Abstract: A method for in-situ generation of microbubbles is disclosed. The method includes preparing an electrochemical apparatus, where the electrochemical apparatus includes a substrate and an integrated three-electrodes array patterned on the substrate. The integrated three-electrodes array includes a working electrode, a reference electrode, and a counter electrode. The method further includes growing a nano-structured layer on the working electrode of the integrated three-electrodes array, putting the electrochemical apparatus in contact with a medium fluid, electrolyzing the medium fluid by applying an instantaneous electrical potential to the electrochemical apparatus, and generating a plurality of microbubbles around the electrochemical apparatus in contact with the medium fluid responsive to electrolyzing of the medium fluid.

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: 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 plating analyzing method is disclosed for analyzing an electroplating system having an anode, a cathode and plating liquid, based on a Laplace's equation. The method comprises the steps of making the Laplace's equation discrete by Finite Volume Method; forming simultaneous equations based on the discrete Laplace's equation; and calculating potential distribution using the simultaneous equations. A plating analyzing apparatus is also disclosed, which comprises a unit for making the Laplace's equation discrete by Finite Volume Method and dividing the system into a plurality of elements; potential calculating unit for forming simultaneous equations based on the discrete Laplace's equation, and calculating potential distribution using the simultaneous equations; and current density calculating unit for calculating current density distribution based on the potential distribution.

Abstract: The 3-mercaptopropylsulfonic acid (MPSA) breakdown product of the bis(sodiumsulfopropyl)disulfide (SPS) additive used in acid copper plating baths accelerates copper electrodeposition and can be detected by cyclic voltammetric stripping (CVS) analysis. In the presence of oxygen, MPSA decomposes rapidly in acid copper sulfate baths so that the CVS stripping peak area (Ar) decreases on successive cycles. The slope of a plot of Ar vs. CVS cycle number (or time) or logarithm of the CVS cycle number (or time) provides a measure of the initial MPSA concentration.

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 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 determining the concentration of an additive X of an electrochemical bath that includes at least one further component Y is set forth. In accordance with the method, a predetermined amount of a starting solution is provided. The starting solution comprises virgin makeup solution that is saturated with the further additive, or forms a mixed solution that is saturated with the further additive when combined with an amount of the electrochemical bath for measurement that is extracted for measurement. A predetermined amount of the extracted electrochemical bath is then added to the predetermined amount of the starting solution to form the mixed solution. At least one electroanalytical measurement cycle it is then executed using the mixed solution and the results of the measurement cycle are compared with a known measurement standard.

Abstract: A method and apparatus for measuring a target constituent of an electroplating solution using an electroanalytical technique is set forth. In accordance with the method, at least two electrodes are employed to execute the electroanalytical technique. Gasses that are trapped or generated at the surface of one or both of the electrodes of the pair are reduced and/or removed by directing a flow of solution toward the electrode surface. This flow of solution against the electrode surface acts to automatically flush the generated gasses (typically in the form of small bubbles) from the electrode surface and generally eliminates the need for manual purging by an operator. Elimination of these gasses reduces or eliminates variability in the open circuit potential, and concomitant noise that would otherwise occur in the electroanalytical measurements.

Abstract: The concentration of a reducing agent in an electroless bath for plating a first metal is determined from the effect of the reducing agent on the electrodeposition rate of a second metal. For electroless cobalt and nickel baths, a sample of the electroless plating bath is added to an acid copper plating solution and the copper electrodeposition rate is measured by cyclic voltammetric stripping (CVS) analysis. Separate analyses for hypophosphite and dimethylamineborane in baths employing both reducing agents are attained via selective decomposition of the dimethylamineborane in acidic solution.

Abstract: A crystalline Ni alloy particle for an anisotropic conductive film comprising Ni and a metalloid element such as P, B, etc. and having a structure in which a Ni intermetallic compound phase is precipitated can be produced by preparing substantially amorphous Ni alloy particle by an electroless reduction method, and heat-treating the substantially amorphous Ni alloy particle. The Ni alloy particle is preferably heat-treated after disintegration, and preferably coated with Au.

Abstract: The concentration of a leveler in a plating liquid that is used by a plating apparatus for filling metal such as copper in interconnection trenches and holes defined in the surface of a semiconductor substrate or the like is determined based on a peak area (Ar value) in a peel-off region of the plating liquid measured according to a CV or CVS process.

Abstract: A device for detecting an end point of electro-plating comprises a mandrel having a substrate and a patterned conductive layer with a main conductive area and an insulated conductive area on the substrate, an insulation region interposed between the main conductive area and the insulated conductive area, and a sensor electrically connected to the insulated conductive area for detecting a signal which indicates the end point of electro-plating.

Abstract: This invention is directed to a method and apparatus for measuring the rate of calcium oxalate scale formation in a continuously flowing solution having a pH of from about 2 to about 3 comprising measuring the rate of deposition of calcium oxalate scale from the solution on to a quartz crystal microbalance having a top side comprising a working electrode in contact with the solution and a second, bottom side isolated from the solution, wherein the pH of the solution proximate to the microbalance is measured using a pH measuring module and is controlled electrochemically at from about 3.5 to about 9 and wherein the working electrode is coated with or made of a conductive material on which the intensive evolution of hydrogen gas proceeds at potentials more negative than those necessary to achieve a pH of 3.5-9 proximate to the microbalance.

Abstract: An apparatus and method for the indirect determination of concentrations of additives in metal plating electrolyte solutions, particularly organic additives in Cu-metalization baths for semiconductor manufacturing. The apparatus features a reference electrode housed in an electrically isolated chamber and continuously immersed in the base metal plating solution (without the additive to be measured). An additive concentration determination method comprises electroplating a test electrode at a constant or known current in a mixing chamber wherein the base metal plating solution is mixed with small volumes of the sample and various calibration solutions containing the additive to be measured. Plating potentials between the electrodes are measured and plotted for each of the solution mixtures, and data are extrapolated to determine the concentration of the additive in the sample.

Abstract: In one embodiment, a method of electrowinning a metal from an electrolyte comprises the steps of measuring the redox potential of the electrolyte to obtain a measured value, comparing the measured value with a predetermined optimum value and adding a redox agent to the electrolyte to adjust the redox potential of the electrolyte to the optimum value. One embodiment of apparatus (10) for carrying out the method comprises a redox potential measuring device (20) having a housing for the flow of electrolyte therethrough and including a pair of electrodes (22, 24) for measuring the redox potential of an electrolyte flowing through the housing to produce an output measurement value and a redox controller (26) responsive to the output measurement value for controlling the addition of redox agent to the electrolyte of an electrolysis cell (12).

Abstract: A method for monitoring the constituents present in an electroless plating bath solution. The method involves measuring ac spectra using a working electrode which has a high hydrogen overvoltage. First, a selected dc potential is applied to a working electrode which has been subjected to pretreatment and which is present in the electroless bath being analyzed. The electrode must have a high hydrogen overvoltage and is preferably an alloy of a low hydrogen overvoltage noble metal and a high overvoltage metal. A constant ac signal is superimposed on the dc potential. The dc potential is then swept over a chosen range at a selected sweep rate. The various constituents in the bath are then monitored by measuring the ac current at one or more reference phase angles with respect to the constant ac signal between the working electrode and a reference electrode as the dc potential is varied. The resulting ac spectra provides a useful measurement of the make-up of the constituents in the electroless plating solution.

Abstract: A method for monitoring the constituents present in conversion coating bath solutions. The method involves using specific ac and dc voltammetry and using platinum or other noble metal working electrodes. First, a selected dc potential is applied to a working electrode which has been subjected to pretreatment and which is present as an in-tank sensor in the bath being analyzed. A constant ac signal is superimposed on the dc potential. The dc potential is then swept over a chosen range at a selected sweep rate. The various constituents in the bath are then monitored by measuring dc current and the ac current at one or more reference phase angles with respect to the constant ac signal between the working electrode and a reference electrode as the dc potential is varied. The resulting dc and ac spectra provide a useful measurement of the make-up of the constituents in the bath solutions.

Abstract: A large amplitude sine wave is applied as the excitation potential to a amperometric measurement to produce a current output that is a phase shifted sine wave containing faradaic information at many frequencies. A current obtained from a conventional potentiostat coupled to the electrode is coupled to a lock-in amplifier that monitors the signal at one frequency at a specified phase angle. Since most of the background remains at the fundamental frequency, a higher harmonic of the fundamental frequency of the sinusoidal sweep frequency is monitored. By locking in on the higher harmonic components, the faradaic signal is therefore distinguished from the background signal. The background is diminished thereby allowing signal recognition at low analyte concentrations and increasing the signal-to-noise ratio.