decoration process and an ion extraction process from each other during decoration of defective regions of a wafer and circulate an electrolyte in the ion extraction device, in which ion extraction has been completed, thus minimizing time consumed for the decoration process, thereby greatly reducing an overall time taken to perform decoration and thus shortening a wafer defect analysis time and improving efficiency of defect analysis. The wafer defect analysis apparatus, the ion extraction device used therein and the wafer defect analysis method using the same improve activity of ions during extraction of the ions for the decoration process, thereby considerably shortening an ion extraction time.

Abstract: A method and apparatus are described that use cell voltage and/or current as monitor to prevent electrochemical deposition (e.g., electroplating) tools from deplating wafers with no or poor metal (e.g., Cu) seed coverage.

Abstract: The present invention relates to a sample measurement system. In particular the invention relates to a sample measurement system for measuring certain selected properties of a liquid substrate, such as the glucose levels in a blood sample. More particularly the invention relates to a sample measurement system for performing electrochemical measurements on a sample, the system comprising a sampling plate with a loading port for receiving a liquid substrate; and a measurement device; wherein the sampling plate comprises a sample zone with at least two discrete testing zones, which sample zone is arranged, in use, to separate the liquid substrate into at least two discrete samples, such that each sample occupies a respective testing zone; and the measurement device is operable to communicate with the sampling plate to measure one or more selected properties of any of the at least two samples.

Abstract: An electrochemical gas sensor (9) has improved electrochemical measurement properties and housing tightness for an electrolyte at the sites at which the connection lines (11, 21, 31) pass through. The sensor (9) includes a housing (4), containing at least one measuring electrode (1) and a counterelectrode (2) and with electric connection lines (11, 21, 31) from the electrodes (1, 2, 3) to a measuring unit (8) arranged outside the housing (4). The electric connection lines (11, 21, 31) include carbon nanotubes (CNT, Carbon Nanotubes) at least in some sections in the housing (4) in the area of the electrolyte wetting.

Abstract: An auto-calibration system for diagnostic test strips is described for presenting data individually carried on each test strip readable by a diagnostic meter. The carried data may include an embedded code relating to data particular to that individual strip. The data is presented so as to be read by a meter associated with the diagnostic test strip in order to avoid manually inputting the information.

Abstract: A sampling system for measuring the presence and concentration of inorganic ion species, including, metals, metalloids and non-metals, in a liquid solution including a first sampling unit. The first sampling unit includes a potentiometric subsystem configured to gather environmental metrics of the liquid sample, a preparation subsystem, coupled to the potentiometric module, the preparation subsystem being configured to prepare and isolate contaminants of concern in a flow of a liquid sample into metal, metalloid, or non-metal ionic forms; and a voltammetric subsystem selectively coupled to the preparation subsystem, potentiometric subsystem and a sample source, the voltammetric subsystem being configured to identify and determine a concentration of metal, metalloid, or non-metal ionic species through stripping voltammetry. The system is configured to compare a value of a stripping signal of the sample with a predetermined value to determine if dilution of the sample is required.

Abstract: This invention provides an electrochemical analysis method for accurately detecting a harmful substance such as arsenic contained in a solution. In the electrochemical analysis method, a working electrode and a counter electrode are disposed in an object electrolytic solution. A negative potential is applied to the working electrode to electrodeposit the electrolyte onto the surface of the working electrode and thus to form an electrodeposit. Next, the potential of the working electrode is sweeped in a positive potential direction to allow the electrodeposit to elute into the solution and, at the same time, to detect a current change upon a potential change and thus to analyze an object substance dissolved as an electrolyte in the object electrolytic solution. A boron-doped electroconductive diamond electrode or an electrode with gold deposited on its surface is used as the working electrode.

Abstract: A support for a thin element in an electrically conducting or semi-conducting material, one face of which is intended to be put into contact with a liquid or gas medium, the support has a first part provided with a central through-passage with a longitudinal axis, said passage including at least one first and one second portion with a different diameter connected to each other through a shoulder, said shoulder being intended for supporting said thin element; a second part penetrating into the passage with the end opposite to the one intended to be exposed to the liquid solution, capable of maintaining the thin element on the shoulder; and a seal between the thin element and the shoulder.

Abstract: An additive breakdown product in an acid copper plating bath sample is detected by performing a voltammetric analysis for the leveler additive in two measurement solutions comprising different volume fractions of the copper plating bath sample in a background electrolyte. When the plating bath sample contains a substantial concentration of the additive breakdown product, the analyses for the first and second measurement solutions indicate different concentrations for the leveler additive in the plating bath sample. A comparison of the leveler additive concentrations indicated by the two analyses provides a measure of the concentration of the additive breakdown product.

Abstract: This invention provides an electrochemical analysis method for accurately detecting a harmful substance such as arsenic contained in a solution. In the electrochemical analysis method, a working electrode and a counter electrode are disposed in an object electrolytic solution. A negative potential is applied to the working electrode to electrodeposit the electrolyte onto the surface of the working electrode and thus to form an electrodeposit. Next, the potential of the working electrode is sweeped in a positive potential direction to allow the electrodeposit to elute into the solution and, at the same time, to detect a current change upon a potential change and thus to analyze an object substance dissolved as an electrolyte in the object electrolytic solution. A boron-doped electroconductive diamond electrode or an electrode with gold deposited on its surface is used as the working electrode.

Abstract: Methods and systems for screening for the effect of bath composition on the performance of electroplating, electroless-plating, electrochemical-etching, electropolishing, and chemical-etching processes are provided. The methods and systems use microfluidic channels that allow for etching or plating studies on an electrode exposed to a multitude of bath compositions at different positions on its surface. After deposition or etching, the electrode surface can be quickly and easily detached from the device for analysis of deposited or etched film properties.

Abstract: An observation sample is prepared by immobilizing a nanomaterial on a substrate 10 by applying a voltage between a nanomaterial dispersion liquid 13, filled in an interior of an electrostatic spray nozzle 20, and the observation substrate 10 to electrostatically spray and dry the dispersion liquid 13 and electrostatically deposit the nanomaterial. With respect to the observation substrate 10, including a conductive grid portion 11 and a supporting film 12, a reference electrode 81 is disposed below the substrate 10 and a bias voltage of the same polarity as the electrostatic spraying voltage is applied to the grid portion 11 of the substrate 10 to adjust immobilization positions of the nanomaterial on the substrate 10. An observation sample, with which the nanomaterial is immobilized in a satisfactory state on the substrate, can thereby be prepared.

Abstract: The invention relates to a method of producing a nanoparticle film on a substrate, to a sensor based on such nanoparticle film and to uses thereof. The invention furthermore relates to a method of enhancing the sensitivity and/or selectivity of a nanoparticle film based sensor. Moreover, the present invention relates to a method of detecting an analyte or a mixture of analytes using the film or the sensor.

Abstract: A method for providing a two dimensional spatially varying surface potential on a surface of a conductive substrate and use thereof. The method comprises providing a conductive substrate having a first conductive surface and comprising an array of“n” electrical potential contact points spatially arranged in two dimensions on the first conductive surface, wherein “n” is at least 3. An electrical potential is then applied to each of the “n” electrical contact points, wherein the electrical potentials applied to at least two of the “n” electrical potential contact points are different. Also disclosed are methods and applications for use of the methods disclosed herein.

Abstract: Methods and systems for monitoring electrolyte bath fluids are provided. The electrolyte bath fluids can be electroplating, electroless plating or etching solutions. The monitoring systems employ microfluidic devices, which have built in microfluidic channels and microfabricated thin-film electrodes. The devices are configured with fluid pumps to control the movement and mixing of test fluids through the microfluidic channels. The microfabricated thin-film electrodes are configured so that the plating or etching bath fluid composition can be characterized by electrochemical measurements. The monitoring methods and system provide faster measurement times, generate minimal waste, and occupy dramatically reduced physical space compared to conventional bath-monitor systems. The monitoring systems and method also provide low-cost system and methods for measuring or monitoring electroless plating bath rates.

Abstract: A precious metal assay method which includes the steps of forming an electrolytic cell comprising an anode specimen and a reference cathode, driving a ramp input into the electrolytic cell, measuring a resulting current through the electrolytic cell over a period of the ramp input. The assay value may be determined by comparing the locality, slope and peak or area of a current response of the resulting current against the localities, slopes and peaks or areas of a list of current responses of known precious metal compositions from an empirical look-up table and displaying the assay value on an electronics display.

Abstract: The present invention relates in general to real-time analysis of electrochemical deposition (ECD) metal plating solutions, for the purpose of reducing plating defects and achieving high quality metal deposition. The present invention provides various new electrochemical analytical cell designs for reducing cross-contamination and increasing analytical signal strength. The present invention also provides improved plating protocols for increasing potential signal strength and reducing the time required for each measurement cycle. Further, the present invention provides new methods and algorithms for simultaneously determining concentrations of suppressor, accelerator, and leveler in a sample ECD solution within three experimental runs.

Abstract: An electrochemical drive circuitry and method, such as may be employed in electroplating bath chemical monitoring. A microcontroller can be utilized to selectively apply galvanostatic or potentiostatic conditions on the electrochemical cell, for measurement of response of the electrochemical cell to such conditions, with the microcontroller arranged to generate an offset potential to control potential across the electrochemical cell within a range of potential accommodated by a unipolar power supply, and/or a CMOS analog switch can be employed in combination with individual digital-to-analog converters for each of the current-controlled and potential-controlled conditions, to provide high-speed, dual mode operating capability.

Abstract: A method and apparatus are described that use cell voltage and/or current as monitor to prevent electrochemical deposition (e.g., electroplating) tools from deplating wafers with no or poor metal (e.g., Cu) seed coverage.

Abstract: Analytical methods are disclosed for determining the quantity of brightener and leveler in an electroplating bath in the presence of other organic additives, such as accelerators, brighteners and suppressors. The methods improve the reproducibility of measuring brighteners and levelers in electroplating baths.

Abstract: Devices and methods for evaluating an electrochemical reaction are disclosed. A device includes an electrochemical cell having a cavity for containing a liquidus electrolyte, a first working electrode having at least one electrolytic surface at least partially within the cavity, and a second counter electrode having at least one electrolytic surface at least partially within the cavity. The first working electrode includes a body and an insert supported by the body. The electrolytic surface of the working electrode is formed on or integral with the insert. The insert and body are each formed from a high-temperature material which allows for preparation or processing of the electrolytic surface at a temperature of at least 300° C. The device further includes a drive system detachably coupled to the first working electrode or a portion thereof for effecting relative motion between the electrolytic surface of the working electrode and a bulk portion of the liquidus electrolyte.

Abstract: A method for manufacturing a negative electrode for a non-aqueous electrolyte secondary battery is provided. A negative electrode precursor of the non-aqueous electrolyte secondary battery is allowed to absorb lithium ions, the negative electrode precursor includes a current collector and an active material layer formed on the current collector. The precursor is provided with an exposed portion of the current collector. In this method, a negative electrode active material layer is allowed to absorb lithium ions by electrolysis in the non-aqueous electrolyte solution. At this time, by measuring a potential of a portion immersed in the non-aqueous electrolyte solution, the exposed portion is detected and an electric current of the electrolysis is controlled. Thereby, the deposition of lithium metal on the exposed portion is suppressed.

Abstract: A method for measuring a target constituent of an electroplating solution using an electroanalytical technique is set forth in which the electroplating solution includes one or more constituents whose by-products skew an initial electrical response to an energy input of the electroanalytical technique. The method comprises a first step in which an electroanalytical measurement cycle of the target constituent is initiated by providing an energy input to a pair of electrodes disposed in the electroplating solution. The energy input to the pair of electrodes is provided for at least a predetermined time period corresponding to a time period in which the electroanalytical measurement cycle reaches a steady-state condition. In a subsequent step, an electroanalytical measurement of the energy output of the electroanalytical technique is taken after the electroanalytical measurement cycle has reached the steady-state condition.

Abstract: A counter electrode for use in an electrochemical cell suitable for analysis of an electroplating composition, the counter electrode comprising a conductor; a sheath disposed about the conductor; an electrolyte disposed within the sheath; and an optionally porous element on the sheath, the porous element providing signal communication between the electrolyte and an analyte.

Abstract: The present invention relates to a process analyzer for analyzing composition of sample electrochemical deposition solutions, comprising at least one microelectrode having a radius of not more than about 5 ?m. The process analyzer preferably comprises: (1) two or more independent analytical modules for analyzing fluid samples, (2) a primary manifold communicatively connected to the analytical modules for introducing fluid samples thereinto, and (3) a computational device communicatively associated with the analytical modules for colleting and processing analytical data therefrom, and therefore can be used to conduct automatic and simultaneous analysis of two or more sample solutions.

Abstract: An electrochemical cell assembly including a plurality of testing cells, a reference cell, and fluid connections between the testing cells and the reference cell. Each of the testing cells includes a working electrode, which is a rotating disk or ring-disk electrode, and a counter electrode. A chemical composition, whose intrinsic kinetic properties under defined mass-transfer are to be investigated, is deposited on the working electrode. The reference cell holds a reference electrode that serves as a common reference electrode for each of the testing cells. The assembly permits simultaneous testing of many chemical compositions under identical environment.

Abstract: A microstructured electrode coupled with an analytical method designed to simulate the actual conditions on the wafer and to measure critical parameters such as mass transfer of the active plating components, deposition rates of the copper in the plating bath solutions, and/or additive concentration is disclosed. Thus, an offline method for process control is provided. Additionally, the electrode and method can be incorporated into a copper interconnect bath tool or copper interconnect bath distribution system for online control of the process chemistry. The microstructured electrode design consists of a patterned electrode surface that simulates the dimensions of the interconnects and vias. The analytical method can be any type of method that allows diffusion or kinetic information to be obtained, such as electrochemical impedance, electrochemical noise, and other voltammetric or galvanostatic methods.

Abstract: A method and apparatus for analyzing plating solutions. The apparatus generally includes a plating cell, a reference electrolyte input, one or more external additive pumps, and a process controller. In one embodiment, the plating cell includes a cavity therein having a larger volumetric portion adjacent a smaller volumetric portion adapted to hold one or more solutions therein. The plating cell also includes a base disposed adjacent the bottom of the plating cell and adapted to receive and mix one or more test solutions as part of the plating solution analysis. In one configuration, the base includes electrical ports adapted to connect stimulation signals to a working electrode, counter electrode, and reference electrode disposed within the cell. The base also includes a thermal sensor in thermal contact with test solutions contained within the vessel.

Abstract: A method and apparatus for measuring the deposit forming propensity of a continuously flowing fluid having a bulk pH of about 1 to about 12 comprising measuring the rate at which deposit forms on a quartz crystal microbalance having a top side comprising a working electrode in contact with the fluid and a bottom side isolated from the fluid, wherein the pH of the fluid proximate to the microbalance is controlled electrochemically at about 1 to about 14 by applying to the working electrode a cathodic current of about ?0.001 to about ?100 mA/cm2 or an anodic current of from about 0.001 to about 100 mA/cm2 and wherein the working electrode is coated with or made of a conductive material on which the rate of hydrogen gas evolution is at least 10 times lower than on a gold cathode in acidic solution.

Abstract: A method for measuring a target constituent of an electroplating solution using an electroanalytical technique is set forth in which the electroplating solution includes one or more constituents whose by-products skew an initial electrical response to an energy input of the electroanalytical technique. The method comprises a first step in which an electroanalytical measurement cycle of the target constituent is initiated by providing an energy input to a pair of electrodes disposed in the electroplating solution. The energy input to the pair of electrodes is provided for at least a predetermined time period corresponding to a time period in which the electroanalytical measurement cycle reaches a steady-state condition. In a subsequent step, an electroanalytical measurement of the energy output of the electroanalytical technique is taken after the electroanalytical measurement cycle has reached the steady-state condition.