EP2821530A1 - Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens - Google Patents

Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens Download PDF

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Publication number
EP2821530A1
EP2821530A1 EP13175010.1A EP13175010A EP2821530A1 EP 2821530 A1 EP2821530 A1 EP 2821530A1 EP 13175010 A EP13175010 A EP 13175010A EP 2821530 A1 EP2821530 A1 EP 2821530A1
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EP
European Patent Office
Prior art keywords
galvanic
electrolyte
electrodes
conditioning
activation
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13175010.1A
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English (en)
French (fr)
Inventor
Stefan Grüßner
Ferdinand Wiener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP13175010.1A priority Critical patent/EP2821530A1/de
Priority to PCT/EP2014/063764 priority patent/WO2015000817A1/en
Priority to TW103123199A priority patent/TW201508100A/zh
Publication of EP2821530A1 publication Critical patent/EP2821530A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

  • the present invention relates to a device for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device, which comprises at least a reaction container filled with such a galvanic electrolyte, wherein said galvanic device is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated.
  • the present invention is further directed to a method for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device, which comprises at least a reaction container filled with such a galvanic electrolyte, wherein said galvanic device is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated.
  • Galvanic devices of the prior art which are supposed to be used for the deposition of a galvanic metal on a substrate to be treated, are always underlying the challenge to ensure that the galvanic electrolyte and the electrodes, which are supposed to be used for the deposition of a galvanic metal, has to be kept efficient and active for the desired purpose.
  • the individual galvanic electrolyte components such as brighteners, levelers and other additives, have to be surveyed for their active state.
  • a known problem is that such an active galvanic electrolyte for a galvanic deposition process is not easily available by just mixing the required basic electrolyte with certain amounts of further additives and individual electrolyte components, such as brighteners and levelers. Even when all components of the galvanic electrolyte are mixed to a homogenous final electrolyte solution, it is up to now still necessary for prior art devices to conduct the so-called "dummy panel plating" procedure.
  • a significant number of regular panels or substrates to be treated have to be transported through the whole galvanic plating device during such a "dummy panel plating" procedure.
  • the conditioning and activation of the electrolyte and the electrodes takes commonly place by the generated decomposition products of certain electrolyte components, such as brighteners and levelers, during this procedure.
  • certain electrolyte components such as brighteners and levelers
  • the galvanic plating device has been stopped for an intermediate period of time, such as for maintenance or for a weekend, wherein no substrates to be treated are plated by such a galvanic plating device.
  • the galvanic electrolyte in particular individual electrolyte components such as brighteners or levelers, is/are commonly less active than before. It is then not sufficient to just readjust the individual components back to their original higher amounts or concentrations in order to reactivate the galvanic electrolyte, in particular the brighteners.
  • the "dummy panel plating" procedure has to be conducted to recondition or reactivate the galvanic electrolyte and the electrodes of the galvanic plating device.
  • Said dummy panel plating wastes a large amount of panels, which have to be thrown away after the process. Furthermore, the galvanic plating device is occupied by said process and wastes time, energy, water and chemicals during and by said dummy panel process, which makes it to a certain extent ineffective and costly.
  • the present invention accordingly provides a device for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device, which comprises at least a reaction container filled with such a galvanic electrolyte, wherein said galvanic device is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated characterized in that the device comprises at least a first reaction tank, which is filled with such a galvanic electrolyte, at least a first anode, at least a first cathode, at least a rectifier for adjusting and/or controlling direct current or alternating current, at least a current source, at least an electrical connection for said electrodes, a circular pump system for circulating the electrolyte via at least a first and at least a second connection between the reaction container of the galvanic device and the first reaction tank of the device for conditioning and activation; wherein decomposition products of galvanic electrolyte components are generated in
  • the device and the method are able to condition a galvanic electrolyte and to activate the electrodes of a galvanic device, which is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated, while at the same time the so-called "dummy plating", as discussed above, can be avoided.
  • the device and the method for conditioning and activation of the present invention is generally suitable for all different kind of known horizontal or vertical galvanic plating devices, wherein the device can comprise an additional external add-on module or an additional internally integrable unit.
  • the device and the method of the present invention comprises solely a minimum of device elements and method steps, which are as cheap and as simply constructed, in case of device elements, as possible.
  • the device and the method of the present invention is suitable to tremendously reduce cost of any kind of galvanic plating process by avoiding the so-called "dummy plating" whereby no dummy panels have to be wasted no more.
  • the waste of man power and material is also achieved by reducing the required amount of time, chemistry, water and energy, which normally have to be spend for all pretreatment and post treatment steps in such known galvanic plating devices and processes, wherein the common "dummy panel plating" had to be conducted up to now.
  • galvanic metal when applied in accordance with the present invention, refers to metals which are known to be generally suitable for a galvanic metal deposition method.
  • galvanic metals can comprise gold, nickel, and copper, preferably copper.
  • substrate to be treated when applied in accordance with the present invention, refers to substrates which are round, preferably circular, or angular, preferably polyangular, such as rectangular, quadratic or triangular, or a mixture of round and angular structure elements, such as semicircular.
  • Such substrates have a diameter ranging from 50 mm to 1000 mm, preferably from 100 mm to 700 mm, and more preferably from 120 mm to 500 mm, in case of a round structure; or a side length ranging from 10 mm to 1000 mm, preferably from 25 mm to 700 mm, and more preferably from 50 mm to 500 mm, in case of an angular, preferably polyangular, structure.
  • Such substrates can be a printed circuit board, a printed circuit foil, a semiconductor wafer, a solar cell, a photoelectric cell or a monitor cell.
  • Electrodes when applied in accordance with the present invention, refers to electrodes, which are generally suitable for a galvanic metal plating process making use of any kind of a galvanic metal plating device, independently if the galvanic metal plating process is a vertical or horizontal process. Electrodes can be comprised of an insoluble material, such as titanium coated with iridium oxide, and/or of a soluble material, such as a soluble anode composed of copper (sacrificial anode).
  • the electrodes are arranged vertically inside of the first reaction tank of the inventive device for conditioning and activation.
  • galvanic device when applied in accordance with the present invention, refers to any kind of galvanic device, which is suitable for a galvanic metal plating process, independently if the galvanic metal plating process is a vertical or horizontal process.
  • galvanic electrolyte when applied in accordance with the present invention, refers to any kind of galvanic electrolyte, which is suitable for a galvanic metal plating process, independently if the galvanic metal plating process is a vertical or horizontal process.
  • This general definition shall include all kind of generally suitable individual electrolyte components known in the prior art, such as brighteners and levelers.
  • the galvanic electrolyte in the reaction container of the galvanic device is identical to the galvanic electrolyte in the first reaction tank of the inventive device for conditioning and activation.
  • both provided galvanic electrolytes could also be different at the beginning of the inventive method.
  • both galvanic electrolytes would become identical again over time by circulating the electrolytes between the galvanic device and the device for conditioning and activation via the at least first and the at least second connection by applying the circular pump system.
  • inventive device and method is different to known prior art devices and methods, which are commonly focusing on a circulation circle for refreshing a galvanic electrolyte.
  • a refreshing offers solely a possibility to refresh the respective galvanic electrolyte during the galvanic metal plating process by adding galvanic metal ions, preferably copper ions, in order to replace the consumed metal, preferably copper, ions, which have been already used during the galvanic metal plating process for metal, preferably copper, deposition on a substrate to be treated.
  • the device and method of the present invention focusses on a circulation circle of the electrolyte in order to condition and activate the galvanic electrolyte prior to the start of a galvanic metal plating process by generating decomposition products of individual electrolyte components.
  • the device further comprises at least a first connecting port for connecting the device to at least a second identical device for balancing the electrolyte level inside of both devices.
  • the device further comprises at least a first means for adjusting, monitoring and/or controlling of the conditioning and activation process taking place in said device.
  • the first means can comprise a measurement tool or device, which is suitable to measure the progress of the conditioning and activation in-situ by analyzing the individual electrolyte components, such as by online titration via an ancolyzer.
  • a function could also be fulfilled by manpower, wherein an user at customer site shall conduct such measurements in-situ in the classical way by common methods, such as titrations.
  • the device is externally connected as separated unit to the galvanic device and/or the device is a modular unit, which is connectable as internal unit to an existing galvanic device.
  • the internal alternative would save total space while the external alternative offers a higher flexibility for installing and arranging such additional devices to existing galvanic devices.
  • the ratio of the total anode area versus the total cathode area of the device is equal to the ratio of the total anode area versus the total cathode area of the respective galvanic device to which the device is operative connectable.
  • Such an embodiment would offer the advantage of similarity to known process parameters of the galvanic device itself, which could be easily transferred and/or adapted to the inventive device for conditioning and activation due to the equality of the above-cited area ratios.
  • the ratio of the total anode area versus the total cathode area of the device is unequal to the ratio of the total anode area versus the total cathode area of the respective galvanic device to which the device is operative connectable, preferably ranging from 1.1:1 to 4:1 or from 1:1.1 to 1:4, more preferably from 1.5:1 to 3:1 or from 1:1.5 to 1:3.
  • Such an embodiment would offer the advantage of flexibility regarding the adjusting of known process parameters of the galvanic device itself by changing the area ratios in such a way that modified process parameters shall be easily available for the inventive device for conditioning and activation due to the disparity of the above-cited area ratios.
  • the total anode area and the total cathode area of the device are equal to the respective total anode area and the respective total cathode area of the respective galvanic device to which the device is operative connectable.
  • Such an embodiment would offer the advantage of similarity to known process parameters of the galvanic device itself, which could be easily transferred and/or adapted to the inventive device for conditioning and activation due to the equality of the above-cited total electrode areas.
  • the total anode area and the total cathode area of the device are unequal to the respective total anode area and the respective total cathode area of the respective galvanic device to which the device is operative connectable.
  • the total anode area and the total cathode area of the device are larger than the respective total anode area and the respective total cathode area of the respective galvanic device to which the device is operative connectable, there is needed more space at customer sites to arrange the respective inventive device and there is required more galvanic electrolyte to fill said larger inventive device, which makes this alternative more costly.
  • the conditioning and the activation takes place faster, which saves again costs.
  • the total anode area and the total cathode area of the device are in contrast to the above-cited alternative smaller than the respective total anode area and the respective total cathode area of the respective galvanic device to which the device is operative connectable, there is needed less space at customer sites to arrange the respective inventive device and there is required less galvanic electrolyte to fill said smaller inventive device, which makes this alternative cheaper.
  • the conditioning and the activation takes place slower, which increases again costs.
  • the device comprises at least a first electrolysis device unit, which comprises one cathode and one anode, one cathode and two anodes or two cathodes and one anode; wherein the device further comprises at least one separating plate between neighbored electrolysis device units as electromagnetic shielding for the electrodes, if said electrodes of neighbored electrolysis device units possess the same polarity.
  • the inventive device comprises more than one electrolysis device unit, there is a need for a parallel connection for the current supply of said at least two electrolysis device units. If a connection in series is desired, it has to be noted that a complete electrical separation of the individual electrolysis device units would be necessary, which would require more space and generate more costs. Thus, parallel connection shall be preferred for the present invention.
  • the electromagnetic shielding relates to a shielding of the electric flux lines between neighbored electrodes of same polarity, not to a complete separation of the individual electrolysis device units from each other.
  • the object of the present invention is also solved by a method for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device, which comprises at least a reaction container filled with such a galvanic electrolyte, wherein said galvanic device is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated characterized by the following method steps:
  • step iii) and iv) could also be executed in reversed order, but solely if the difference in the chronology is not getting too high, meaning that step iii) follows step iv) very lately, such as a couple hours later. Then, there would be the risk that the electrolyte in the inventive device is getting depleted without starting the circulation of the electrolyte on time.
  • the method further comprises an intermediate step (vii') between step vii) and step viii) if the galvanic electrolyte comprises an oxidizing agent, preferably Fe 3+ ions; wherein the device according to the present invention stays so long connected to the galvanic device during the subsequently started galvanic metal deposition process until all copper which had been before deposited on the surface of the at least one cathode in the first reaction tank of the device according to the present invention has been dissolved again to the galvanic electrolyte by oxidizing the deposited copper to copper ions.
  • an oxidizing agent preferably Fe 3+ ions
  • the applied current in method step iv) can be direct current or alternating current.
  • Alternating current has been found advantageous, if it is desired to redissolve deposited galvanic metal, preferably copper, from the cathode of the inventive device in the electrolyte during the conditioning and activation method in order to minimize the amount of consumed galvanic metal, preferably copper, which can reduce the costs of the inventive method. It shall also save the amount of required electrolyte.
  • the current is applied to the electrodes of the device according to the present invention by a parallel connection, if the device according to the present invention comprises more than one electrolysis device units, which comprises one cathode and one anode, one cathode and two anodes or two cathodes and one anode; wherein the device according to the present invention further comprises at least one separating plate between neighbored electrolysis device units as electromagnetic shielding for the electrodes, if said electrodes of neighbored electrolysis device units possess the same polarity.
  • method steps iii), iv), v) and vi) are conducted for a certain period of time to be specified, which can be adjusted, monitored and/or controlled manually by an user and/or automatically by an at least first means for adjusting, monitoring and/or controlling.
  • the object of the present invention is also solved by making use of a method according to according to the present invention, which makes use of a device according to the present invention, for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device, which comprises at least a reaction container filled with such a galvanic electrolyte, wherein said galvanic device is supposed to be subsequently used for a galvanic metal, in particular copper, deposition process for depositing said galvanic metal on a substrate to be treated.
  • the present invention thus addresses the problem of avoiding the so-called "dummy panel plating", wherein a plurality of panels have to be run through the entire respective galvanic plating device in order to condition the galvanic electrolyte and to activate the electrodes of the reaction container of such a galvanic device for depositing a galvanic metal on a substrate to be treated.
  • the inventive device and method offer a way to avoid the main part of the generated costs which have been arising up to now by the force to conduct the dummy panel plating and thereby being forced to waste manpower, water, chemistry and energy.
  • Figure 1 shows a schematic illustrative side view of a device (1) for conditioning of a galvanic electrolyte (6) and for activation of electrodes of a galvanic device in accordance with a preferred embodiment of the present invention, wherein the device (1) comprises a first reaction tank (5), which is filled with a galvanic electrolyte (6).
  • the device (1) further comprises six electrolysis device units, wherein each electrolysis device unit comprises one cathode (8) and two anodes (7). Between each of these neighbored electrolysis device units has to be arranged a separating plate (12, not shown in this Figure) as electromagnetic shielding for the neighbored anodes (7) due to their same polarity.
  • the device (1) additionally comprises a rectifier (2) for adjusting and/or controlling direct current or alternating current, at least a current source (not shown) for providing current to the electrodes, one electrical connection (3) for the anodes and one electrical connection (4) for the cathodes of the electrolysis device units of the device (1).
  • a circular pump system (9) for circulating the electrolyte (6) via a first (10) and a second (11) connection between the reaction container of the galvanic device (not shown) and the first reaction tank (5) of the device (1) for conditioning and activation, wherein the first connection (10) represents an inlet while the second connection (11) represents an outlet for the electrolyte flowing in or out of the device (1).
  • Figure 2 shows a top view of a device (1') for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device in accordance with another preferred embodiment of the present invention, wherein the device (1') comprises a first reaction tank (5'), which is filled with a galvanic electrolyte.
  • the device (1') further comprises three electrolysis device units, wherein each electrolysis device unit comprises two cathodes (8') and one anode (7'). Between each of these neighbored electrolysis device units is a separating plate (12) arranged as electromagnetic shielding for the neighbored cathodes (8') due to their same polarity.
  • a circular pump system (9') for circulating the electrolyte via a first (10') and a second (11') connection between the reaction container of the galvanic device (not shown) and the first reaction tank (5') of the device (1') for conditioning and activation, wherein the first connection (10') represents an inlet while the second connection (11') represents an outlet for the electrolyte flowing in or out of the device (1').
  • the device (1') comprises a first connecting port (19) for connecting the device (1') to at least a second identical device (1', not shown) for balancing the electrolyte level inside of both devices (1').
  • the device (1') further comprises an electrolyte level sensor (13) for monitoring the level of the electrolyte inside of the first reaction tank (5') of the device (1'). If the electrolyte level highly decreases, the electrolyte level sensor (13) shuts down the circular pump system (9'). If the electrolyte level highly increases, the electrolyte level sensor (13) shuts down the valves (not shown) to avoid damaging and/or contaminating them.
  • an electrolyte level sensor (13) for monitoring the level of the electrolyte inside of the first reaction tank (5') of the device (1'). If the electrolyte level highly decreases, the electrolyte level sensor (13) shuts down the circular pump system (9'). If the electrolyte level highly increases, the electrolyte level sensor (13) shuts down the valves (not shown) to avoid damaging and/or contaminating them.
  • the device (1') further comprises an exhaust suction device element (14) for removing of possibly generated vapors.
  • the device (1) comprises as well an outer casing (16) and electrical contact rails (15), preferably composed of copper, which are connected via connecting cables (not shown) to the current contact rail for the anodes (17) and the cathodes (18). Said current contact rails (17,18) are themselves again in electrical contact to a rectifier (not shown).
  • Figure 3 shows a perspective side view of a device (1') for conditioning of a galvanic electrolyte and for activation of electrodes of a galvanic device in accordance with the same preferred embodiment of the present invention as shown in Figure 2 , wherein the device (1') comprises a first reaction tank (5'), which is filled with a galvanic electrolyte.
  • the device (1') further comprises three electrolysis device units, wherein each electrolysis device unit comprises two cathodes (8') and one anode (7'). Between each of these neighbored electrolysis device units is a separating plate (12) arranged as electromagnetic shielding for the neighbored cathodes (8') due to their same polarity.
  • a circular pump system (9') for circulating the electrolyte via a first (10') and a second (11') connection between the reaction container of the galvanic device (not shown) and the first reaction tank (5') of the device (1') for conditioning and activation, wherein the first connection (10') represents an inlet while the second connection (11') represents an outlet for the electrolyte flowing in or out of the device (1').
  • the device (1') comprises a first connecting port (19) for connecting the device (1') to at least a second identical device (1', not shown) for balancing the electrolyte level inside of both devices (1').
  • the device (1') further comprises an electrolyte level sensor (13) for monitoring the level of the electrolyte inside of the first reaction tank (5') of the device (1'). If the electrolyte level highly decreases, the electrolyte level sensor (13) shuts down the circular pump system (9'). If the electrolyte level highly increases, the electrolyte level sensor (13) shuts down the valves (not shown) to avoid damaging and/or contaminating them.
  • an electrolyte level sensor (13) for monitoring the level of the electrolyte inside of the first reaction tank (5') of the device (1'). If the electrolyte level highly decreases, the electrolyte level sensor (13) shuts down the circular pump system (9'). If the electrolyte level highly increases, the electrolyte level sensor (13) shuts down the valves (not shown) to avoid damaging and/or contaminating them.
  • the device (1') further comprises an exhaust suction device element (14) for removing of possibly generated vapors.
  • the device (1) comprises as well an outer casing (16) and electrical contact rails (15), preferably composed of copper, which are connected via connecting cables (not shown) to the current contact rail for the anodes (17) and the cathodes (18). Said current contact rails (17,18) are themselves again in electrical contact to a rectifier (not shown).

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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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Metals (AREA)
EP13175010.1A 2013-07-04 2013-07-04 Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens Withdrawn EP2821530A1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP13175010.1A EP2821530A1 (de) 2013-07-04 2013-07-04 Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens
PCT/EP2014/063764 WO2015000817A1 (en) 2013-07-04 2014-06-27 Method for conditioning of a galvanic electrolyte and activation of electrodes prior to the start of a galvanic metal deposition process
TW103123199A TW201508100A (zh) 2013-07-04 2014-07-04 在流電金屬沉積製程開始前用於調控流電電解質及電極活化之方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP13175010.1A EP2821530A1 (de) 2013-07-04 2013-07-04 Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens

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Publication Number Publication Date
EP2821530A1 true EP2821530A1 (de) 2015-01-07

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EP13175010.1A Withdrawn EP2821530A1 (de) 2013-07-04 2013-07-04 Vorrichtung und Verfahren zur Konditionierung eines galvanischen Elektrolyts und Aktivierung von Elektroden vor Beginn eines galvanischen Metallabscheidungsverfahrens

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EP (1) EP2821530A1 (de)
TW (1) TW201508100A (de)
WO (1) WO2015000817A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011003800A1 (en) * 2009-07-07 2011-01-13 Basf Plant Science Company Gmbh Plants having modulated carbon partitioning and a method for making the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067782A (en) * 1977-05-09 1978-01-10 Xerox Corporation Method of forming an electroforming mandrel
JPS6436798A (en) * 1987-07-30 1989-02-07 Nec Toyama Ltd Copper sulfate plating method
US20020139683A1 (en) * 2000-05-05 2002-10-03 Akihisa Hongo Substrate plating apparatus
EP1264918A1 (de) * 2001-06-07 2002-12-11 Shipley Co. L.L.C. Verfahren zur elektrolytischen Kupferplatierung
US7147827B1 (en) * 1998-05-01 2006-12-12 Applied Materials, Inc. Chemical mixing, replenishment, and waste management system
GB2454141A (en) * 2006-10-19 2009-04-29 Honda Motor Co Ltd Plating apparatus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067782A (en) * 1977-05-09 1978-01-10 Xerox Corporation Method of forming an electroforming mandrel
JPS6436798A (en) * 1987-07-30 1989-02-07 Nec Toyama Ltd Copper sulfate plating method
US7147827B1 (en) * 1998-05-01 2006-12-12 Applied Materials, Inc. Chemical mixing, replenishment, and waste management system
US20020139683A1 (en) * 2000-05-05 2002-10-03 Akihisa Hongo Substrate plating apparatus
EP1264918A1 (de) * 2001-06-07 2002-12-11 Shipley Co. L.L.C. Verfahren zur elektrolytischen Kupferplatierung
GB2454141A (en) * 2006-10-19 2009-04-29 Honda Motor Co Ltd Plating apparatus

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WO2015000817A1 (en) 2015-01-08

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