WO2002086196A1 - Bains acides de cuivre, systeme et procede d'electrodeposition sur des substrats a rapport d'aspect eleve - Google Patents

Bains acides de cuivre, systeme et procede d'electrodeposition sur des substrats a rapport d'aspect eleve Download PDF

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Publication number
WO2002086196A1
WO2002086196A1 PCT/US2002/012355 US0212355W WO02086196A1 WO 2002086196 A1 WO2002086196 A1 WO 2002086196A1 US 0212355 W US0212355 W US 0212355W WO 02086196 A1 WO02086196 A1 WO 02086196A1
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WO
WIPO (PCT)
Prior art keywords
bath
copper
electrolyte
cuprous
solution
Prior art date
Application number
PCT/US2002/012355
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English (en)
Inventor
Douglas W. Mckesson
Joseph Cole
Rudolf P. Sedlak
Original Assignee
Rd Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rd Chemical Company filed Critical Rd Chemical Company
Publication of WO2002086196A1 publication Critical patent/WO2002086196A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/003—Electroplating using gases, e.g. pressure influence
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method

Definitions

  • the present invention relates generally to the field of electroplating, and more particularly to electroplating copper in an acidic bath to achieve improved plating uniformity.
  • Aspect ratio usually applied to a through-hole, or a blind (not completely drilled through) hole, also known as a "via”, refers to the ratio of the height, or depth of the hole to the diameter of the hole.
  • any aspect ratio higher than 8 or 10 is referred to as "high”.
  • An exemplary copper plating bath comprises sulfuric acid, copper sulfate, 50 ppm of chloride (a cuprous ligand), organic additives for leveling and brightening, and water.
  • an electroless copper plating procedure is generally used to establish conductivity by plating having a thickness of about 50 millionths of an inch to make the hole well conductive.
  • Other replacement technologies for electroless copper are currently being used to make the hole walls conductive, and may be used with this new technology.
  • a copper electroplating procedure is used, which is a much faster process and is much less expensive than electroless plating.
  • the trend for such holes has been to reduce the diameter of the hole as well as to increase the length of them, because of the increasing layers on the board and the higher density of interconnects (e.g., more holes per square inch of printed circuit board).
  • Fig. 1 is a schematic representation showing the inconsistent plating of copper that occurs along a through hole of a printed circuit board when plated by using current plating baths known in the art, in this case a sulfuric acid bath as described above.
  • copper 50 deposits at a greater rate on the walls in the regions of the ends 114,116 (entrance and exit portions of the hole, respectively) and therefor accumulates more in these regions compared with the center portion.
  • it may require the electroplating process to continue until the accumulations at the end of the holes are unacceptably thick, sometimes to the degree where the hole can actually be partially or totally closed by the deposits. Additionally, it is known to those skilled in the art that slowing the electroplating process gives a more uniform deposit, and allows improved throwing power.
  • pulse plating Another approach toward achieving a more uniform deposition of copper on high aspect ratio conformations in an acidic bath is what is known in the art as "pulse plating".
  • a pulse plating procedure a known acid bath is set up according to current methods and the copper is initially plated at low voltage. After a predetermined time, when a greater thickness of copper has accumulated at the openings/surfaces of the high aspect ratio conformations than at the centers of the conformations, the current in the system is reversed and a deplating procedure is carried out at relatively high voltage, which has the effect of removing copper plating from the thicker areas (i.e., openings) at a higher rate than the removal rate from the centers.
  • the current is again reversed and applied at relatively low voltage to plate copper again.
  • a greater accumulation/plating thickness of copper at the center regions is built up, relative to the deposits at the openings/surfaces.
  • this process is time consuming, thereby still causing a bottle neck in a production line.
  • the pattern of plating and deplating changes for each different substrate to be plated, causing set up to be expensive and complicated.
  • special organic brighteners are required in this process, because the brighteners currently used in the art will decompose during the current switching cycles. Also, rectifiers for driving the cycling are expensive compared to those currently used.
  • the present invention is directed to improved electrolyte baths for the electroplating of copper, and systems and methods using such baths for electroplating copper with sufficient throwing power to effectively electroplate high aspect ratio conformations on substrates having photoresist on a portion thereof.
  • Such a bath is disclosed to include copper ions and at least one ligand capable of binding copper ions in the electrolyte bath, wherein the electrolyte bath has a pH less than about 6.
  • the ligand of choice will have a very high metal chelate stability constant, and if the ligand is an acid, it will have a pKa low enough that there is enough free, non-protonated ligand available to react with the copper present to keep the free, un-complexed copper levels down to a small fraction ( ⁇ 50%, preferably less than 20% and more preferably less than 1%) of the total Copper in the bath.
  • the electrolyte baths preferably have a pH of about 0 to 4, more preferably about 0.
  • the copper ions may comprise cuprous ions or cupric ions, more preferably cuprous ions.
  • a ligand used may be hydrochloric acid, potassium chloride, or ammonium chloride.
  • cuprous ions For use with cuprous ions, bipyridyl and cuprous methane sulfonate may be employed, or chloride ions, for example.
  • a step is preferably taken to prevent cuprous ions in the bath solution from being oxidized to cupric ions by atmospheric oxygen. Preferably such step is accomplished by bubbling nitrogen through the bath.
  • One example of an electrolyte bath according to the present invention includes methane sulfonic acid, bipyridyl, cuprous methane sulfonate, and deionized water.
  • Another example of an electrolyte bath according to the present invention includes hydrochloric acid; cuprous chloride, and deionized water.
  • Another example of an electrolyte bath according to the present invention includes
  • cupric ion electrolyte bath includes hydrochloric acid, cupric chloride, and deionized water.
  • a cupric ion bath may include hydrochloric acid and cupric chloride at a ratio of about 1.5M:1.0M, respectively.
  • a method of electroplating copper with sufficient throwing power to effectively electroplate high aspect ratio conformations on substrates having photoresist on a portion thereof is described as providing an electrolyte bath having cuprous ions in solution and a pH less than about 6, providing a copper anode, submerging the copper anode and the substrate in the electrolyte bath, electrically connecting the copper anode and the substrate with an electric current source; and applying current to plate copper on the substrate.
  • Fig. 1 is a schematic sectional representation of a hole in a printed circuit board having been copper plated by a prior art technique.
  • Fig. 2 is a schematic representation of a cutaway of an electroplating system.
  • Fig. 3 is a schematic sectional representation of a hole in a printed circuit board illustrating the potential differential between the openings of the hole and the central wall portions of the hole.
  • Fig. 4 is a simplified schematic representation of an overhead view of an electroplating system.
  • Fig. 5 is a graph showing the plating thickness distribution over various cathode plates, one of which was plated in a HCl/ cupric chloride electrolyte bath according to the present invention, and one of which was plated in a known copper sulfate/sulfuric acid electrolyte bath.
  • Fig. 6 is a graph showing the plating thickness distribution over various cathode plates, two of which were plated in a methane sulfonic acid/bipyridyl electrolyte bath according to the present invention, and one of which was plated in a known copper sulfate/sulfuric acid electrolyte bath.
  • Fig. 7 is a schematic sectional representation of a hole in a printed circuit board showing an ideal, uniform copper plating thereon.
  • throwing power is used to describe the extent to which an electroplating system can effectively plate regions within crevices, cracks, holes, etc.
  • aspect ratio refers to the ratio of the depth of a hole to the diameter of the hole.
  • high aspect ratio plating refers to the extent to which an electroplating system can effectively plate regions within holes and on other high aspect ratio features that occur in printed circuit boards and semiconductor devices. Thus “high aspect ratio plating” requires the system to have good throwing power.
  • cuprous refers to the monovalent anion of copper, i.e., Cu + .
  • cupric refers to the divalent anion of copper, i.e., Cu "1" .
  • current efficiency refers to the percentage of current in the system that is used in the plating reaction, rather than to produce hydrogen gas at the cathode, or oxygen gas at the anode.
  • FIG. 2 a simple schematic of a copper electrode plating system 200 is shown.
  • An electrolyte bath 210 is provided in a container 220. Copper anodes 230 and a substrate 240 to be electroplated are submerged in the bath 210.
  • Anodes 230 are electrically connected to one pole (i.e., negative pole) of a rectifier 250 and the substrate 240 is electrically connected to the opposite pole. Electric power is supplied to the system by the rectifier, by which copper ions enter the bath 210.
  • the portion of the substrate 240 which is electrically conductive and connected to the rectifier 250 functions as a cathode in the system, where copper ions are reduced, with copper plating resulting on the substrate.
  • the sulfate In a simple system using copper sulfate and sulfuric acid in the bath, for example, the sulfate has no ability to complex the copper ions in solution and therefor there is a great availability of copper ions for reaction at the cathode. Such an arrangement lacks sufficient throwing power for adequate high aspect ratio plating, since the available copper ions plate readily to the areas of lower voltage drop, respectively of the substrate 240 to be plated.
  • Fig. 3 illustrates the effective voltages that result along a through hole 260 or other high aspect ratio feature to be electroplated.
  • the voltage at locations 262,266, the openings of the hole is greater than the voltage at location 264, near the center portion of the hole, because of the greater distance through the electrolyte that the ions must travel, which presents a greater resistance and, hence, a greater voltage drop.
  • aspect ratio and voltage drop there is a direct relationship between aspect ratio and voltage drop; thus, the higher the aspect ratio, the greater is the voltage drop between a surface/opening of the high aspect ratio conformation and the center or feature to be plated which is furthest from the surface/opening.
  • the present invention addresses several aspects to achieving a greater throwing power in order to effectively electroplate high aspect ratio features with copper.
  • One such aspect is to effectively reduce the ready availability of copper ions in the bath so as to slow the electroplating process down at the entrances of the holes, thereby allowing plating in the centers of the holes to progress and develop more evenly with the openings.
  • the copper must be complexed in solution with the electrolyte, such as with a ligand or chelating agent.
  • the electrolyte must be acidic so as not to disrupt any photoresist 60 that may be present on the substrate to be electroplated.
  • a pH of 6 or less is needed to prevent damage to the photoresist, with the systems preferably using a bath having a pH in the range of about 0 to 4, and more preferably about 0.
  • an effective ligand must also be very soluble in the bath solution, i.e., the electrolyte producing the ligand must be strongly acidic so as to provide an adequate supply of the ligand, since both copper ions and hydrogen ions will be competing to react with the ligand in solution.
  • chloride is used as the ligand. The reaction that occurs during the electroplating at the surface of the substrate is:
  • N surf ace + ⁇ N, and ⁇ N represents the voltage drop between the opening 262 and the center
  • the differential plating rates between locations on or near the surface of the substrate (e.g., 262 and 266) and locations furthest from the surface in a high aspect ratio conformation (e.g., center portion 264) can be minimized, because ⁇ N remains substantially constant and becomes a less significant component of N ⁇ as Nsurface is made larger, i.e., . ⁇ N/ N su r face + ⁇ N becomes smaller as Nsurface increases.
  • the side reaction (2) becomes more prevalent, and, at some level can even become the dominant reaction. This greatly reduces the current efficiency, as most of the power of the operation is being directed toward producing hydrogen at this point and not for electroplating copper.
  • the amount of voltage used is a function of many variables, including the specific electrolyte being used, the distance from the anode to the cathode, as well as the temperature of the bath.
  • the absolute voltage used in any given application may be determined by those of ordinary skill in the art, given the above parameters.
  • the present invention may decrease the current efficiency on the upper, more available sites, but it is not a uniform effect.
  • the current efficiency at the sites of electroplating is decreased by the present invention, by binding up the copper ions to make them less available for reduction at the cathode (i.e., substrate where the electroplating is taking place).
  • An electrolyte used must contain a ligand that will not only bind copper, but will also provide a ready supply of non-protonated species at the acidity level that the electroplating is being performed at.
  • the electroplating will proceed with the same disadvantages inherent in the known sulfuric acid bath systems, i.e., the ready availability of copper ions at the surface of the substrate will result in a rapid electroplating process with insufficient throwing power.
  • An electroplating system that has sufficient throwing power to effectively electroplate high aspect ratio conformations on substrates having photoresist on a portion thereof, will therefore be an acidic system, having a pH of less than about 6, and usually around 0-4, more usually about 0, and is characterized by a slower electrodeposition rate, relative to the known sulfuric acid electroplating systems described above, at the surface of the substrate, or in the locations of highest current density, while exhibiting a faster deposition rate, relative to the known sulfuric acid electroplating systems described above, at the center of a hole or location on the high aspect ratio conformation that is furthest from the surface or highest current density location, and thus has the lowest relative current density, or, at least the deposition at the center relative to the openings will be greater than that of known systems.
  • the Hull Cell or Larry Cell 300 is a four sided chamber adapted to contain an anode 310, cathode 320 and electrolytic bath 330. Parallel sides 302 and 304 join non-parallel sides 306 and 308. Anode 310 (i.e., a copper plate) was mounted against side 306, which is perpendicular to sides 302 and 304.
  • Cathode 320 (e.g., a conducting plate which was, in this example, a brass plate, although other conductive materials can be used) was mounted against wall 308, which joins walls 302 and 304 and angles away from wall 306. This configuration sets up a current density gradient along cathode 320 when anode 310 and cathode 320 are connected to a rectifier and electricity is provided to the system to begin the electroplating process. That is, the highest current density occurring on cathode 320 is that location that is closest to the anode, i.e., end 320a of cathode 320 in this example.
  • the current density decreases along the length of cathode 320, with the decreasing gradient being a function of the angle of wall 308 with respect to wall 306, which causes a gradual increase in the distance of the cathode 320 from the anode 310 in travelling from end 320a to 320b.
  • the lowest relative current density occurs at the furthest location from the anode 310, i.e., end 320b of anode 320.
  • Cell 300 is configured to hold 267 ml of electrolyte when the anode and cathode plates 310,320 are in position.
  • Each electrolyte bath is generally operated at room temperature during the tests, although it may prove preferable to heat the electrolyte bath in a production environment.
  • a DC rectifier having no greater than about 5%, and preferably less than about 1% variation (ripple) in output amperage is used to provide 1 amp of electrical energy to the system.
  • the plating tests were generally run at one ampere for about 83 minutes for a divalent species (the time to theoretically plate the cathode with 1 mil (.001") of copper uniformly, in a system with sufficient throwing power to uniformly plate the cathode in the cell 300), 41.5 minutes for a monovalent species. Running these tests at one ampere total is typical, and results in the high current density end of the test panel receiving about 40 amps per square foot current density, with the low current density end of the panel receiving about 0.5 Amps/square foot.
  • Tests were performed without organic brightener added, since this varies with each specific application.
  • An important goal of the present invention is to achieve more plating at lower current density (relative increase in plating rate) and/or to relatively decrease the plating rate at higher current density, relative to the standard sulfuric acid model.
  • the fact that tests were performed without brightener is not to be considered a limitation, as this was done merely to confirm the theory of this technology. It is understood that an organic brightener system will be added in commercial applications of the present invention. After running the electroplating process for the prescribed period, the rectifier was shut down and the cathode 320 was removed from the system.
  • the thickness of the copper plating that was electroplated on the cathode 320 was then measured, using a micrometer to plot the variation in thickness of the plating deposited as a function of distance from the anode 310, thereby measuring the throwing power of the system.
  • a cupric bath comprising 1.0 Molar cupric chloride, 1.5M HCl, 0.1% Polyethylene Glycol 400 q.s. and deionized water did not exhibit a desirable bath life before the composition of the bath needed to be adjusted, e.g., about 20 minutes.
  • One way of protecting the bath is to bubble nitrogen through the bath, at least during electroplating, and preferably continuously.
  • a flow rate of about 0.2 liters per minute of nitrogen is preferably used in the Hull cell testing.
  • gases such as inert gases, like argon or neon could alternatively be used, as could carbon dioxide, or any other medium that would be non interfering with the electroplating process, safe, and would ensure an oxygen free environment for the bath.
  • Fig. 5 shows the plating results using a HCl/cuprous chloride electrolyte bath according to the present invention, compared with the results using a known copper sulfate/sulfuric acid electrolyte bath.
  • Plot 410 is a measurement of the thicknesses of copper deposited on cathode 320, according to the distance from the highest current density edge 320a, using the copper sulfate/sulfuric acid electrolyte bath. This bath was made up of 1 M sulfuric acid, 1 M copper sulfate, 50 ppm chloride ions supplied in the form of HCl and a balance of water (preferably deionized water) to make up the total volume of 267 ml.
  • Plot 400 is a measurement of the thicknesses of copper deposited on cathode 320, according to the distance from the highest current density edge 320a, using an HCl/CuCl electrolyte bath. This bath was made up of 3 M HCl (hydrochloric acid), 0.1 M CuCl,(cuprous chloride) and a balance of water (preferably deionized water) to make up the total volume of 267 ml. Nitrogen was bubbled into the bath at a rate of about 0.2 liters per minute.
  • a comparison of the plots 400,410 reveals that the thickness of the copper plating nearest the highest current density edge 320a for the l ⁇ iown copper sulfate/sulfuric acid electrolyte bath 410 is greater than the thickness of the copper plating in corresponding locations on the cathode 320, for the HCl/CuCl electrolyte bath according to the present invention. More specifically, up to about 1.9" (i.e. from 0.0" up to about 1.9”) from the highest current density edge 320a, the copper plating using the known bath 410 is thicker than the copper plating using the HCL/CuCl bath 400.
  • the thickness of the copper plating at the distant end portion is substantially thicker on the cathode subjected to the HCL/CuCl bath 400, compared to the same locations on the cathode subjected to the known copper sulfate/sulfuric acid electrolyte bath 410, indicating the superior throwing power of the HCl/CuCl bath 400.
  • Fig. 6 shows the plating results of a run 500 using a methane sulfonic acid/ bipyridyl electrolyte bath according to the present invention, compared with the results using a known copper sulfate/sulfuric acid electrolyte bath 520.
  • Plot 500 indicates the measures thicknesses of copper deposited on cathode 320 in the methane sulfonic acid/bipyridyl runs 500, according to the distance from the highest current density edge 320a.
  • the electrolyte bath was made up of 1 M (Normal) methane sulfonic acid, 0.12 M bipyridyl, 0.05 M cuprous methane sulfonate, 0.2% polyethylene glycol 200 (used to enhance the smoothness of the plating deposition, simply to facilitate the measurement of thickness of plating deposits), and a balance of water (preferably deionized water) to make up the total volume of 267 ml. Nitrogen was bubbled into the bath at a rate of 0.2 liters per minute.
  • Plot 520 is a measurement of the thicknesses of copper deposited on cathode 320, according to the distance from the highest current density edge 320a, using a copper sulfate/sulfuric acid electrolyte bath. This bath was made up of 1 M sulfuric acid, 1 M copper sulfate, 50 ppm chloride ions supplied in the form of HCl, 0.2% polyethylene glycol
  • the copper plating using the known bath 520 is thicker than the copper plating using the methane sulfonic acid/bipyridyl bath 500.
  • the thickness of the copper plating at the distant end portion is thicker on the cathode subjected to the methane sulfonic acid/bipyridyl bath 500, compared to the same locations on the cathode subjected to the known copper sulfate/sulfuric acid electrolyte bath 520, indicating the superior throwing power of the methane sulfonic acid/bipyridyl bath 500.
  • Fig. 7 is a schematic representation showing an ideal, consistent plating of copper along a through hole of a printed circuit board. This is a distribution of copper that would result using a system that would be characterized on any of the graphs in Figs. 5-6 by a perfectly horizontal line. As can be seen, the thickness of the copper plating 50 on the walls in the center region 112 of the hole 110 is equal to the thickness of the copper plating 50 in the regions of the ends 114,116 (entrance and exit portions of the hole, respectively) and also the thickness of the plating 50 adjacent the photoresist 60.
  • bromide may be combined in a cuprous system, or an electrolyte that complexes cupric and doesn't stabilize cuprous may be used in a cupric system that does not utilize cuprous ions.
  • Bromide-bipyridyl systems may be used with cuprous electrolyte baths, similar to chloride-bipyridyl cuprous baths.
  • many modifications may be made to adapt a particular situation, material, composition of matter, process, process step or steps, to the objective, spirit and scope of the present invention. All such modifications are intended to be within the scope of the claims appended hereto.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'invention concerne des bains d'électrodéposition, un système et un procédé d'électrodéposition de cuivre sur un substrat (240) présentant des confirmations de rapport d'aspect élevées, ainsi qu'une photorésine déposée sur des parties de ce substrat. Ledit substrat (240) est immergé dans un système d'électrodéposition (200) à électrode de cuivre (230). Ce système (200) comporte un conteneur (220) conçu pour contenir un bain électrolytique (210) présentant un pH acide. Ces bains, système et procédé d'électrodéposition permettent d'obtenir un pouvoir de dépôt uniforme amélioré par l'utilisation des bains acides et des adjuvants d'électrodéposition selon l'invention.
PCT/US2002/012355 2001-04-19 2002-04-18 Bains acides de cuivre, systeme et procede d'electrodeposition sur des substrats a rapport d'aspect eleve WO2002086196A1 (fr)

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US28565101P 2001-04-19 2001-04-19
US60/285,651 2001-04-19

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2006032346A1 (fr) * 2004-09-20 2006-03-30 Atotech Deutschland Gmbh Procédé de galvanisation pour le remplissage de trous traversants avec des métaux, en particulier de cartes à circuit imprimé avec du cuivre
US20130264214A1 (en) * 2012-04-04 2013-10-10 Rohm And Haas Electronic Materials Llc Metal plating for ph sensitive applications
US20140322912A1 (en) * 2008-11-26 2014-10-30 Enthone Inc. Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers
CN105745336A (zh) * 2013-11-27 2016-07-06 豪夫迈·罗氏有限公司 用于从混合物富集突变核酸的方法
EP2514856A3 (fr) * 2011-04-19 2016-09-21 Rohm and Haas Electronic Materials LLC Placage de cuivre sur des semi-conducteurs

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US6113771A (en) * 1998-04-21 2000-09-05 Applied Materials, Inc. Electro deposition chemistry
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US4384930A (en) * 1981-08-21 1983-05-24 Mcgean-Rohco, Inc. Electroplating baths, additives therefor and methods for the electrodeposition of metals
US4923576A (en) * 1988-07-06 1990-05-08 Technic, Inc. Additives for electroplating compositions and methods for their use
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032346A1 (fr) * 2004-09-20 2006-03-30 Atotech Deutschland Gmbh Procédé de galvanisation pour le remplissage de trous traversants avec des métaux, en particulier de cartes à circuit imprimé avec du cuivre
US9445510B2 (en) 2004-09-20 2016-09-13 Atotech Deutschland Gmbh Galvanic process for filling through-holes with metals, in particular of printed circuit boards with copper
US9526183B2 (en) 2004-09-20 2016-12-20 Atotech Deutschland Gmbh Galvanic process for filling through-holes with metals, in particular of printed circuit boards with copper
US20140322912A1 (en) * 2008-11-26 2014-10-30 Enthone Inc. Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers
US9613858B2 (en) * 2008-11-26 2017-04-04 Enthone Inc. Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers
EP2514856A3 (fr) * 2011-04-19 2016-09-21 Rohm and Haas Electronic Materials LLC Placage de cuivre sur des semi-conducteurs
US20130264214A1 (en) * 2012-04-04 2013-10-10 Rohm And Haas Electronic Materials Llc Metal plating for ph sensitive applications
CN103484902A (zh) * 2012-04-04 2014-01-01 罗门哈斯电子材料有限公司 用于pH敏感应用的金属镀覆
CN105745336A (zh) * 2013-11-27 2016-07-06 豪夫迈·罗氏有限公司 用于从混合物富集突变核酸的方法
CN105745336B (zh) * 2013-11-27 2019-03-01 豪夫迈·罗氏有限公司 用于从混合物富集突变核酸的方法

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