Rockwell International Corporation

Rockwell Scientific Licensing LLC

Innovative Technology Licensing LLC

Rockwell Technologies, Inc.

Rockwell Science Center, Inc.

Other

Teledyne Scientific and Imaging, LLC

Teledyne Licensing, LLC

Eci Technology, Inc.

D Morgan Tench

Leslie F Warren, Jr

Dennis P Anderson

Michael A Cunningham

John White

Young J Chung

Petra V Rowell

Frederick Michael Discenzo

Jeffrey DeNatale

Martin William Kendig

Greg W Davis

Eugene Shalyt

Maureen R Brongo

Peter Bratin

Michael Pavlov

Vladimir Dozortsev

Ichiro Sugioka

Dieter Dornisch

Paul H Kobrin

Alex P Moffatt

Chuan-hua Chen

John T White

Petra V Jambazian

Egbert U Beske

The thickness of a palladium coating on copper (or another substrate) is measured by passing a cathodic current through a predetermined area of the coating in contact with an electrolytic solution and measuring the potential as a function of time. Protons from the electrolytic solution are electrochemically reduced to palladium hydride at cathodic potentials less negative than required for evolution of hydrogen. As formation of the PdHbeta-phase throughout the Pd coating is completed, the cathodic potential increases rapidly to a cathodic potential plateau corresponding to evolution of hydrogen gas on the PdHsurface. This step in the cathodic potential provides an endpoint time for the measurement. The absolute thickness of the Pd coating is calculated from the integrated cathodic charge passed up to the endpoint time and the predetermined area of the coating in contact with the electrolytic solution.

Palladium coating thickness measurement

Electrochemical devices, methods, and systems for detecting and quantifying analytes are disclosed. A chemical detection reagent is locally generated in a test solution by electrochemical reaction of a precursor compound caused to migrate into the test solution from a precursor solution separated from the test solution by a cell separator. This approach provides precise metering of the reagent, via the charge passed, and avoids the need to store a reagent solution that may be chemically unstable. In one embodiment, the starch concentration in a colloidal solution can be measured via spectroscopic detection of a blue complex formed by the interaction of starch with iodine produced, on demand, by electrochemical oxidation of iodide ion. The approach may also be used to characterize certain types of analytes. The invention is amenable to automation and is particularly useful for on-line monitoring of production processes, including the inclusion of feed back loop mechanisms for process control.

Analyte detection via electrochemically transported and generated reagent

Switching uniformity of an optical modulation device for controlling the propagation of electromagnetic radiation is improved by use of an electrode comprising an electrically resistive layer that is transparent to the radiation. The resistive layer is preferably an innerlayer of a wide-bandgap oxide sandwiched between layers of indium tin oxide or another transparent conductor, and may be of uniform thickness, or may be graded so as to provide further improvement in the switching uniformity. The electrode may be used with electrochromic and reversible electrochemical mirror (REM) smart window devices, as well as display devices based on various technologies.

Electrode with transparent series resistance for uniform switching of optical modulation devices

A locally distributed electrode is made by placing a conducting metallic oxide layer and a counter electrode in contact with a noble metal electroplating solution and applying a negative potential to the metallic oxide layer relative to the counter electrode, such that the noble metal is electrodeposited from the solution preferentially at defect sites on a surface of the metallic oxide layer. The noble metal nuclei are selectively electrodeposited at the defect sites to form a locally distributed electrode made up of a dot matrix of metallic islands. For reversible electrochemical mirror (REM) devices, the presence of the noble metal renders mirror metal electrodeposition at the defect sites reversible so that the defects become part of the dot matrix electrode and extraneous deposition of the mirror metal on the conducting metallic oxide is avoided. This method avoids the use of expensive photolithography, is readily scalable to large areas, and produces electrodes that offer the optimum compromise between high current carrying capability and high light transmission.

Locally-distributed electrode and method of fabrication

A new cell assembly for semiconductor wafer electroplating in the plated-side-up configuration utilizes a narrow passageway around the perimeter of the wafer through which solution is forced so as to provide the laminar flow needed for effective Damascene copper plating. In addition, use of a cylindrical insulating cell wall whose inside diameter matches that of the wafer area being plated avoids overplating of the wafer periphery. Anode isolation in a compartment separated via a solution transport barrier prevents introduction of particulates and holds anolyte in place during wafer changes. This cell assembly is readily amendable to automated wafer plating.

Semiconductor wafer plating cell assembly

The present invention is a reversible electrodeposition optical modulation device employing a segmented counter electrode that permits localized areas of a continuous optical modulation electrode to be switched independently of each other. Such devices can be configured to enable practically seamless switching over the entire device for smart window and adjustable mirror applications, or to minimize cross-talk and pixel overlap for display applications. Since the electrical contacts and switching circuitry are located on the counter electrode, more active area is available for optical modulation.

Locally-switched reversible electrodeposition optical modulator

Reversible electrochemical mirror (REM) devices typically comprise a conductive oxide mirror electrode that is substantially transparent to radiation of some wavelengths, a counter electrode that may also be substantially transparent, and an electrolyte that contains ions of an electrodepositable metal. A voltage applied between the two electrodes causes electrodeposition of a mirror deposit on the mirror electrode and dissolution of the mirror deposit on the counter electrode, and these processes are reversed when the polarity of the applied voltage is changed. Such REM devices provide precise control over the reflection and transmission of radiation and can be used for a variety of applications, including smart windows and automatically adjusting automotive mirrors. According to the present invention, REM mirror uniformity is improved with minimal sacrifice in switching speed by utilizing a lower drive voltage when the mirror electrode sheet resistance is high, and a higher drive voltage when sufficient mirror metal is present to appreciably reduce the sheet resistance. Faster switching without damage to the electrode or decomposition of the electrolyte is provided by adjusting the applied voltage by the resistive loss in the electrolyte. Optimum results are provided by adjusting the drive voltages for the mirror metal plating and erasure processes based on real-time measurements of cell current, mirror electrode sheet resistance and temperature. Such sheet resistance measurements can also be used to monitor and control the reflectance of the device.

Optimum switching of a reversible electrochemical mirror device

The acid copper sulfate solutions used for electroplating copper circuitry in trenches and vias in IC dielectric material in the Damascene process are replaced with a type of plating system based on the use of highly complexing anions (e.g., pyrophosphate, cyanide, sulfamate, etc.) to provide an inherently high overvoltage that effectively suppresses runaway copper deposition. Such systems, requiring only one easily-controlled organic additive species to provide outstanding leveling, are more efficacous for bottom-up filling of Damascene trenches and vias than acid copper sulfate baths, which require a minimum of two organic additive species. The highly complexed baths produce fine-grained copper deposits that are typically much harder than large-grained acid sulfate copper deposits, and which exhibit stable mechanical properties that do not change with time, thereby minimizing &ldquo;dishing&rdquo; and giving more consistent CMP results. The mechanical properties and texture of the fine-grained deposits are also much less substrate dependent, which minimizes the effects of variations and flaws in the barrier and seed layers. The resistivity of pyrophosphate and annealed acid sulfate copper deposits are approximately equivalent.

Integrated circuit plating using highly-complexed copper plating baths

A cathode assembly for semiconductor wafer plating employs a polymer coating on a metal structural ring to provide a low-profile seal to the perimeter of the wafer surface to be plated. The polymer coating also electrically insulates the metal so that it can be used in contact with the plating solution and still be part of the electrical contact system, eliminating the need for a protective plastic housing. This invention permits the dimensions of the cathode assembly to be minimized. A compact cathode assembly with minimum protrusion above the wafer plated surface enables modifications to the plating cell and agitation system providing more uniform copper deposits across the wafer surface and facilitating automation of the wafer plating process.

Semiconductor wafer plating cathode assembly

The present invention is a reversible electrodeposition optical modulation device employing an ionic liquid electrolyte, which is comprised of a mixture of an ionic organic compound and the salt of an electrodepositable metal. The solventless ionic liquid can contain very high concentrations of electrodepositable metal ions and provides the high current carrying capability needed for fast device switching. Switching uniformity is also significantly improved since the electrolyte resistance is at least an order of magnitude higher than that of typical solvent-based electrolytes. Fast switching and good cycle life for high quality mirror electrodeposits in reversible electrochemical mirror (REM) devices was demonstrated. Best results were obtained for novel silver halide electrolytes employing pyrrolidinium and N-methylpyrrolidinium cations.

Reversible electrodeposition device with ionic liquid electrolyte

A direct displacement plating process provides a uniform, adherent coating of a relatively stable metal (e.g., nickel) on a highly reactive metal (e.g., aluminum) that is normally covered with a recalcitrant oxide layer. The displacement reaction proceeds, preferably in a nonaqueous solvent, as the oxide layer is dissolved by a fluoride activator. Halide anions are used to provide high solubility, to serve as an anhydrous source of stable metal ions, and to control the rate of the displacement reaction. A low concentration of activator species and little or no solution agitation are used to cause depletion of the activator species within pores in the surface oxide so that attack of the reactive metal substrate is minimized. Used in conjunction with electroless nickel deposition to thicken the displacement coating, this process can be used to render aluminum pads on IC chips solderable without the need for expensive masks and vacuum deposition operations. Such coatings can also be used to preserve or restore wire bondability, or for corrosion protection of aluminum and other reactive structural metals and alloys. A thin layer of immersion gold can be used to protect the thickened coating from oxidation. The solderable aluminum IC chip pads provide the basis for a maskless bumping process for flip chip attachment.

Controlled plating on reactive metals

A reversible electrochemical mirror (REM) includes a first electrode and a second electrode, one of which is substantially transparent to at least a portion of the spectrum of electromagnetic radiation. An essentially nonaqueous electrolytic solution, disposed between the first and second electrodes, contains ions of an electrodepositable metal having a molar concentration of more than 0.5 M. The electrolytic solution also contains halide and/or pseudohalide anions having a total molar concentration ratio of at least 2:1 relative to the concentration of the electrodepositable metal cations. A negative electrical potential applied to the first electrode causes deposited metal to be dissolved from the second electrode into the electrolytic solution and to be electrodeposited from the solution onto the first electrode to form a mirror deposit, thereby affecting the reflectivity of the REM device for electromagnetic radiation. A positive electrical potential applied to the first electrode causes deposited metal to be dissolved from the first electrode into the solution and electrodeposited from the solution onto the second electrode, thereby decreasing the reflectivity of the REM mirror. It is usually necessary to apply a surface modification layer to the first electrode to ensure uniform nucleation so that a mirror electrodeposit having high reflectivity is obtained. The high molar concentration of mirror metal cations attained in essentially nonaqueous solvents by use of at least a 2:1 molar ratio of halide and/or pseudohalide anions to electrodepositable metal ions in the electrolyte provides the fast switching speed, inherent electrolyte stability, high deposit quality, good deposit erasure and long cycle life needed for practical applications. Increases above this 2:1 molar ratio may be required to optimize the device performance.

Fast-switching reversible electrochemical mirror (REM)

Reversible electrochemical mirror (REM) devices typically comprise a conductive oxide mirror electrode that is substantially transparent to radiation of some wavelengths, a counter electrode that may also be substantially transparent, and an electrolyte that contains ions of an electrodepositable metal. A voltage applied between the two electrodes causes electrodeposition of a mirror deposit on the mirror electrode and dissolution of the mirror deposit on the counter electrode, and these processes are reversed when the polarity of the applied voltage is changed. Such REM devices provide precise control over the reflection and transmission of radiation and can be used for a variety of applications, including smart windows and automatically adjusting automotive mirrors. According to the present invention, measurements of the sheet resistance of the mirror electrode in a REM device are correlated with the thickness of electrodeposited mirror metal and can be used to monitor the reflectance of the device. Sheet resistance measurements can be performed while the mirror state of the device is being switched if adequate isolation between the measurement and switching circuits is provided. This can be accomplished by use of external resistors or more sophisticated circuitry, or by taking advantage of the relatively high sheet resistance of the mirror electrode itself. Monitoring the reflectance of REM devices according to this invention provides significant cost and performance advantages.

Reversible electrochemical mirror (REM) state monitoring

A reversible electrochemical mirror device includes a substantially transparent first electrode having a textured surface, and a second electrode which may be distributed in localized areas. An electrolytic solution, disposed between the first and second electrodes, contains ions of a metal which can electrodeposit on the electrodes. A negative electrical potential applied to the first electrode causes deposited metal to be dissolved from the second electrode into the electrolytic solution and to be electrodeposited from the solution onto the textured surface of the first electrode, thereby affecting the reflectivity of the device for electromagnetic radiation. Because of the textured surface, light striking the first electrode is diffusely reflected, making the device desirable for architectural and automotive glass applications. A surface modification layer applied to the first electrode ensures that the electrodeposit is substantially uniform. A positive electrical potential applied to the first electrode causes deposited metal to be dissolved from the first electrode and electrodeposited from the solution onto the second electrode, thereby decreasing the reflection of radiation by the device.

Diffusely-reflecting reversible electrochemical mirror

Electrochemical surface analysis using a deoxygenated gel electrolyte provides advantages over a liquid electrolyte in processes such as sequential electrochemical reduction analysis. In sequential electrochemical reduction analysis, a solderable portion of an electronic component or circuit board to be tested is placed in contact with a deoxygenated gel electrolyte such as a borate buffer solution having a gelling agent. The gel electrolyte prevents capillary attraction up or along a lead of the component so that the power source cathode lead does not contact the electrolyte and electrochemical analysis can be localized to the area of interest, such as the portion of the component lead to be soldered. Interfering effects of atmospheric oxygen are minimized for deaerated gel electrolytes because convection mixing is practically absent and diffusion is generally a very slow process in a gel. For a gel electrolyte saturated with inert gas and including an oxygen scavenger, brief exposure to oxygen as test specimens are changed does not affect the electrochemical analysis. In some cases, it is be possible to perform electrochemical analysis in ambient atmosphere rather than in an inert gas as generally required by the prior art.

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Camarillo, CA, United States of America

D Morgan Tench