|Publication number||US3328273 A|
|Publication date||Jun 27, 1967|
|Filing date||Aug 15, 1966|
|Priority date||Aug 15, 1966|
|Publication number||US 3328273 A, US 3328273A, US-A-3328273, US3328273 A, US3328273A|
|Inventors||Hans-Gerhard Crentz, Romanowski Edward A, Stevenson Richard M|
|Original Assignee||Udylite Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (9), Referenced by (164), Classifications (5), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,328,273 ELECTRO-DEPOSHTKQN OF COPPER FRUM ACHDHC BATH Hans-Gerhard Creutz, Wayne, Richard M. Stevenson,
Grosse Pointe Woods, and Edward A. Romanowski,
Troy, Mich, assignors to The Udylite Corporation,
Warren, Mich, a corporation of Delaware No Drawing. Filed Aug. 15, 1966, Ser. No. 572,201
Claims. (Cl. 204--52) This application is a continuation-in-part of our c0- pending application, Ser. No. 187,926 filed Apr. 16, 1962 which is now U.S. Patent No. 3,267,010.
This invention relates to the electrodeposition of copper from aqueous acidic baths, especially from copper sulfate and fiuoborate baths. More particularly it relates to the combined use of certain organic compounds in such baths to make possible bright, highly ductile, low stress, good leveling copper deposits.
While a rather large number of organic compounds have been previously proposed and used to decrease the grain size and increase the luster of copper deposits from acidic baths, nevertheless, much remains to be desired from the standpoint of obtaining lustrous leveling copper plate without striations and ribbing and without substantially decreasing the very high ductility of the copper plate.
In our copending application Ser. No. 187,926, we have described certain organic sulfide compounds containing at least one sulfonic group which when used in combination with certain bath soluble polyether compounds produce bright, ductile copper electrodeposits. The baths described therein have excellent brightness and ductility and are operable over a fairly wide current density range. While these baths have been adequate to meet the requirements of most commercial applications, very complex parts require that a plating bath have an extremely wide current range. Thus, there have been instances wherein the current density of the above described baths has not been sufficient to satisfactorily plate some extremely complicated articles and the plate has proved to be inadequate in the deeply recessed areas.
Another limitation with the baths described in our copending application is that the concentration of the sulfide component therein should be kept below about 0.04 gram per liter. At concentrations much above this level, there is a tendency to form harmful breakdown deposits on extended electrolysis which results in a reduced brightness, especially in the low current density areas.
An object of this invention is to provide copper plating baths from which are obtained bright, ductile copper deposits free of striations and ribbing. Another object is to provide plating baths from which such copper deposits are obtained over a wide current density range.
We have discovered that certain specific baths of the general type described in our aforementioned pending application uniquely have several outstanding and unexpected properties. These baths, to be fully described below, have a markedly wider current density plating range, i.e., produce a bright deposit in the extremely deeply recessed areas, as well as allowing the plating to be carried out at higher current densities. Thus not only are the most complicated articles fully plated, but since the plating can be carried out at higher current densities, the actual plating time is significantly reduced. Moreover, the sulfide compound used is of such a stable nature that up to 1.0 gram per liter and above can be used without formation of harmful breakdown products. In other words, the concentration of the specific sulfide component of this invention is not critical as is the case with sulfide compounds in general.
The plating baths of this invention comprise aqueous acidic copper plating baths containing dissolved therein 3,328,273 Patented June 27, 1967 a bath-soluble polyether compound containing at least 6 ether oxygen atoms and being free from alkyl chains having more than 6 carbon atoms together with from about 0.0005 to about 1.0 gram per liter of an organic polysulfide compound of the formula wherein R and R are the same or different and are alkylene groups containing 1-6 carbon atoms, X is hydrogen or SO H, and n is an integer of 2-5 inclusive.
The sulfide compounds of the invention are aliphatic polysulfides wherein at least two divalent sulfur atoms are vicinal, and wherein the molecule has one or two terminal sulfonic acid groups. The alkylene portion of the molecule may be substituted with groups such as methyl, ethyl, chloro, bromo, ethoxy, hydroxy etc., but preferably R and R are unsubstituted polymethylene groups containing 3 carbon atoms. The various sulfonic compounds may be added to the plating baths as the free acid or the alkali metal salts or the organic amine salts etc. Generally, it is preferred to use the free acids. Ex amples of some of the preferred polysulfide compounds of the invention are shown in Table I.
TABLE I.ORGANIC POLYSULFIDE COMPOUNDS The sulfide compounds of the invention are known compounds and may be prepared by any of several well known techniques. For example, compound 4 in the above table may be prepared by reaction of sodium sulfide with propane sultone at about F. to obtain mercaptopropane sulfonic acid, which is then oxidized With H 0 to obtain the disulfide.
The organic sulfide compounds illustrated in Table I when used alone in copper plating baths do not produce adequate brightness. However, when used in combination with from about 0.01 to 5 grams per liter of the hereinafter described bath soluble polyether compounds, full bright, ductile deposits are obtained over an extremely wide current density range. The bath can be operated at a higher current density than is possible using seemingly similar sulfides which are not polysulfides of this invention. Moreover, if the same amount of polyether were used by itself, a somewhat dull irregular deposit is obtained.
A second outstanding benefit of the baths of this invention is that the aliphatic polysulfides can be used at concentrations of more than 1 gram per liter without the formation of harmful breakdown deposits which otherwise tend to reduce brightness, especially in the low current density area. When using other sulfide compounds not of the invention, their concentration must be quite limited in order to avoid the formation of detrimental breakdown products.
It has been found that the organic polysulfide compounds of Table I when used in concentrations of 0.0005 to about 1.0 gram/liter, prevent the harmful striations and ribbing effects that polyethers such as polyethylene ethanols and glycols cause in the absence of at least 0.02 to 0.1 gram/ liter of chloride or bromide ion. By the use of the addition agents of the invention not only are the striations and ribbing effects eliminated without the need of chloride or bromide ions, but a very bright deposit is obtained. This is an unexpected result because with either material used alone in the bath, there is no indication of the remarkable enhancement of brightness which occurs when the two materials are used together. It will be appreciated that the elimination of the ribbing or striations effects is, in itself, an unexpected and important result, and this result is obtained with all of the compounds of Table I, though the matter of obtaining the highest brightness, not all of the compounds of Table I are equally effective.
The polyethers which are useful for the purposes of this invention, include polyether compounds containing at least 6 ether oxygen atoms and which are free from alkyl chains having more than 6 carbon atoms. It has been found that compounds containing alkyl chains of more than 6 carbon atoms tend to overfoam with air agitation.
In Table II are listed representative examples of the bath soluble polyether derivatives which can be used in combination with the compounds of Table I to give bright, ductile copper plate. The preferred compounds of Table II, from the standpoint of best cooperation with the compounds of Table I, to give smooth, striation-free, bright, ductile copper are the polypropylene propanols and glycols of average molecular weight of about 360 to about 1,000, i.e., polyethers which contain the group (C H O) where y is an integer of from 6 to about 20. Outstanding results are also obtained with polyethers containing the group (C H O) where x is an integer of at least 6.
It was further found that if low concentrations (0.001
to 0.05 gram/liter) of phenazine dye such as Janus Green B (see US. Patent 2,707,166) are used in conjunction with both of the above described additives of Table I and II, brightness and leveling is further improved and brilliant, high leveling, ductile copper plate is obtained over a still wider plating range. This type of brilliance and extremely wide bright plate range is not obtained when the Janus Green B is used just with the onganic sulfide compounds carrying sulfonic groups (the compounds of TableI), or when used just with the compounds of Table II. Also, the brilliance and ductility far exceed that obtained with Janus Green B type dyes used together with thiourea or such thiourea derivatives or acetyl or propionyl thioureas. (US. Patent 2,738,318, Mar. 13, 1956.)
The dyes of the phenazine class (the Safranine type) and more especially the phenazine azo dyes (the Janus Green B type) which make possible the greatly improved leveling and extended bright plating range can be represented by the following formula.
R is H, CH or C H D is H, CH C H OH, NH N(CH N(C H 80002115, SH, and N=NZ where Z:a coupling group, such as dimethyl aniline, aniline, phenylene diamine, and substituted anilines and phenylene diamines, naphthols and substituted naphthols, phenols and substituted phenols, thiazoles, benzothiazoles and aminobenzothiazoles, coupled to the azo linkage The preferred phenazine dyes are the Janus Green B type (Diethyl Safranine .Azo Dimethyl Aniline or Dimethyl Safranine Azo Dimethyl Aniline, C. 1. Nos. 11045, 11050), or the Janus Black R type, also C. I. 11975 (Colour Index, second edition, vol. 3, 1956-57), as these compounds make possible the highest leveling and the widest bright plate range.
The inorganic composition of the acid copper plating baths such as the acidic sulfate or acidic fluoborate may vary over rather wide limits. However, when very low acid contents are used, higher tank voltages are needed. In the examples listed below as illustrations of lustrous copper plating baths, the standard types of acidic copper sulfate and fluoborate baths are used for the inorganic composition. However, other acidic copper plating baths such as copper sulfonate, copper methane sulfonates, copper ethane sulfonates, copper propane sulfonates with excess acidity supplied by the free sulfonic acids, can be used with the combinations of additives of this invention to give highly lustrous plate.
Many inorganic cations which do not plate out from the normal acidic copper plating baths, may be present in concentrations as high as at least 25 grams/ liter without detrimental effects, for example, ferrous nickel, cobalt,
zinc and cadium cations. Chloride and/ or bromide anions should in general be kept below about 0.1 gram/ liter, and preferably at about 0.02 gram/liter. Air agitation or cathode-rod agitation, or solution agitation and cathode-rod agitation is desirable for highest speed plating and optimum results. The best bath temperatures are 25-30 C., though lower or higher (even up to 50 C. in some cases) temperatures can be used.
With the use of the combination of additives from Tables I and II and the combinations with the phenazine dyes, especially the Janus Green B types, it is preferred not to use surfaceactive agents, even though such anionic types as sodium octyl sulfate, sulfonated non-ionic types such as Triton 720 (U.S. Patent 2,489,538, Nov. 29, 1949), and similar materials, or polyoxy non-ionic wetting agents, have often been previously used in acidic copper plating baths with good results, they are not needed in the present type baths.
Below are some examples of a number of acid copper plating baths producing highly ductile, lustrous copper deposits over a wide current density range.
Example A Concentration grams/liter CuS0 .5I-I O 150-250 H 50 30-75 1,3-dioxolane polymer av. mol. wt. 5,000 0.05-0.15 (CH )-(CH SS(CH SO H 0.001-0.01
Temp. 20-50 C. Av. cathode current density 15 amps/sq. dm.
Example B CuBR, 150-225 HBF 10-30 H BO 0-30 1,3-dioxolane polymer av. mol. wt. 5,000 0.1-0.3 HO S(CH ).;S-S-S(CH SO H 0.001-0.02
Janus Green B 0.001-0.02 Temp. 20-50 C. Av. cathode current density, 15 amps./ sq. dm.
Example C CuSO .5H O 150-250 H 30-75 Polypropylene glycol, av. mol. wt. 350-750 0.05-0.2
HO S(CH SS(CH -SO H 0.001-002 Dimethyl Safranine azo dimethyl aniline 0.001-0.01 Temp. 20-50 C.
Av. cathode current density, 20 amps/sq. dm.
5 The addition agents of Tables I and II can be combined in the same molecule or combined with one the phenazine dyes, or they may be used as individual molecules as listed in Tables I and II mixed together in the same solution with or without the phenazine dyes because they 5 all deplete from the solution at very nearly the same rate. The compounds of Table I used in the very low concentrations of 0.0005 to about 0.025 .gram/ liter deplete practically exactly at the same rate as the phenaz-ine dyes used in the concentration range of 0.001 to 0.05 gram/liter.
TABLE II.POLY-ETHERS (Concentration range 0.01 to 5 grams/liter. The lower concentration for the higher molecular weight species) H c OBB-02114 2134) xoH z=5100 N SOaH l 0 a u(0CaHu);OH 1:4-10
r l 18 HO osnao CaHr-NOSO- What is claimed is:
1. A bath for electrodepositing ductile, lustrous copper comprising an aqueous acidic copper plating bath containing dissolved therein from about 0.01 to 5 grams per liter of a bath-soluble polyether compound containing at least 6 ether oxygen atoms and being free from alkyl chains having more than -6 carbon atoms together with from about 0.0005 to about 1.0 gram per liter of an organic sulfide compound of the formula:
wherein R and R are the same or different and are alkylene groups containing 1-6 carbon atoms, X is hydrogen or SO H, and n is an integer of 2-5 inclusive.
2. A bath as in claim 1 wherein R and R are polymethylene groups and X is SO H.
3. A bath as in claim 2 wherein said polyether contains the group (C H wherein y is an integer equal to from about 6 to 20.
4. A bath as in claim 1 wherein said organic sulfide is H0 S(C H S1S-'(CH SO H.
5. A bath as in claim 4 additionally containing a bath soluble phenazine dye.
6. A method for electrodepositing ductile, lustrous copper comprising the step of electrodepositing copper from an aqueous acid copper plating bath containing dissolved there-in from about 0.01 to 5 grams per liter of a bathsoluble polyether compound containing at least 6 ether oxygen atoms and being free from alkyl chains having more than 6 carbon atoms together with from about 0.0005 to about 1.0 gram perliter of an organic sulfide compound of the formula:
XR (S) R -SO H wherein R and R are the same or different and are alkylene groups containing 1-6 carbon atoms, X ishydrogen or SO H and n is an integer of 2-5 inclusive.
7. A method as claimed in claim 6, wherein R and R are polymethylene groups and X is -SO H.
8. A method as claimed in claim 7 wherein said polyether contains the group (C;,H O) wherein y is an inte-.
ger equal to about 6 to 20.
9. A method as claimed in claim 6 wherein said organic sulfide is HO S(CH S--S(CH -SO H. 10. A method as claimed in claim 9 wherein said bath additionally contains a soluble phenazine dye.
References Cited UNITED STATES PATENTS JOHN H. MACK, Primary Examiner. G. KAPLAN, Assistant Examiner.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2424887 *||Oct 11, 1941||Jul 29, 1947||Houdaille Hershey Corp||Method and electrolyte for the electrodeposition of metals|
|US2707166 *||May 26, 1952||Apr 26, 1955||Udylite Corp||Electrodeposition of copper from an acid bath|
|US2707167 *||May 26, 1952||Apr 26, 1955||Udylite Corp||Electrodeposition of copper from an acid bath|
|US2738318 *||Dec 28, 1954||Mar 13, 1956||Udylite Res Corp||Electrodeposition of copper from an acid bath|
|US2805193 *||Jul 18, 1955||Sep 3, 1957||Beaver John F||Bright copper plating|
|US2805194 *||Jul 18, 1955||Sep 3, 1957||Dayton Bright Copper Company||Bright copper plating|
|US2882209 *||May 20, 1957||Apr 14, 1959||Udylite Res Corp||Electrodeposition of copper from an acid bath|
|US2931760 *||Sep 25, 1957||Apr 5, 1960||Westbrook Leon R||Acid copper plating|
|US3081240 *||May 31, 1960||Mar 12, 1963||Debydag Deutsche Hydrierwerke||Acid copper electroplating baths|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3542655 *||Apr 29, 1968||Nov 24, 1970||M & T Chemicals Inc||Electrodeposition of copper|
|US3715289 *||Feb 8, 1971||Feb 6, 1973||Stauffer Chemical Co||Brightener composition for acid copper electroplating baths|
|US3725220 *||Apr 27, 1972||Apr 3, 1973||Lea Ronal Inc||Electrodeposition of copper from acidic baths|
|US3743584 *||Jun 2, 1971||Jul 3, 1973||Schering Ag||Acid bright copper plating bath|
|US3770598 *||Jan 21, 1972||Nov 6, 1973||Oxy Metal Finishing Corp||Electrodeposition of copper from acid baths|
|US3940320 *||Nov 21, 1974||Feb 24, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US3956078 *||Nov 21, 1974||May 11, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US3956079 *||Nov 21, 1974||May 11, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US3956084 *||Nov 21, 1974||May 11, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US3956120 *||Nov 21, 1974||May 11, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US3966565 *||Nov 21, 1974||Jun 29, 1976||M & T Chemicals Inc.||Electrodeposition of copper|
|US4009087 *||Dec 24, 1975||Feb 22, 1977||M&T Chemicals Inc.||Electrodeposition of copper|
|US4014760 *||Feb 17, 1976||Mar 29, 1977||M & T Chemicals Inc.||Electrodeposition of copper|
|US4036710 *||Dec 24, 1975||Jul 19, 1977||M & T Chemicals Inc.||Electrodeposition of copper|
|US4036711 *||Sep 17, 1976||Jul 19, 1977||M & T Chemicals Inc.||Electrodeposition of copper|
|US4334966 *||May 19, 1981||Jun 15, 1982||Mcgean Chemical Company, Inc.||Method of copper plating gravure cylinders|
|US4336114 *||Mar 26, 1981||Jun 22, 1982||Hooker Chemicals & Plastics Corp.||Electrodeposition of bright copper|
|US4374709 *||May 1, 1980||Feb 22, 1983||Occidental Chemical Corporation||Process for plating polymeric substrates|
|US4376685 *||Jun 24, 1981||Mar 15, 1983||M&T Chemicals Inc.||Acid copper electroplating baths containing brightening and leveling additives|
|US4469564 *||Aug 11, 1982||Sep 4, 1984||At&T Bell Laboratories||Copper electroplating process|
|US4540473 *||Nov 22, 1983||Sep 10, 1985||International Business Machines Corporation||Copper plating bath having increased plating rate, and method|
|US4673469 *||Jul 17, 1985||Jun 16, 1987||Mcgean-Rohco, Inc.||Method of plating plastics|
|US4786746 *||Sep 18, 1987||Nov 22, 1988||Pennsylvania Research Corporation||Copper electroplating solutions and methods of making and using them|
|US4897165 *||Aug 23, 1988||Jan 30, 1990||Shipley Company Inc.||Electroplating composition and process for plating through holes in printed circuit boards|
|US4948474 *||Aug 28, 1989||Aug 14, 1990||Pennsylvania Research Corporation||Copper electroplating solutions and methods|
|US5004525 *||Nov 20, 1989||Apr 2, 1991||Shipley Company Inc.||Copper electroplating composition|
|US5024736 *||May 24, 1989||Jun 18, 1991||Raschig Ag||Process for electroplating utilizing disubstituted ethane sulfonic compounds as electroplating auxiliaries and electroplating auxiliaries containing same|
|US5068013 *||Jan 29, 1990||Nov 26, 1991||Shipley Company Inc.||Electroplating composition and process|
|US5252196 *||Dec 5, 1991||Oct 12, 1993||Shipley Company Inc.||Copper electroplating solutions and processes|
|US5328589 *||Dec 23, 1992||Jul 12, 1994||Enthone-Omi, Inc.||Functional fluid additives for acid copper electroplating baths|
|US5417841 *||Oct 25, 1994||May 23, 1995||Mcgean-Rohco, Inc.||Copper plating of gravure rolls|
|US5730854 *||May 30, 1996||Mar 24, 1998||Enthone-Omi, Inc.||Alkoxylated dimercaptans as copper additives and de-polarizing additives|
|US5985126 *||Sep 30, 1997||Nov 16, 1999||Semitool, Inc.||Semiconductor plating system workpiece support having workpiece engaging electrodes with distal contact part and dielectric cover|
|US6354916||Apr 6, 2000||Mar 12, 2002||Nu Tool Inc.||Modified plating solution for plating and planarization and process utilizing same|
|US6358388 *||Nov 16, 1999||Mar 19, 2002||Semitool, Inc.||Plating system workpiece support having workpiece-engaging electrodes with distal contact-part and dielectric cover|
|US6413388||Feb 23, 2000||Jul 2, 2002||Nutool Inc.||Pad designs and structures for a versatile materials processing apparatus|
|US6413403||Jul 21, 2000||Jul 2, 2002||Nutool Inc.||Method and apparatus employing pad designs and structures with improved fluid distribution|
|US6454926||Sep 30, 1997||Sep 24, 2002||Semitool Inc.||Semiconductor plating system workpiece support having workpiece-engaging electrode with submerged conductive current transfer areas|
|US6478936||May 11, 2000||Nov 12, 2002||Nutool Inc.||Anode assembly for plating and planarizing a conductive layer|
|US6497800||Oct 11, 2000||Dec 24, 2002||Nutool Inc.||Device providing electrical contact to the surface of a semiconductor workpiece during metal plating|
|US6565729||Dec 7, 2000||May 20, 2003||Semitool, Inc.||Method for electrochemically depositing metal on a semiconductor workpiece|
|US6610190||Jan 17, 2001||Aug 26, 2003||Nutool, Inc.||Method and apparatus for electrodeposition of uniform film with minimal edge exclusion on substrate|
|US6612915||Dec 27, 1999||Sep 2, 2003||Nutool Inc.||Work piece carrier head for plating and polishing|
|US6632345||Oct 23, 2000||Oct 14, 2003||Semitool, Inc.||Apparatus and method for electrolytically depositing a metal on a workpiece|
|US6638410||Nov 22, 2002||Oct 28, 2003||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US6638411 *||Jan 27, 2000||Oct 28, 2003||Ebara Corporation||Method and apparatus for plating substrate with copper|
|US6663762||Mar 19, 2002||Dec 16, 2003||Semitool, Inc.||Plating system workpiece support having workpiece engaging electrode|
|US6695962||May 1, 2001||Feb 24, 2004||Nutool Inc.||Anode designs for planar metal deposits with enhanced electrolyte solution blending and process of supplying electrolyte solution using such designs|
|US6709562||Jul 6, 1999||Mar 23, 2004||International Business Machines Corporation||Method of making electroplated interconnection structures on integrated circuit chips|
|US6736954||Oct 2, 2001||May 18, 2004||Shipley Company, L.L.C.||Plating bath and method for depositing a metal layer on a substrate|
|US6773576||Sep 20, 2002||Aug 10, 2004||Nutool, Inc.||Anode assembly for plating and planarizing a conductive layer|
|US6776892||Mar 14, 2000||Aug 17, 2004||Semitool, Inc.||Semiconductor plating system workpiece support having workpiece engaging electrode with pre-conditioned contact face|
|US6802946||May 15, 2001||Oct 12, 2004||Nutool Inc.||Apparatus for controlling thickness uniformity of electroplated and electroetched layers|
|US6806186||Mar 23, 2001||Oct 19, 2004||Semitool, Inc.||Submicron metallization using electrochemical deposition|
|US6811675||Jun 20, 2001||Nov 2, 2004||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US6863795 *||Mar 21, 2002||Mar 8, 2005||Interuniversitair Microelektronica Centrum (Imec)||Multi-step method for metal deposition|
|US6866763||Apr 30, 2003||Mar 15, 2005||Asm Nutool. Inc.||Method and system monitoring and controlling film thickness profile during plating and electroetching|
|US6919013||Feb 3, 2003||Jul 19, 2005||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a workpiece|
|US6932892||Oct 27, 2003||Aug 23, 2005||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US6936153||Sep 30, 1997||Aug 30, 2005||Semitool, Inc.||Semiconductor plating system workpiece support having workpiece-engaging electrode with pre-conditioned contact face|
|US6942780||Jun 11, 2003||Sep 13, 2005||Asm Nutool, Inc.||Method and apparatus for processing a substrate with minimal edge exclusion|
|US6946716||Feb 9, 2004||Sep 20, 2005||International Business Machines Corporation||Electroplated interconnection structures on integrated circuit chips|
|US6974769||Sep 16, 2003||Dec 13, 2005||Asm Nutool, Inc.||Conductive structure fabrication process using novel layered structure and conductive structure fabricated thereby for use in multi-level metallization|
|US7025866||Aug 21, 2002||Apr 11, 2006||Micron Technology, Inc.||Microelectronic workpiece for electrochemical deposition processing and methods of manufacturing and using such microelectronic workpieces|
|US7074246||May 28, 2002||Jul 11, 2006||Semitool, Inc.||Modular semiconductor workpiece processing tool|
|US7115196||Feb 27, 2003||Oct 3, 2006||Semitool, Inc.||Apparatus and method for electrochemically depositing metal on a semiconductor workpiece|
|US7128822||Jun 4, 2003||Oct 31, 2006||Shipley Company, L.L.C.||Leveler compounds|
|US7141146||Mar 31, 2004||Nov 28, 2006||Asm Nutool, Inc.||Means to improve center to edge uniformity of electrochemical mechanical processing of workpiece surface|
|US7144805||Jul 1, 2004||Dec 5, 2006||Semitool, Inc.||Method of submicron metallization using electrochemical deposition of recesses including a first deposition at a first current density and a second deposition at an increased current density|
|US7195696||Nov 26, 2003||Mar 27, 2007||Novellus Systems, Inc.||Electrode assembly for electrochemical processing of workpiece|
|US7204924||Dec 22, 2003||Apr 17, 2007||Novellus Systems, Inc.||Method and apparatus to deposit layers with uniform properties|
|US7264698||May 31, 2001||Sep 4, 2007||Semitool, Inc.||Apparatus and methods for electrochemical processing of microelectronic workpieces|
|US7282124||Jun 10, 2003||Oct 16, 2007||Novellus Systems, Inc.||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US7309413||Jun 10, 2003||Dec 18, 2007||Novellus Systems, Inc.||Providing electrical contact to the surface of a semiconductor workpiece during processing|
|US7311811||Apr 16, 2004||Dec 25, 2007||Novellus Systems, Inc.||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US7329335||Jun 10, 2003||Feb 12, 2008||Novellus Systems, Inc.||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US7332066||Feb 7, 2005||Feb 19, 2008||Semitool, Inc.||Apparatus and method for electrochemically depositing metal on a semiconductor workpiece|
|US7338585 *||May 17, 2006||Mar 4, 2008||Intel Corporation||Electroplating chemistries and methods of forming interconnections|
|US7378004||May 23, 2002||May 27, 2008||Novellus Systems, Inc.||Pad designs and structures for a versatile materials processing apparatus|
|US7425250||Apr 23, 2004||Sep 16, 2008||Novellus Systems, Inc.||Electrochemical mechanical processing apparatus|
|US7427337||Apr 12, 2004||Sep 23, 2008||Novellus Systems, Inc.||System for electropolishing and electrochemical mechanical polishing|
|US7435323||Jun 18, 2004||Oct 14, 2008||Novellus Systems, Inc.||Method for controlling thickness uniformity of electroplated layers|
|US7438788||Mar 29, 2005||Oct 21, 2008||Semitool, Inc.||Apparatus and methods for electrochemical processing of microelectronic workpieces|
|US7476304||Sep 21, 2004||Jan 13, 2009||Novellus Systems, Inc.||Apparatus for processing surface of workpiece with small electrodes and surface contacts|
|US7491308||May 5, 2005||Feb 17, 2009||Novellus Systems, Inc.||Method of making rolling electrical contact to wafer front surface|
|US7578923||Mar 18, 2003||Aug 25, 2009||Novellus Systems, Inc.||Electropolishing system and process|
|US7648622||Jul 1, 2005||Jan 19, 2010||Novellus Systems, Inc.||System and method for electrochemical mechanical polishing|
|US7754061||Sep 6, 2005||Jul 13, 2010||Novellus Systems, Inc.||Method for controlling conductor deposition on predetermined portions of a wafer|
|US7947163||Aug 6, 2007||May 24, 2011||Novellus Systems, Inc.||Photoresist-free metal deposition|
|US8236160||May 24, 2010||Aug 7, 2012||Novellus Systems, Inc.||Plating methods for low aspect ratio cavities|
|US8500985||Jul 13, 2007||Aug 6, 2013||Novellus Systems, Inc.||Photoresist-free metal deposition|
|US20020061715 *||Jan 11, 2002||May 23, 2002||Nu Tool Inc.||Modified plating solution for plating and planarization and process utilizing same|
|US20020175080 *||Mar 21, 2002||Nov 28, 2002||Ivo Teerlinck||Multi-step method for metal deposition|
|US20020194716 *||May 28, 2002||Dec 26, 2002||Berner Robert W.||Modular semiconductor workpiece processing tool|
|US20030015435 *||Sep 20, 2002||Jan 23, 2003||Rimma Volodarsky||Anode assembly for plating and planarizing a conductive layer|
|US20030029732 *||Jun 10, 2002||Feb 13, 2003||Ritzdorf Thomas L.||Semiconductor plating system workpiece support having workpiece-engaging electrode with submerged conductive current transfer areas|
|US20030070930 *||Nov 22, 2002||Apr 17, 2003||Homayoun Talieh||Device providing electrical contact to the surface of a semiconductor workpiece during metal plating and method of providing such contact|
|US20030141194 *||Feb 3, 2003||Jul 31, 2003||Chen Linlin||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US20030209425 *||Jun 10, 2003||Nov 13, 2003||Homayoun Talieh||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US20030209429 *||Jun 11, 2003||Nov 13, 2003||Basol Bulent M.||Method and apparatus for processing a substrate with minimal edge exclusion|
|US20030209445 *||Jun 10, 2003||Nov 13, 2003||Homayoun Talieh||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US20030217932 *||Jun 10, 2003||Nov 27, 2003||Homayoun Talieh||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US20030230491 *||Apr 30, 2003||Dec 18, 2003||Basol Bulent M.||Method and system monitoring and controlling film thickness profile during plating and electroetching|
|US20040007478 *||Mar 18, 2003||Jan 15, 2004||Basol Bulent M.||Electroetching system and process|
|US20040035708 *||Apr 17, 2003||Feb 26, 2004||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US20040035710 *||May 28, 2003||Feb 26, 2004||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US20040038052 *||Aug 21, 2002||Feb 26, 2004||Collins Dale W.||Microelectronic workpiece for electrochemical deposition processing and methods of manufacturing and using such microelectronic workpieces|
|US20040040857 *||May 31, 2003||Mar 4, 2004||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US20040050711 *||Sep 12, 2003||Mar 18, 2004||Koji Mishima||Method and apparatus for plating substrate with copper|
|US20040052930 *||Sep 16, 2003||Mar 18, 2004||Bulent Basol||Conductive structure fabrication process using novel layered structure and conductive structure fabricated thereby for use in multi-level metallization|
|US20040074775 *||Oct 21, 2002||Apr 22, 2004||Herdman Roderick Dennis||Pulse reverse electrolysis of acidic copper electroplating solutions|
|US20040092065 *||Oct 27, 2003||May 13, 2004||Semitool, Inc.||Apparatus and method for electrolytically depositing copper on a semiconductor workpiece|
|US20040104124 *||Nov 24, 2003||Jun 3, 2004||Shipley Company, L.L.C.||Plating bath and method for depositing a metal layer on a substrate|
|US20040108136 *||Dec 4, 2002||Jun 10, 2004||International Business Machines Corporation||Structure comprising a barrier layer of a tungsten alloy comprising cobalt and/or nickel|
|US20040168926 *||Dec 22, 2003||Sep 2, 2004||Basol Bulent M.||Method and apparatus to deposit layers with uniform properties|
|US20040187731 *||Apr 14, 2004||Sep 30, 2004||Wang Qing Min||Acid copper electroplating solutions|
|US20040195111 *||Apr 16, 2004||Oct 7, 2004||Homayoun Talieh||Device providing electrical contact to the surface of a semiconductor workpiece during processing|
|US20040211657 *||Apr 11, 2003||Oct 28, 2004||Ingelbrecht Hugo Gerard Eduard||Method of purifying 2,6-xylenol and method of producing poly(arylene ether) therefrom|
|US20040229456 *||Feb 9, 2004||Nov 18, 2004||International Business Machines||Electroplated interconnection structures on integrated circuit chips|
|US20040249177 *||Jun 4, 2003||Dec 9, 2004||Shipley Company, L.L.C.||Leveler compounds|
|US20040266193 *||Mar 31, 2004||Dec 30, 2004||Jeffrey Bogart||Means to improve center-to edge uniformity of electrochemical mechanical processing of workpiece surface|
|US20050006244 *||Nov 26, 2003||Jan 13, 2005||Uzoh Cyprian E.||Electrode assembly for electrochemical processing of workpiece|
|US20050016868 *||Apr 23, 2004||Jan 27, 2005||Asm Nutool, Inc.||Electrochemical mechanical planarization process and apparatus|
|US20050040049 *||Aug 10, 2004||Feb 24, 2005||Rimma Volodarsky||Anode assembly for plating and planarizing a conductive layer|
|US20050061675 *||Nov 18, 2003||Mar 24, 2005||Bleck Martin C.||Semiconductor plating system workpiece support having workpiece-engaging electrodes with distal contact part and dielectric cover|
|US20050092611 *||Nov 3, 2003||May 5, 2005||Semitool, Inc.||Bath and method for high rate copper deposition|
|US20050133379 *||Apr 12, 2004||Jun 23, 2005||Basol Bulent M.||System for electropolishing and electrochemical mechanical polishing|
|US20050269212 *||May 5, 2005||Dec 8, 2005||Homayoun Talieh||Method of making rolling electrical contact to wafer front surface|
|US20060006060 *||Sep 13, 2005||Jan 12, 2006||Basol Bulent M||Method and apparatus for processing a substrate with minimal edge exclusion|
|US20060006073 *||Jul 1, 2005||Jan 12, 2006||Basol Bulent M||System and method for electrochemical mechanical polishing|
|US20060017169 *||Jun 29, 2005||Jan 26, 2006||International Business Machines Corporation||Electroplated interconnection structures on integrated circuit chips|
|US20060070885 *||Dec 6, 2005||Apr 6, 2006||Uzoh Cyprian E||Chip interconnect and packaging deposition methods and structures|
|US20060118425 *||Jan 30, 2006||Jun 8, 2006||Basol Bulent M||Process to minimize and/or eliminate conductive material coating over the top surface of a patterned substrate|
|US20060131177 *||Nov 18, 2005||Jun 22, 2006||Jeffrey Bogart||Means to eliminate bubble entrapment during electrochemical processing of workpiece surface|
|US20060144714 *||Feb 24, 2006||Jul 6, 2006||Akihisa Hongo||Substrate plating method and apparatus|
|US20060182879 *||Feb 6, 2006||Aug 17, 2006||Collins Dale W||Microelectronic workpiece for electrochemical deposition processing and methods of manufacturing and using such microelectronic workpieces|
|US20060208272 *||May 23, 2006||Sep 21, 2006||Semitool, Inc.||Method for filling recessed micro-structures with metallization in the production of a microelectronic device|
|US20070051635 *||Sep 6, 2005||Mar 8, 2007||Basol Bulent M||Plating apparatus and method for controlling conductor deposition on predetermined portions of a wafer|
|US20070131563 *||Nov 28, 2006||Jun 14, 2007||Asm Nutool, Inc.||Means to improve center to edge uniformity of electrochemical mechanical processing of workpiece surface|
|US20070267297 *||May 17, 2006||Nov 22, 2007||Akolkar Rohan N||Electroplating Chemistries and Methods of Forming Interconnections|
|US20080099344 *||Mar 18, 2003||May 1, 2008||Basol Bulent M||Electropolishing system and process|
|US20080237048 *||Mar 30, 2007||Oct 2, 2008||Ismail Emesh||Method and apparatus for selective electrofilling of through-wafer vias|
|US20080237053 *||May 27, 2008||Oct 2, 2008||International Business Machines Corporation||Structure comprising a barrier layer of a tungsten alloy comprising cobalt and/or nickel|
|US20090020437 *||Jul 29, 2004||Jan 22, 2009||Basol Bulent M||Method and system for controlled material removal by electrochemical polishing|
|US20090065365 *||Sep 11, 2007||Mar 12, 2009||Asm Nutool, Inc.||Method and apparatus for copper electroplating|
|US20090277801 *||Aug 6, 2007||Nov 12, 2009||Novellus Systems, Inc.||Photoresist-free metal deposition|
|US20090280243 *||Nov 12, 2009||Novellus Systems, Inc.||Photoresist-free metal deposition|
|US20100224501 *||Sep 9, 2010||Novellus Systems, Inc.||Plating methods for low aspect ratio cavities|
|US20110054397 *||Mar 17, 2007||Mar 3, 2011||Menot Sebastien||Medical liquid injection device|
|CN102703938A *||Jun 7, 2012||Oct 3, 2012||上海交通大学||Stress relieving agent for copper sulfate electroplate liquid|
|CN102703938B *||Jun 7, 2012||Apr 22, 2015||上海交通大学||Stress relieving agent for copper sulfate electroplate liquid|
|CN102703939A *||Jun 7, 2012||Oct 3, 2012||上海交通大学||Stress relieving agent for copper methane sulfonate electroplate liquid and use method thereof|
|CN102703939B *||Jun 7, 2012||Dec 24, 2014||上海交通大学||Stress relieving agent for copper methane sulfonate electroplate liquid and use method thereof|
|DE3420999A1 *||Jun 6, 1984||Dec 13, 1984||Omi Int Corp||Waessriges saures galvanisches kupferbad und verfahren zur galvanischen abscheidung eines glaenzenden eingeebneten kupferueberzugs auf einem leitfaehigen substrat aus diesem bad|
|DE3421017A1 *||Jun 6, 1984||Dec 13, 1984||Omi Int Corp||Verfahren zur galvanischen abscheidung eines technischen kupferueberzugs|
|DE3518193A1 *||May 21, 1985||Dec 5, 1985||Omi Int Corp||Waessriger saurer kupfer enthaltender elektrolyt und ein verfahren zur galvanischen abscheidung von kupfer unter verwendung dieses elektrolyten|
|DE4343946C2 *||Dec 22, 1993||Oct 29, 1998||Enthone Omi Inc||Galvanisches Kupferbad und Verfahren zur galvanischen Abscheidung von Kupfer|
|EP0068807A2 *||Jun 23, 1982||Jan 5, 1983||M & T CHEMICALS, INC.||Acid copper electroplating baths containing brightening and levelling additives|
|EP0107109A2 *||Sep 30, 1983||May 2, 1984||LeaRonal, Inc.||Electrolytic copper plating solutions and a method for their application|
|EP0355804A2 *||Aug 23, 1989||Feb 28, 1990||Shipley Company Inc.||Electroplating composition and process|
|EP1118696A1 *||Sep 3, 1999||Jul 25, 2001||Ebara Corporation||Method for plating substrate and apparatus|
|EP1126512A2 *||Aug 11, 1999||Aug 22, 2001||Ebara Corporation||Wafer plating method and apparatus|
|EP1308540A1 *||Oct 4, 2001||May 7, 2003||Shipley Co. L.L.C.||Plating bath and method for depositing a metal layer on a substrate|
|WO1989007162A1 *||Jan 18, 1989||Aug 10, 1989||Jct Controls Limited||Electrochemical processes|
|U.S. Classification||205/298, 205/296|
|Nov 20, 1983||AS||Assignment|
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY
Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733
Effective date: 19830930
|Oct 6, 1983||AS||Assignment|
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD,
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827
Effective date: 19830915
|May 5, 1983||AS||Assignment|
Owner name: OCCIDENTAL CHEMICAL CORPORATION
Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054
Effective date: 19820330
|Apr 19, 1982||AS||Assignment|
Owner name: HOOKER CHEMICALS & PLASTICS CORP.
Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885
Effective date: 19801222