Utilizing Organic Compound-containing Bath Patents (Class 205/296)
  • Patent number: 6562222
    Abstract: In filling fine via holes or trenches of the wiring (LSI) pattern formed on a semiconductor wafer, a copper electroplating is carried out by using a copper electroplating solution. containing an azole or a silane coupling agent, or a copper electroplating is carried out after the immersion into a pretreatment solution containing an azole or a silane coupling agent. As illustratively shown above, the addition of a component having the action to inhibit the dissolution of copper to an electroplating solution or the pretreatment by a solution containing a component having the action to inhibit the dissolution of copper can inhibit the dissolution of a copper seed layer covering poorly, and thus can prevent the occurrence of defects such as voids and seams.
    Type: Grant
    Filed: December 5, 2001
    Date of Patent: May 13, 2003
    Assignee: Nikko Materials Company, Limited
    Inventors: Jyunnosuke Sekiguchi, Syunichiro Yamaguchi
  • Publication number: 20030085132
    Abstract: A metal plating bath and metal plating process that contains aldehyde compounds that prevent or reduce the consumption of metal plating bath additives. The metal plating baths provide for an efficient plating method because the plating process need not be interrupted to replenish the plating bath with additives. The Metal plating baths may be employed to plate metals such as copper, gold, silver, palladium, cobalt, chromium, cadmium, bismuth, indium, rhodium, iridium, and ruthenium.
    Type: Application
    Filed: October 2, 2001
    Publication date: May 8, 2003
    Applicant: Shipley Company, L.L.C.
    Inventors: Andrew J. Cobley, Mark J. Kapeckas, Erik Reddington, Wade Sonnenberg, Leon R. Barstad, Thomas Buckley
  • Publication number: 20030085133
    Abstract: The present invention provides a copper plating solution for embedding fine wiring, wherein it contains copper sulfate at 100 to 300 g/L as copper sulfate pentahydrate, sulfuric acid at 5 to 300 g/L, chlorine at 20 to 200 mg/L, a macromolecular surfactant at 0.05 to 20 g/L for controlling the electrodeposition reaction, sulfur-based saturated organic compound at 1 to 100 mg/L for accelerating the electrodeposition reaction, leveling agent composed of a macromolecular amine compound at 0.01 to 10 mg/L and reductant at 0.025 to 25 g/L for stabilizing the copper plating solution. The copper plating solution of the present invention for embedding fine wiring can plate the wafer surface provided with fine wiring patterns with sub-micron order gaps in-between and coated with copper serving as the metallic seed film, to fill the gaps neither leaving any defect therein nor dissolving the metallic seed film.
    Type: Application
    Filed: April 25, 2002
    Publication date: May 8, 2003
    Applicant: Electroplating Engineers of Japan Limited (Japanese Corporation)
    Inventors: Takashi Totsuka, Toshio Kuzushima
  • Publication number: 20030075450
    Abstract: The interior of cavities and through-holes in electrically conductive substrates having high-aspect ratios of 8:1 or greater can be electroplated with a uniform layer of metal on their interior surfaces by using a pulse reverse voltage waveform having a pulse train of long cathodic pulses followed by short anodic pulses even in the absence of conventional additives such as levelers and brighteners.
    Type: Application
    Filed: October 15, 2001
    Publication date: April 24, 2003
    Inventors: E. Jennings Taylor, Jenny J. Sun
  • Publication number: 20030066756
    Abstract: A metal plating bath and method for plating a metal on a substrate. The metal plating bath contains hydroxylamines that inhibit the consumption of additive bath components to improve the efficiency of metal plating processes. The additive bath components are added to metal plating baths to improve brightness of plated metal as well as the micro-throwing and macro-throwing power of the bath. In addition to brighteners, the additive bath components may include levelers, suppressors, hardeners, and the like. The hydroxylamines that inhibit additive consumption may be employed in metal plating baths for plating copper, gold, silver, platinum, palladium, cobalt, cadmium, nickel, bismuth, indium, tin, rhodium, iridium, ruthenium and alloys thereof.
    Type: Application
    Filed: October 4, 2001
    Publication date: April 10, 2003
    Applicant: Shipley Company, L.L.C.
    Inventors: David R. Gabe, Andrew J. Cobley, Leon R. Barstad, Mark J. Kapeckas, Erik Reddington, Wade Sonnenberg, Thomas Buckley
  • Publication number: 20030052013
    Abstract: An R—T—B magnet (R is at least one kind of rare-earth elements including Y, and T is Fe or Fe and Co.) has an electrolytic copper-plating film where the ratio [I(200)/I(111)] of the X-ray diffraction peak intensity I(200) from the (200) plane to the X-ray diffraction peak intensity I(111) from the (111) plane is 0.1-0.45 in the X-ray diffraction by CuKal rays. This electrolytic copper-plating film is formed by an electrolytic copper-plating method using an electrolytic copper-plating solution which contains 20-150 g/L of copper sulphate and 30-250 g/L of chelating agent and contains no agent for reducing copper ions and has a pH adjusted to 10.5-13.5.
    Type: Application
    Filed: September 9, 2002
    Publication date: March 20, 2003
    Inventors: Setsuo Ando, Minoru Endoh, Tsutomu Nakamura, Toru Fukushi
  • Patent number: 6531046
    Abstract: Disclosed are methods of repairing metal seed layers prior to subsequent metallization. Such repair methods provide metal seed layers disposed on a substrate that are substantially free of metal oxide and substantially free of discontinuities.
    Type: Grant
    Filed: December 15, 2000
    Date of Patent: March 11, 2003
    Assignee: Shipley Company, L.L.C.
    Inventors: Denis Morrissey, David Merricks, Leon R. Barstad, Eugene N. Step, Jeffrey M. Calvert, Robert A. Schetty, III, James G. Shelnut, Mark Lefebvre, Martin W. Bayes, Donald E. Storjohann
  • Patent number: 6527939
    Abstract: A method of producing copper foil, and more particularly, in an electrochemical cell containing organic substituents, is provided herein. The metal may be deposited on an electrode that comprises an electrode base having at least one undercoating layer of an active coating and at least one topcoating layer of no significant activity. The copper electrodeposition cell can operate without an adverse affect on electrode potential.
    Type: Grant
    Filed: June 22, 2000
    Date of Patent: March 4, 2003
    Assignee: Eltech Systems Corporation
    Inventor: Kenneth L Hardee
  • Patent number: 6511588
    Abstract: A plating method comprising using a plating solution containing an additive satisfying the following conditions: 0.005×h2/w<D/&kgr;<0.5×h2/w, and 0.01≦&THgr;≦0.
    Type: Grant
    Filed: April 7, 2000
    Date of Patent: January 28, 2003
    Assignee: Hitachi, Ltd.
    Inventors: Kinya Kobayashi, Akihiro Sano, Takeyuki Itabashi, Toshio Haba, Haruo Akahoshi, Shinichi Fukada
  • Publication number: 20030015433
    Abstract: Electrolytic copper plating methods are provided, wherein copper is electrolytically deposited on a substrate, and the electrolytic copper plating solution supplied to said electrolytic copper plating is subjected to dummy electrolysis using an insoluble anode. The method described above can maintain and restore the electrolytic copper plating solution so as to maintain satisfactory appearance of plated copper, fineness of deposited copper film, and via-filling.
    Type: Application
    Filed: June 7, 2002
    Publication date: January 23, 2003
    Applicant: Shipley Company, L.L.C.
    Inventors: Hideki Tsuchida, Masaru Kusaka, Shinjiro Hayashi
  • Patent number: 6491806
    Abstract: The present invention relates to a copper electroplating bath composition and method of using it for microelectronic device fabrication. In particular, the present invention relates to copper electroplating in the fabrication of interconnect structures in semiconductor devices. By use of the inventive copper electroplating bath composition, the incidence of voids in the interconnect structures is reduced.
    Type: Grant
    Filed: April 27, 2000
    Date of Patent: December 10, 2002
    Assignee: Intel Corporation
    Inventors: Valery Dubin, Kimin Hong, Nate Baxter
  • Publication number: 20020153259
    Abstract: The present invention is related to a method for the preparation of a composition for electroplating a copper-containing layer on a substrate. This method makes use of an aqueous solution that has at least: a source of copper Cu (II) ions, an additive to adjust the pH to a predetermined value, and a complexing agent for complexing Cu (II) ions.
    Type: Application
    Filed: December 12, 2001
    Publication date: October 24, 2002
    Inventors: Roger Palmans, Yuri Lantasov
  • Patent number: 6444110
    Abstract: The present invention provides methods for the use of copper electroplating compositions. Electroplating compositions of the invention contain an increased brightener concentration that can provide effective copper plate on difficult-to-plate aperture walls, including high aspect ratio, small diameter microvias.
    Type: Grant
    Filed: May 17, 1999
    Date of Patent: September 3, 2002
    Assignee: Shipley Company, L.L.C.
    Inventors: Leon R. Barstad, James E. Rychwalski, Mark Lefebvre, Stephane Menard, James L. Martin, Robert A. Schetty, III, Michael Toben
  • Patent number: 6425996
    Abstract: For the uniform electrolytic deposition of copper coatings, especially on printed circuit boards, an aqueous deposition bath is used which contains as constituents at least one source of copper ions, at least one compound increasing the electrical conductivity of the deposition bath as well as at least one additive, at least one transformation product, formed from epihalohydrins, dihalohydrins or respectively 1-halogen-2,3-propanediols and polyamidoamines being contained as the additive. The polyamidoamines are formed by the condensation reaction of dicarboxylic acids with polyalkylene polyamines. When copper coatings are deposited from this bath, copper layers of uniform layer thickness can be deposited.
    Type: Grant
    Filed: July 28, 2000
    Date of Patent: July 30, 2002
    Assignee: Atotech Deutschland GmbH
    Inventors: Wolfgang Dahms, Michael Jonat, Gerd Senge, Detley Nitsche
  • Publication number: 20020084191
    Abstract: An object of the present invention is to improve the reliability and the yield of production of semiconductor integrated circuit devices by filling copper in the inside of features having a high aspect ratio for forming multi-layer interconnections composed of a plurality of interconnection layers which are connected to one another and to a copper electroplating bath suitable therefor. In the present invention, when the features are filled with copper, the use of a copper electroplating bath with an addition of cyanine dyes, for example, indolium compounds allows the copper plating to proceed preferentially from the bottoms of the features.
    Type: Application
    Filed: June 26, 2001
    Publication date: July 4, 2002
    Inventors: Toshio Haba, Takeyuki Itabashi, Haruo Akahoshi, Shinichi Fukada
  • Patent number: 6406609
    Abstract: The present invention provides an aqueous electroplating solution. The aqueous electroplating solution includes a copper salt comprising a weight by weight percent of the electroplating solution between about 0.1% to about 2.5%. The electroplating solution also includes an inorganic acid having a dissociation constant of less than about 2.0, and comprising a weight by weight percent of the electroplating solution between about 0.1% to about 10%. The electroplating solution further includes a hydrogenated halide and a modulator, each that comprises a weight by weight percent of the electroplating solution between about 0.0001% to about 1%.
    Type: Grant
    Filed: February 25, 2000
    Date of Patent: June 18, 2002
    Assignee: Agere Systems Guardian Corp.
    Inventors: Jennifer S. Obeng, Yaw S. Obeng
  • Patent number: 6402924
    Abstract: The present invention relates to a method of electrodepositing metal onto a substrate, which comprises applying a pulsed periodic reverse current across the electrodes of a plating cell utilizing a peak reverse current density and peak forward current density; and varying the ratio of peak reverse current density to peak forward current density in periodic cycles to provide metal deposits of uniform thickness and appearance upon the substrate. The invention also relates to a process for improving the properties of an electrodeposit, particularly on substrates having uneven surfaces or apertures, by using programmed pulse periodic reverse current modulation. More particularly, it involves varying the anodic to cathodic current density ratio, in order to improve the surface uniformity appearance, grain structure and levelling of the deposit while maintaining high current density throwing power.
    Type: Grant
    Filed: May 1, 2000
    Date of Patent: June 11, 2002
    Assignee: Shipley Company LLC
    Inventors: James L. Martin, Stephane Menard, David N. Michelen
  • Publication number: 20020063064
    Abstract: The present invention provides plating solutions, particularly metal plating solutions, designed to provide uniform coatings on substrates and to provide substantially defect free filling of small features, e.g., micron scale features and smaller, formed on substrates with none or low supporting electrolyte, i.e., which include no acid, low acid, no base, or no conducting salts, and/or high metal ion, e.g., copper, concentration. Additionally, the plating solutions may contain small amounts of additives which enhance the plated film quality and performance by serving as brighteners, levelers, surfactants, grain refiners, stress reducers, etc.
    Type: Application
    Filed: November 13, 2001
    Publication date: May 30, 2002
    Applicant: Applied Materials, Inc.
    Inventors: Uziel Landau, John J. D'Urso, David B. Rear
  • Publication number: 20020043468
    Abstract: Disclosed are compositions useful for repair and electroplating of seed layers. Also disclosed are methods of repairing and electroplating such seed layers.
    Type: Application
    Filed: October 12, 2001
    Publication date: April 18, 2002
    Applicant: Shipley Company, L.L.C.
    Inventors: Robert D. Mikkola, Jeffrey M. Calvert
  • Patent number: 6372113
    Abstract: Treated copper foil produced by electrodepositing on a matte surface of a base copper foil a “corrective” copper layer having a surface roughness different from the surface roughness of the matte surface of the base foil and which has a peak count greater than the peak count of the matte surface of the base foil. In the electrodeposition there are used a unique electrolyte composition and plating conditions effective to control the micro-throwing process of the plating process so that the surface roughness of the corrective is substantially constant from one batch of base foil to another.
    Type: Grant
    Filed: September 13, 1999
    Date of Patent: April 16, 2002
    Assignee: Yates Foil USA, Inc.
    Inventors: Charles B. Yates, George Gaskill, Chinsai T. Cheng, Ajesh Shah, Adam M. Wolski, Paul DuFresne
  • Publication number: 20020036145
    Abstract: The present invention relates to a copper electroplating bath composition and method of using it for microelectronic device fabrication. In particular, the present invention relates to copper electroplating in the fabrication of interconnect structures in semiconductor devices. By use of the inventive copper electroplating bath composition, the incidence of voids in the interconnect structures is reduced.
    Type: Application
    Filed: October 3, 2001
    Publication date: March 28, 2002
    Inventors: Valery Dubin, Kimin Hong, Nate Baxter
  • Publication number: 20020036144
    Abstract: A copper-plating electrolyte includes an aqueous copper salt solution, a water-soluble &bgr;-naphtholethoxylate compound having the formula 1
    Type: Application
    Filed: July 6, 2001
    Publication date: March 28, 2002
    Inventors: Sun-Jung Lee, Kyu-Hwan Chang, Hyeon-Deok Lee
  • Publication number: 20020027081
    Abstract: There is provided a copper-plating liquid free from an alkali metal and a cyanide which, when used in plating of a substrate having an outer seed layer and fine recesses of a high aspect ratio, can reinforce the thin portion of the seed layer and can embed copper completely into the depth of the fine recesses.
    Type: Application
    Filed: June 29, 2001
    Publication date: March 7, 2002
    Inventors: Mizuki Nagai, Shuichi Okuyama, Ryoichi Kimizuka, Takeshi Kobayashi
  • Patent number: 6350366
    Abstract: The present invention provides plating solutions, particularly metal plating solutions, designed to provide uniform coatings on substrates and to provide substantially defect free filling of small features, e.g., micron scale features and smaller, formed on substrates with none or low supporting electrolyte, ie., which include no acid, low acid, no base, or no conducting salts, and/or high metal ion, e.g., copper, concentration. Additionally, the plating solutions may contain small amounts of additives which enhance the plated film quality and performance by serving as brighteners, levelers, surfactants, grain refiners, stress reducers, etc.
    Type: Grant
    Filed: January 18, 2000
    Date of Patent: February 26, 2002
    Assignee: Applied Materials, Inc.
    Inventors: Uziel Landau, John J. D'Urso, David B. Rear
  • Patent number: 6344129
    Abstract: A method for plating copper conductors on an electronic substrate and devices formed are disclosed. In the method, an electroplating copper bath that is filled with an electroplating solution kept at a temperature between about 0° C. and about 18° C. is first provided. A copper layer on the electronic substrate immersed in the electroplating solution is then plated either in a single step or in a dual-step deposition process. The dual-step deposition process is more suitable for depositing copper conductors in features that have large aspect ratios, such as a via hole in a dual damascene structure having an aspect ratio of diameter/depth of more than ⅓ or as high as {fraction (1/10)}. Various electroplating parameters are utilized to provide a short resistance transient in either the single step deposition or the dual-step deposition process.
    Type: Grant
    Filed: October 13, 1999
    Date of Patent: February 5, 2002
    Assignee: International Business Machines Corporation
    Inventors: Kenneth P. Rodbell, Panayotis C. Andricacos, Cyril Cabral, Jr., Lynne M. Gignac, Cyprian E. Uzoh, Peter S. Locke
  • Publication number: 20020004145
    Abstract: The invention relates to use of capture compounds such as a crown ether to facilitate selected compositions and processes employed in manufacture of electronic packaging devices such as printed circuit boards, semiconductor integrated circuit systems, multichip modules, lead frames and other interconnection devices, flat panel display substrates, and the like.
    Type: Application
    Filed: May 8, 2001
    Publication date: January 10, 2002
    Applicant: Shipley Company, L.L.C.
    Inventors: Steven M. Florio, Gary S. Calabrese, Jeffrey Doubrava
  • Publication number: 20020000382
    Abstract: Disclosed are methods of repairing metal seed layers prior to subsequent metallization. Such repair methods provide metal seed layers disposed on a substrate that are substantially free of metal oxide and substantially free of discontinuities.
    Type: Application
    Filed: December 15, 2000
    Publication date: January 3, 2002
    Applicant: Shipley Company, L.L.C. of Marlborough
    Inventors: Denis Morrissey, David Merricks, Leon R. Barstad, Eugene N. Step, Jeffrey M. Calvert, Robert A. Schetty, James G. Shelnut, Mark Lefebvre, Martin W. Bayes, Donald E. Storjohann
  • Publication number: 20010047943
    Abstract: The present invention provides inter alia copper electroplating compositions, methods for use of the compositions and products formed by the compositions. Electroplating compositions of the invention contain an increased brightener concentration that can provide effective copper plate on difficult-to-plate aperture walls, including high aspect ratio, small diameter microvias.
    Type: Application
    Filed: May 17, 1999
    Publication date: December 6, 2001
    Inventors: LEON BARSTAD, JAMES RYCHWALSKI, MARK LEFEBVRE, STEPHANE MENARD, JAMES MARTIN, ROBERT SCHETTY, MICHAEL TOBEN
  • Patent number: 6294220
    Abstract: A post-treatment method for copper on printed circuit boards is disclosed. The method comprises forming a cupric-based organometallic conversion coating on a copper surface of a printed circuit board, and then converting the cupric-based organometallic conversion coating to a cuprous-based organometallic conversion coating. The resulting cuprous-based organometallic conversion coating is desirable in that it improves copper to dielectric bond integrity.
    Type: Grant
    Filed: June 30, 1999
    Date of Patent: September 25, 2001
    Assignee: Alpha Metals, Inc.
    Inventors: Peter T. McGrath, Abayomi Owei, Saeed Sardar, Eric Yakobson
  • Patent number: 6290833
    Abstract: This invention employs a novel approach to the copper metallization of a workpiece, such as a semiconductor workpiece. In accordance with the invention, an alkaline electrolytic copper bath is used to electroplate copper onto a seed layer, electroplate copper directly onto a barrier layer material, or enhance an ultra-thin copper seed layer which has been deposited on the barrier layer using a deposition process such as PVD. The resulting copper layer provides an excellent conformal copper coating that fills trenches, vias, and other microstructures in the workpiece. When used for seed layer enhancement, the resulting copper seed layer provide an excellent conformal copper coating that allows the microstructures to be filled with a copper layer having good uniformity using electrochemical deposition techniques. Further, copper layers that are electroplated in the disclosed manner exhibit low sheet resistance and are readily annealed at low temperatures.
    Type: Grant
    Filed: August 31, 1999
    Date of Patent: September 18, 2001
    Assignee: Semitool, Inc.
    Inventor: Linlin Chen
  • Publication number: 20010015321
    Abstract: Electroplating methods using an electroplating bath containing metal ions and a suppressor additive, an accelerator additive, and a leveler additive, together with controlling the current density applied to a substrate, avoid defects in plated films on substrates having features with a range of aspect ratios, while providing good filling and thickness distribution. The methods include, in succession, applying DC cathodic current densities optimized to form a conformal thin film on a seed layer, to provide bottom-up filling, preferentially on features having the largest aspect ratios, and to provide conformal plating of all features and adjacent field regions. Including a leveling agent in the electroplating bath produces films with better quality after subsequent processing.
    Type: Application
    Filed: February 28, 2001
    Publication date: August 23, 2001
    Inventors: Jonathan D. Reid, David Smith, Steven T. Mayer, Jon Henri, Sesha Varadarajan
  • Patent number: 6277263
    Abstract: This invention employs a novel approach to the copper metallization of a workpiece, such as a semiconductor workpiece. In accordance with the invention, an alkaline electrolytic copper bath is used to electroplate copper onto a seed layer, electroplate copper directly onto a barrier layer material, or enhance an ultra-thin copper seed layer which has been deposited on the barrier layer using a deposition process such as PVD. The resulting copper layer provides an excellent conformal copper coating that fills trenches, vias, and other microstructures in the workpiece. When used for seed layer enhancement, the resulting copper seed layer provide an excellent conformal copper coating that allows the microstructures to be filled with a copper layer having good uniformity using electrochemical deposition techniques. Further, copper layers that are electroplated in the disclosed manner exhibit low sheet resistance and are readily annealed at low temperatures.
    Type: Grant
    Filed: August 31, 1999
    Date of Patent: August 21, 2001
    Assignee: Semitool, Inc.
    Inventor: LinLin Chen
  • Publication number: 20010009724
    Abstract: Deposition of metal in a preferred shape, including coatings on parts, or stand-alone materials, and subsequent heat treatment to provide improved mechanical properties. In particular, the method gives products with relatively high yield strength. The products often have relatively high elastic modulus, and are thermally stable, maintaining the high yield strength at temperatures considerably above 25° C. This technique involves depositing a material in the presence of a selected additive, and then subjecting the deposited material to a moderate heat treatment. This moderate heat treatment differs from other commonly employed “stress relief” heat treatments in using lower temperatures and/or shorter times, preferably just enough to reorganize the material to the new, desired form. Coating and heat treating a spring-shaped substrate provides a resilient, conductive contact useful for electronic applications.
    Type: Application
    Filed: January 29, 2001
    Publication date: July 26, 2001
    Inventors: Jimmy Kuo-Wei Chen, Benjamin N. Eldridge, Thomas H. Dozier, Junjye J. Yeh, Gayle J. Herman
  • Patent number: 6251253
    Abstract: The use of alkali metal, alkaline earth metal, ammonium and substituted ammonium salts of alkyl and alkanol sulfonic acids as additives in pure metal and metal alloy sulfate electroplating baths has a number of unexpected benefits including wider useful current density range, improved appearance and in the case of tin improved oxidative stability. The metals and alloys include but are not limited to tin, nickel, copper, chromium, cadmium, iron, rhodium, ruthenium, iron/zinc and tin/zinc.
    Type: Grant
    Filed: March 19, 1999
    Date of Patent: June 26, 2001
    Assignees: Technic, Inc., Specialty Chemical Systems, Inc.
    Inventors: Hyman D. Gillman, Brenda Fernandes, Kazimierz Wikiel
  • Patent number: 6248228
    Abstract: The use of alkali metal, alkaline earth metal, ammonium and substituted ammonium salts of alkyl and alkanol sulfonic acids as additives in pure metal and metal alloy halide electroplating baths has a number of unexpected benefits including wider useful current density range and improved appearance. The metals and metal alloys include but are not limited to tin, lead, copper, nickel, zinc, cadmium, tin/zinc, zinc/nickel and tin/nickel.
    Type: Grant
    Filed: March 19, 1999
    Date of Patent: June 19, 2001
    Assignee: Technic, Inc. and Specialty Chemical System, Inc.
    Inventors: Hyman D. Gillman, Brenda Fernandes, Kazimierz Wikiel
  • Patent number: 6194056
    Abstract: A high tensile strength copper foil having a matte side roughness Rz of 2.5 &mgr;m or less and a tensile strength of 40,000 Kgf/mm2 after heating one hour at 180° C. is produced by a process in which copper is electrodeposited from a solution containing predetermined small amounts of a polyether glycol and tin and iron ions. The chloride ion content is maintained below 0.1 wt. ppm. The copper foil is characterized by having copper crystals with atomic cells having a predominently (111) orientation.
    Type: Grant
    Filed: July 9, 1999
    Date of Patent: February 27, 2001
    Assignee: Mitsui Mining & Smelting Co., Ltd.
    Inventors: Hisao Sakai, Toshiko Yokota, Tsutomu Asai, Susumu Takahashi, Mitsuo Suzuki, Makoto Dobashi, Yasuji Hara
  • Patent number: 6183622
    Abstract: A method of electrowinning, electrorefining or electroforming of ductile copper deposits. The method uses an adduct of a tertiary alkyl amine with polyepichlorohydrin in amounts effective for ductilizing a copper deposit form a copper electrolyte.
    Type: Grant
    Filed: July 13, 1998
    Date of Patent: February 6, 2001
    Assignee: Enthone-OMI, Inc.
    Inventor: Robert Janik
  • Patent number: 6183545
    Abstract: An aqueous solution for the reductive deposition of metals comprising, besides water, (A) a phosphine of the general formula (1)  in which R1, R2, and R3 denote lower alkyl groups, at least one of which being hydroxy-or amino-substituted lower alkyl group, and (B) a soluble compound of a metal or a compound of a metal solubilized through the formation of a soluble complex by said phosphine.
    Type: Grant
    Filed: June 28, 1999
    Date of Patent: February 6, 2001
    Assignee: Daiwa Fine Chemicals Co., Ltd.
    Inventors: Yoshiaki Okuhama, Takao Takeuchi, Masakazu Yoshimoto, Shigeru Takatani, Emiko Tanaka, Masayuki Nishino, Yuji Kato, Yasuhito Kohashi, Kyoko Kuba, Tetsuya Kondo, Keiji Shiomi, Keigo Obata, Mitsuo Komatsu, Hidemi Nawafune
  • Patent number: 6179985
    Abstract: The use of alkali metal, alkaline earth metal, ammonium and substituted ammonium salts of alkyl and alkanol sulfonic acids as additives in pure metal and metal alloy fluoroborate electroplating baths has a number of unexpected benefits including wider useful current density range and improved appearance. The metals and metal alloys include but are not limited to tin, lead, copper, cadmium, indium, iron, tin/lead and tin/lead copper.
    Type: Grant
    Filed: March 19, 1999
    Date of Patent: January 30, 2001
    Assignees: Technic, Inc., Specialty Chemical Systems, Inc.
    Inventors: Hyman D. Gillman, Brenda Fernandes, Kazimierz Wikiel
  • Patent number: 6113771
    Abstract: The present invention provides plating solutions, particularly metal plating solutions, designed to provide uniform coatings on substrates and to provide substantially defect free filling of small features, e.g., micron scale features and smaller, formed on substrates with none or low supporting electrolyte, i.e., which include no acid, low acid, no base, or no conducting salts, and/or high metal ion, e.g., copper, concentration. Additionally, the plating solutions may contain small amounts of additives which enhance the plated film quality and performance by serving as brighteners, levelers, surfactants, grain refiners, stress reducers, etc.
    Type: Grant
    Filed: July 13, 1998
    Date of Patent: September 5, 2000
    Assignee: Applied Materials, Inc.
    Inventors: Uziel Landau, John J. D'Urso, David B. Rear
  • Patent number: 6071398
    Abstract: The present invention relates to a method of electrodepositing metal onto a substrate, which comprises applying a pulsed periodic reverse current across the electrodes of a plating cell utilizing a peak reverse current density and peak forward current density; and varying the ratio of peak reverse current density to peak forward current density in periodic cycles to provide metal deposits of uniform thickness and appearance upon the substrate. The invention also relates to a process for improving the properties of an electrodeposit, particularly on substrates having uneven surfaces or apertures, by using programmed pulse periodic reverse current modulation. More particularly, it involves varying the anodic to cathodic current density ratio, in order to improve the surface uniformity appearance, grain structure and levelling of the deposit while maintaining high current density throwing power.
    Type: Grant
    Filed: October 6, 1997
    Date of Patent: June 6, 2000
    Assignee: Learonal, Inc.
    Inventors: James L. Martin, Stephane Menard, David N. Michelen
  • Patent number: 6054037
    Abstract: A method and electrolyte bath for depositing Cu.sup.+1 ions from the cathode diffusion layer onto a zinc substrate. Halogen ions are used as additives to organophosphonate alkaline copper electrolytes for stabilizing Cu.sup.+1 in the cathode diffusion layer.
    Type: Grant
    Filed: November 11, 1998
    Date of Patent: April 25, 2000
    Assignee: Enthone-OMI, Inc.
    Inventor: Sylvia Martin
  • Patent number: 6024857
    Abstract: An electroplating system includes a standard electroplating apparatus using an acid copper bath with an additive for leveling. The additive is chosen to have molecules of a size that is about the size of the features to be filled by the electroplating process. The relatively large size of these additive molecules tends to hinder the mass transfer of the additive molecules into the features. Consequently, the additive molecules are preferentially absorbed by the surface of the plating surface relative to the inner surfaces of the features. Accordingly, the electroplating process tends to fill the features relatively quickly compared to the other parts of the target surface so that all of the surface area of the target is equivalent in height. Because little or no additive molecules are within the features, the features tend to be filled without the voids often produced using conventional systems.
    Type: Grant
    Filed: October 8, 1997
    Date of Patent: February 15, 2000
    Assignee: Novellus Systems, Inc.
    Inventor: Jonathan David Reid
  • Patent number: 5958209
    Abstract: A high tensile strength copper foil having a matte side roughness Rz of 2.5 .mu.m or less and a tensile strength of 40,000 Kgf/mm.sup.2 after heating one hour at 180.degree. C. is produced by a process in which copper is electrodeposited from a solution containing predetermined small amounts of a polyether glycol and tin and iron ions. The chloride ion content is maintained below 0.1 wt. ppm. The copper foil is characterized by having copper crystals with atomic cells having a predominantly (111) orientation.
    Type: Grant
    Filed: May 13, 1997
    Date of Patent: September 28, 1999
    Assignee: Mitsui Mining & Smelting Co., Ltd.
    Inventors: Hisao Sakai, Toshiko Yokota, Tsutomu Asai, Susumu Takahashi, Mitsuo Suzuki, Makoto Dobashi, Yasuji Hara
  • Patent number: 5935402
    Abstract: A process and assembly for stabilizing organic additives in an electrolytic solution while electroplating copper. The process includes forming a protective film on a first surface of an anode and minimizing contact between the electrolytic solution and a second surface of the anode which is further from the cathode than the first surface. An anode housing is used to minimize contact between the electrolytic solution and the second surface of the anode. The housing includes two side walls and a bottom wall, each having a groove, and a sealing back plate. The anode is fitted in the grooves such that the first surface of the anode is in contact with the electrolytic solution and the second surface of the anode abuts against the sealing back plate. The anode housing may be used in an electroplating system including the anode housing, a plating tank containing the electrolytic solution, a cathode immersed in the electrolytic solution, and an anode, which preferably is in the shape of a slab.
    Type: Grant
    Filed: October 9, 1998
    Date of Patent: August 10, 1999
    Assignee: International Business Machines Corporation
    Inventor: Lisa A. Fanti
  • Patent number: 5849171
    Abstract: An aqueous acid bath for galvanic precipitation of copper is disclosed. The copper plating composition comprises at least one polymer phenazonium compound and .beta.-naphtholalkoxylate. A method for using such a bath for deposition of copper coatings is also disclosed. The resultant copper coatings are smooth and bright with substantially no fine roughness or pitting.
    Type: Grant
    Filed: October 4, 1996
    Date of Patent: December 15, 1998
    Assignee: Atotech Deutschland GmbH
    Inventors: Wolfgang Dahms, Horst Westphal
  • Patent number: 5834140
    Abstract: The present invention is an electrodeposited copper foil characterised in that roughening treatment is performed on a matte side of an untreated copper foil wherein the surface roughness R.sub.z of the matte side of the untreated copper foil is the same as or less than the surface roughness R.sub.z of the shiny side of this untreated copper foil. The electrodeposited copper foil is made by electrodepositing copper onto a drum from an electrolyte which contains 0.05 to 5 ppm 3-mercapto 1-propanesulfonate; at least one organic compound selected from 0.1 to 15 ppm of a polysaccharide which is a carbohydrate such as starches, celluloses and vegetable rubbers, and 0.3 to 35 ppm of a low molecular weight glue having a weight average molecular weight of 10,000 or less; and 10 to 60 ppm of a chloride ion. The copper foil may be used in making a printed circuit board or as a component of a secondary battery cell.
    Type: Grant
    Filed: September 18, 1996
    Date of Patent: November 10, 1998
    Assignee: Circuit Foil Japan Co., Ltd.
    Inventors: Adam M. Wolski, Michel Streel, Akitoshi Suzuki, Hideo Otsuka
  • Patent number: 5730854
    Abstract: A copper electroplating process using alkoxylated dimercaptan ethers as an additive. The additives prevent dendritic formations which short out electrodes. Also provided is a method for polarizing the electrodes, allowing for current reduction and cost savings.
    Type: Grant
    Filed: May 30, 1996
    Date of Patent: March 24, 1998
    Assignee: Enthone-OMI, Inc.
    Inventor: Sylvia Martin
  • Patent number: 5543522
    Abstract: There are disclosed a process for preparing an ambient temperature molten salt, which comprises treating an ambient temperature molten salt consisting essentially of 20 to 50 mole % of an aluminum halide and 80 to 50 mole % of an onium halide, containing oxygen-containing impurities originating from water with thionyl chloride anda process for preparing an ambient temperature molten salt for effecting aluminum electroplating, which comprises treating mixed ambient temperature molten salts consisting essentially of 30 to 50 mole % of an aluminum halide and 70 to 50 mole % of an onium halide, containing oxygen-containing impurities originating from water with thionyl chloride, and then adding aluminum halide to the molten salt to prepare an ambient temperature molten salt composition consisting essentially of 50 to 80 mole % of an aluminum halide and 50 to 20 mole % of an onium halide.
    Type: Grant
    Filed: August 25, 1994
    Date of Patent: August 6, 1996
    Assignees: Mitsubishi Chemical Corporation, Nisshin Steel Co., Ltd.
    Inventors: Takayuki Kawahara, Hitoshi Suzuki, Asao Kominato
  • Patent number: RE35513
    Abstract: A solution for use in electroplating which comprises at least one monovalent metal such as copper, silver or gold which is complexed by a thiosulfate ion; and a stabilizer of an organic sulfinate compound such as, for example, one having the formula R-SO.sub.2 -X wherein R is an alkyl, heterocyclic or aryl moiety and X is a monovalent cation. The stabilizer is present in an amount sufficient to stabilize the thiosulfate ion when the solution is operated at an acidic pH of less than 7. Also, the solution is substantially free of cyanide.
    Type: Grant
    Filed: April 10, 1996
    Date of Patent: May 20, 1997
    Assignee: Learonal, Inc.
    Inventors: Fred I. Nobel, William R. Brasch, Anthony J. Drago