US20040187731A1 - Acid copper electroplating solutions - Google Patents

Acid copper electroplating solutions Download PDF

Info

Publication number
US20040187731A1
US20040187731A1 US10/823,982 US82398204A US2004187731A1 US 20040187731 A1 US20040187731 A1 US 20040187731A1 US 82398204 A US82398204 A US 82398204A US 2004187731 A1 US2004187731 A1 US 2004187731A1
Authority
US
United States
Prior art keywords
poly
carrier
copper
mercapto
bis
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.)
Abandoned
Application number
US10/823,982
Inventor
Qing Wang
Weiji Huang
Miu Lau
Carol Liu
Ce Ma
Edward Chang
Wenpin Ho
Richard Paciej
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US10/823,982 priority Critical patent/US20040187731A1/en
Publication of US20040187731A1 publication Critical patent/US20040187731A1/en
Abandoned legal-status Critical Current

Links

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

Definitions

  • the present invention is related to an improved acid copper electroplating composition. More particularly, the present invention relates to the use of new carriers, brighteners and levelers as well as molecules that combine carrier/brightener and carrier/leveler functionality.
  • Copper electroplating bath solutions are used in a variety of industries. In the semiconductor industry, there is an increasing need for these baths to meet decreasing device feature size, increasing wafer size and high yield.
  • Various proprietary electroplating bath chemistries are commercially available that claim success with regards to the copper metallization process.
  • the bath chemistry should help to fill with copper small yet high aspect ratio trenches and vias, e.g. ⁇ 0.18 ⁇ m and aspect ratio >5, to obtain uniform and void free plating while maintaining high production rates.
  • the plating bath chemistries should also be relatively chemically stable, less corrosive and easily monitored and replenished.
  • Copper sulfate and sulfuric acid are the basics of the acid copper electroplating bath chemistry.
  • Organic additives such as carriers, brighteners, levelers and combinations of these can offer a plating bath to fill the small and high aspect ratio trenches and vias without voids or seams.
  • As-plated copper deposits are of uniform thickness and fine grain size, and highly ⁇ 111> crystal orientated.
  • Brighteners not only produce fine and orientated grain structure for the as-plated deposits but also provide better chemical stability and solubility in the electroplating bath.
  • Brighteners are typically water-soluble sulfonic acids containing mercapto and/or thio groups.
  • U.S. Pat. No. 5,151,170 teaches a brightener that consists essentially of the hydrogen peroxide oxidation product of a dialkylamino-thioxomethyl-thioalkanesulfonic acid wherein each alkyl and alkane group individually contains 1 to 6 carbon atoms. They can produce fine copper deposits by masking the preferential growth sites/planes.
  • Current brighteners can suffer from poor stability, oxidation by air and electrochemical oxidation at the anode, as well as catalytic decomposition at the copper surface. The decomposed products are often detrimental to copper deposition properties.
  • Levelers play a key role in void and seam free trench filling, i.e., superfilling or bottom-up filling.
  • the deposition rate needs to be much faster at the bottom of the features than on the side wall and shoulder of the trenches and vias.
  • different molecular size levelers are employed to tailor different generation (or size) of trenches and vias.
  • the large molecular size is usually preferred for the filling of larger trenches and vias since the diffusion of the levelers towards the bottom of trenches is much slower, which in turn, results in extremely low leveler flux at the bottom and promotes bottom-up filling or superfilling.
  • the larger molecular size can eventually block the openings and prevent the copper ions from entering the trenches. This consequently creates voids when the size of the trench and vias is greatly reduced (e.g., ⁇ 0.1 ⁇ m).
  • the as-plated copper deposits can complete self-annealing process in several hours to have a stable microstructure at room temperature.
  • U.S. Pat. No. 5,051,154 teaches an aqueous electroplating solution comprising at least one soluble copper salt, an electrolyte and at least one organic additive capable of modifying the charge transfer overpotential of the solution in an amount sufficient to shift the overpotential by at least 150 millivolts and being independent of solution agitation.
  • This reference teaches using a wetting agent as a component additive in the system capable of modifying the charge transfer overpotential.
  • Additional additives can include a brightener along with the wetting agent and this can be selected from the group consisting of n,n-dimethyl-dithiocarbamic acid-(3-sulfopropyl) ester; 3-mercapto-propylsulfonic acid(sodium salt); carbonic acid-dithio-o-ethylester-s-ester with 3-mercapto-1-propane sulfonic acid(potassium salt); bisulfopropyl disulfide; 3-(benzthiazolyl-s-thio) propyl sulfonic acid (sodium salt); and pyridinium propyl sulfobetaine.
  • a brightener along with the wetting agent and this can be selected from the group consisting of n,n-dimethyl-dithiocarbamic acid-(3-sulfopropyl) ester; 3-mercapto-propylsulfonic acid(sodium salt); carbon
  • the three component additive may also include levelers such as those selected from the group including 1-(2-hydroxyethyl)-2-imidazolidinethione; 4-mercaptopyridine; 2-mercaptothiazoline; ethylene thiourea; thiourea; and alkylated polyalkyleneimine.
  • levelers such as those selected from the group including 1-(2-hydroxyethyl)-2-imidazolidinethione; 4-mercaptopyridine; 2-mercaptothiazoline; ethylene thiourea; thiourea; and alkylated polyalkyleneimine.
  • the present invention provides for an improved acid copper electroplating bath composition and method for preparing them.
  • the composition comprises an aqueous solution of acid and copper salt, and the improvement comprises the addition of at least one of a carrier; a water soluble mercapto-containing organic brightener compound; and a leveler which comprises an organic compound containing single or multiply charged centers in acidic bath solution.
  • the present invention provides for a method for copper plating or metallization of advanced interconnects (less than 0.18 microns and having an AR (Aspect Ratio) greater than 6) comprising immersing a substrate intended for advanced interconnects into the copper electroplating composition and conducting an electrochemical deposition process.
  • an acid and copper salt are employed.
  • the acid is typically sulfuric acid while the copper salt can be selected from the group consisting of copper sulfate, copper acetate, copper fluoborate, cupric nitrate and copper pyrophosphate.
  • Additional inorganic additives can include both chloride and alkaline species.
  • the chloride can enhance cathode surface adsorption of organic additives such as the carrier and improve the oxidation of the anodes to improve plating efficiency.
  • Alkaline species such as ammonium hydroxide are added to reduce the acidity and corrosivity of this bath solution. Chloride is added in an amount of about 20 to 100 parts per million parts water in the bath, while the alkaline is added in an amount necessary to reduce the solution's pH.
  • the acid copper electroplating solution will have from about 50 to about 250 grams of copper salt per liter of water and about 60 to about 250 grams of sulfuric acid per liter of water.
  • organic additives such as carriers, brighteners, levelers, and combinations of these are also employed to obtain high throwing power to fill the small and high aspect ratio trenches and vias.
  • the carriers used in this invention can comprise conventional ones in the art, e.g., polyethylene glycol and poly(ethylene oxide), and a new class of carriers—polysaccharides.
  • the polysaccharides consist of simple sugars such as fructose and glucose linked by glycosidic bonds. Representative examples include but are not limited to starch, cellulose, amylopectin and amylose.
  • the brighteners useful in this invention possess both stability and solubility in the copper electroplating bath.
  • the brighteners include both water soluble mercapto-containing organic compounds and other organic sulfides. Representative examples include but are not limited to N-methylallyl-N′-methylthiourea; tetramethylthiuram disulfide; ethylethylthiomethyl sulfoxide; ammonium diethyldithiocarbamate; dimethyl-2-thioxo-1,3-dithiole-4,5-dicarboxylate; 3-mercapto-1-propanesulfonic acid sodium salt; 3-mercapto-1-propanesulfonic acid; bis (2-mercaptoethyl) sulfide; ethylene trithio carbonate; ethanethiol; 2-mercaptoethanol; monothioglycerol (1-thioglycerol); 1,2-ethanedithiol; and thiodiethanol.
  • the most preferred brighteners are ammonium diethyldithiocarbamate, 3-mercapto-1-propanesulfonic acid sodium salt, and its free acid form.
  • 3-Mercapto-1-propanesulfonic acid is prepared from 3-mercapto-1-propanesulfonic acid sodium salt by an ion-exchange process using cation ion-exchange resins such as Dowex DR2030 (20-30 mesh), Dowex HCR-W2 (16-40 mesh), Dowex 50Wx8-100 (50-100 mesh, 1.7 meq/mL, 0.80 g/ML), and Dowex 50Wx8-200 (100-200 mesh, 1.7 meq/mL, 0.80 g/mL).
  • the sodium level can be reduced to a few ppm from ⁇ 1500 ppm in original 1 wt. % aqueous solution. Both a packed column with ion-exchange resin and a reaction flask approach using ion- exchange resin can remove sodium to low ppm levels.
  • the need for a sodium-free brightener is important in avoiding sodium contamination of the copper deposited thin layer.
  • the 3-mercapto-1-propanesulfonic acid was prepared by both ion-exchange column and in a reaction flask, and sodium removal efficiency was better than 99% for both methods. This is important regarding bath life as the buildup of sodium in the bath over time would require the bath to be dumped and replenished once the sodium level becomes unacceptably high.
  • the levelers useful in this invention possess single or multiple positively charged centers that will form single or multiple positively charged sites after protonation in the acidic conditions of the bath.
  • the levelers are divided into three groups—polymeric levelers, low molecular weight levelers, and organic dyes.
  • polymeric levelers include but are not limited to polyethylenimine, 80% ethoxylated; poly(allylamine); poly(allylamine hydrochloride); polyaniline, sulfonated, 5 wt.
  • the most preferred polymeric levelers are poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited, and poly(diallyldimethylammonium chloride).
  • low molecular weight levelers include but are not limited to N-containing acyclic systems, N-containing five-membered heterocyclic systems, and N-containing six-membered heterocyclic systems. Most of them also contains mercapto-, sulfide, or disulfide functionalities.
  • N-containing acyclic systems include 2,5-dithiobiurea, dithiooxamide, 1-phenyl-2-thiourea, and diethylenetriamine. The most preferred one is diethylenetriamine.
  • N-containing five/six-membered heterocyclic systems include p-xylenebis(tetrahydrothiophenium) chloride, 2-thiohydantoin, pseudo thiohydantoin, (R)-(-)-thiazolidine-4-carboxylic acid, 3-(2′-thiopyridinium) propyl sulfonate, 2,2′-dipyridyl disulfide, 4,4′-dipyridyl disulfide, thionicotinamide, 4-(trifluoromethyl) -2-pyrimidinethiol, 2-mercapto-4-methylpyrimidine hydrochloride, 5-phenyl-1H-1,2,4-triazole-3-thiol, 5-(4′-pyridyl)-1H-1,2,4-triazole-3-thiol, 2-amino-6-purinethiol, 4-amino-5-(4′-pyridyl)-4H-1,2,4-triazole
  • organic dyes include but are not limited to Bismarck Brown Y, Chicago Sky Blue 6B, and Acid Violet.
  • the organic additives are constantly consumed due to breakdown and oxidation in the electroplating process.
  • the consumed additives are generally compensated for by a replenishing process to maintain constant bath chemistry. Numerous consumption/replenishment cycles may proceed before a complete replacement of the plating bath is necessary. As a result of this process, there is an accumulation of contaminants which can be a critical problem. The contaminants may interfere with the functioning of organic additives and may cause inconsistent plating that is unacceptable to the semiconductor industry.
  • the invention further comprises the use of molecules that combine brightener/carrier and carrier/leveler functionalities.
  • the combination of brightener/carrier is typically a monomeric to polymeric protein chain where the chain is linked by sulfide and disulfide bridges.
  • the combination of carrier/leveler can help improve the stability of the leveler while simplifying the bath by reducing the number of organic additives.
  • Such materials can be poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited, and poly(melamine-co-formaldehyde), partially methylated.
  • the carrier of the present invention may be added in an amount ranging from about 2 to about 1000 parts per million parts water.
  • the leveler may be added in an amount of about 2 parts to about 1000 parts per million parts of water in the electroplating solution.
  • the brightener may be added in an amount ranging from about 5 parts to about 100 parts per million parts water.
  • the combination carrier/brightener When employed, it is added in an amount ranging from about 5 to about 100 parts per million parts water.
  • the combination carrier/leveler when employed may be added in an amount ranging from about 2 to about 1000 parts per million.
  • additives that are found in the baths include wetting agents such as carboxylic acids and antioxidants.
  • Carboxylic acids such as citric acid improve wetting ability of the cathode and provide better adsorption of the organic additives to the cathode.
  • these are added in a range of about 2 to about 1000 parts per million parts water in the bath.
  • Brighteners tend to be oxidized in the vicinity of the anode during and without plating. Oxidized brighteners lose their functionality and cause an inconsistent plating rate and poor quality of the as-plated object.
  • the oxidizing agents near the cathode are typically hydrogen peroxide and oxygen. The present inventors have discovered that continuously purging the bath solution near the anode side with an inert gas will expel oxygen out of the solution.
  • the additive packages of the present invention may be added to the aqueous acid copper electroplating bath either individually or as combinations depending upon the type of substrate being plated.
  • the plating solutions of this invention are used in a conventional manner. They are preferably used at room temperature or higher temperature. During plating, the bath solution is preferably agitated by inert gas, air sparger or by mechanical means.
  • the plating current density can range between 3 mA/cm 2 and 40 mA/cm 2 depending on aspect ratio of trenches and vias.
  • the wave form can be direct current (DC), pulse current (PC) or pulse reverse current (PRC).

Abstract

Improved acid copper electroplating bath compositions are disclosed. The improved bath solutions contain at least one of a carrier; a water-soluble, mercapto-containing organic brightener; and a leveler which comprises an organic compound containing single or multiply charged centers in acidic bath solution. These electroplating bath compositions are used to copper plate advanced interconnects on semiconductor devices.

Description

  • This application claims priority from Provisional Patent Application No. 60/144,159 filed Jul. 15, 1999.[0001]
    • FIELD OF THE INVENTION
  • The present invention is related to an improved acid copper electroplating composition. More particularly, the present invention relates to the use of new carriers, brighteners and levelers as well as molecules that combine carrier/brightener and carrier/leveler functionality. [0002]
    • BACKGROUND OF THE INVENTION
  • Copper electroplating bath solutions are used in a variety of industries. In the semiconductor industry, there is an increasing need for these baths to meet decreasing device feature size, increasing wafer size and high yield. Various proprietary electroplating bath chemistries are commercially available that claim success with regards to the copper metallization process. Ideally, the bath chemistry should help to fill with copper small yet high aspect ratio trenches and vias, e.g. <0.18 μm and aspect ratio >5, to obtain uniform and void free plating while maintaining high production rates. The plating bath chemistries should also be relatively chemically stable, less corrosive and easily monitored and replenished. [0003]
  • Copper sulfate and sulfuric acid are the basics of the acid copper electroplating bath chemistry. Organic additives such as carriers, brighteners, levelers and combinations of these can offer a plating bath to fill the small and high aspect ratio trenches and vias without voids or seams. As-plated copper deposits are of uniform thickness and fine grain size, and highly <111> crystal orientated. [0004]
  • Carriers typically are water-soluble polymers containing —(CH[0005] 2)n—O— where n=1 to 3 or branched derivatives in the main chains. Carriers can form a monolayer film at the cathode surface, which is a barrier to the diffusion of Cu+2 ions to the surface and polarizes the cathode. The proper polarization of the cathode is a prerequisite for producing fine and orientated grain structure. However, carriers tend to decompose into lower molecular fragments at both the cathode and the anode, and lose polarization effectiveness. As such, carriers with high stability are desired.
  • Brighteners not only produce fine and orientated grain structure for the as-plated deposits but also provide better chemical stability and solubility in the electroplating bath. Brighteners are typically water-soluble sulfonic acids containing mercapto and/or thio groups. U.S. Pat. No. 5,151,170 teaches a brightener that consists essentially of the hydrogen peroxide oxidation product of a dialkylamino-thioxomethyl-thioalkanesulfonic acid wherein each alkyl and alkane group individually contains 1 to 6 carbon atoms. They can produce fine copper deposits by masking the preferential growth sites/planes. Current brighteners can suffer from poor stability, oxidation by air and electrochemical oxidation at the anode, as well as catalytic decomposition at the copper surface. The decomposed products are often detrimental to copper deposition properties. [0006]
  • Levelers play a key role in void and seam free trench filling, i.e., superfilling or bottom-up filling. The deposition rate needs to be much faster at the bottom of the features than on the side wall and shoulder of the trenches and vias. As such, different molecular size levelers are employed to tailor different generation (or size) of trenches and vias. The large molecular size is usually preferred for the filling of larger trenches and vias since the diffusion of the levelers towards the bottom of trenches is much slower, which in turn, results in extremely low leveler flux at the bottom and promotes bottom-up filling or superfilling. However, the larger molecular size can eventually block the openings and prevent the copper ions from entering the trenches. This consequently creates voids when the size of the trench and vias is greatly reduced (e.g., ˜0.1 μm). [0007]
  • Various chemically combined brightener/carrier and/or leveler/carrier can further enhance these functions and goals. The as-plated copper deposits can complete self-annealing process in several hours to have a stable microstructure at room temperature. [0008]
    • DESCRIPTION OF THE RELATED ART
  • U.S. Pat. No. 5,051,154 teaches an aqueous electroplating solution comprising at least one soluble copper salt, an electrolyte and at least one organic additive capable of modifying the charge transfer overpotential of the solution in an amount sufficient to shift the overpotential by at least 150 millivolts and being independent of solution agitation. This reference teaches using a wetting agent as a component additive in the system capable of modifying the charge transfer overpotential. Additional additives can include a brightener along with the wetting agent and this can be selected from the group consisting of n,n-dimethyl-dithiocarbamic acid-(3-sulfopropyl) ester; 3-mercapto-propylsulfonic acid(sodium salt); carbonic acid-dithio-o-ethylester-s-ester with 3-mercapto-1-propane sulfonic acid(potassium salt); bisulfopropyl disulfide; 3-(benzthiazolyl-s-thio) propyl sulfonic acid (sodium salt); and pyridinium propyl sulfobetaine. The three component additive may also include levelers such as those selected from the group including 1-(2-hydroxyethyl)-2-imidazolidinethione; 4-mercaptopyridine; 2-mercaptothiazoline; ethylene thiourea; thiourea; and alkylated polyalkyleneimine.[0009]
    • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention provides for an improved acid copper electroplating bath composition and method for preparing them. The composition comprises an aqueous solution of acid and copper salt, and the improvement comprises the addition of at least one of a carrier; a water soluble mercapto-containing organic brightener compound; and a leveler which comprises an organic compound containing single or multiply charged centers in acidic bath solution. [0010]
  • In addition the present invention provides for a method for copper plating or metallization of advanced interconnects (less than 0.18 microns and having an AR (Aspect Ratio) greater than 6) comprising immersing a substrate intended for advanced interconnects into the copper electroplating composition and conducting an electrochemical deposition process. [0011]
  • In a typical acid copper electroplating bath, an acid and copper salt are employed. The acid is typically sulfuric acid while the copper salt can be selected from the group consisting of copper sulfate, copper acetate, copper fluoborate, cupric nitrate and copper pyrophosphate. Additional inorganic additives can include both chloride and alkaline species. The chloride can enhance cathode surface adsorption of organic additives such as the carrier and improve the oxidation of the anodes to improve plating efficiency. Alkaline species such as ammonium hydroxide are added to reduce the acidity and corrosivity of this bath solution. Chloride is added in an amount of about 20 to 100 parts per million parts water in the bath, while the alkaline is added in an amount necessary to reduce the solution's pH. [0012]
  • For the purposes of the present invention, the acid copper electroplating solution will have from about 50 to about 250 grams of copper salt per liter of water and about 60 to about 250 grams of sulfuric acid per liter of water. [0013]
  • In addition to sulfuric acid, copper salt, and inorganic additives disclosed above, as is known. in the art, one or more of organic additives such as carriers, brighteners, levelers, and combinations of these are also employed to obtain high throwing power to fill the small and high aspect ratio trenches and vias. [0014]
  • The carriers used in this invention can comprise conventional ones in the art, e.g., polyethylene glycol and poly(ethylene oxide), and a new class of carriers—polysaccharides. The polysaccharides consist of simple sugars such as fructose and glucose linked by glycosidic bonds. Representative examples include but are not limited to starch, cellulose, amylopectin and amylose. [0015]
  • The brighteners useful in this invention possess both stability and solubility in the copper electroplating bath. The brighteners include both water soluble mercapto-containing organic compounds and other organic sulfides. Representative examples include but are not limited to N-methylallyl-N′-methylthiourea; tetramethylthiuram disulfide; ethylethylthiomethyl sulfoxide; ammonium diethyldithiocarbamate; dimethyl-2-thioxo-1,3-dithiole-4,5-dicarboxylate; 3-mercapto-1-propanesulfonic acid sodium salt; 3-mercapto-1-propanesulfonic acid; bis (2-mercaptoethyl) sulfide; ethylene trithio carbonate; ethanethiol; 2-mercaptoethanol; monothioglycerol (1-thioglycerol); 1,2-ethanedithiol; and thiodiethanol. The most preferred brighteners are ammonium diethyldithiocarbamate, 3-mercapto-1-propanesulfonic acid sodium salt, and its free acid form. 3-Mercapto-1-propanesulfonic acid is prepared from 3-mercapto-1-propanesulfonic acid sodium salt by an ion-exchange process using cation ion-exchange resins such as Dowex DR2030 (20-30 mesh), Dowex HCR-W2 (16-40 mesh), Dowex 50Wx8-100 (50-100 mesh, 1.7 meq/mL, 0.80 g/ML), and Dowex 50Wx8-200 (100-200 mesh, 1.7 meq/mL, 0.80 g/mL). The sodium level can be reduced to a few ppm from ˜1500 ppm in original 1 wt. % aqueous solution. Both a packed column with ion-exchange resin and a reaction flask approach using ion- exchange resin can remove sodium to low ppm levels. [0016]
  • The need for a sodium-free brightener is important in avoiding sodium contamination of the copper deposited thin layer. The 3-mercapto-1-propanesulfonic acid was prepared by both ion-exchange column and in a reaction flask, and sodium removal efficiency was better than 99% for both methods. This is important regarding bath life as the buildup of sodium in the bath over time would require the bath to be dumped and replenished once the sodium level becomes unacceptably high. [0017]
  • The levelers useful in this invention possess single or multiple positively charged centers that will form single or multiple positively charged sites after protonation in the acidic conditions of the bath. In this invention, the levelers are divided into three groups—polymeric levelers, low molecular weight levelers, and organic dyes. Representative examples of polymeric levelers include but are not limited to polyethylenimine, 80% ethoxylated; poly(allylamine); poly(allylamine hydrochloride); polyaniline, sulfonated, 5 wt. % in water, 75 mole % sulfonated; poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited; poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine; polyacrylamide; poly(acrylamide-co-diallyldimethylammonium chloride); poly(diallyldimethylammonium chloride); poly(melamine-co-formaldehyde), partially methylated; poly(4-vinylpyridine), 25% cross-linked; poly(1,2-dihydro-2,2,4-trimethylquinoline). The most preferred polymeric levelers are poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited, and poly(diallyldimethylammonium chloride). [0018]
  • Representative examples of low molecular weight levelers include but are not limited to N-containing acyclic systems, N-containing five-membered heterocyclic systems, and N-containing six-membered heterocyclic systems. Most of them also contains mercapto-, sulfide, or disulfide functionalities. Representative examples of N-containing acyclic systems include 2,5-dithiobiurea, dithiooxamide, 1-phenyl-2-thiourea, and diethylenetriamine. The most preferred one is diethylenetriamine. Representative examples of N-containing five/six-membered heterocyclic systems include p-xylenebis(tetrahydrothiophenium) chloride, 2-thiohydantoin, pseudo thiohydantoin, (R)-(-)-thiazolidine-4-carboxylic acid, 3-(2′-thiopyridinium) propyl sulfonate, 2,2′-dipyridyl disulfide, 4,4′-dipyridyl disulfide, thionicotinamide, 4-(trifluoromethyl) -2-pyrimidinethiol, 2-mercapto-4-methylpyrimidine hydrochloride, 5-phenyl-1H-1,2,4-triazole-3-thiol, 5-(4′-pyridyl)-1H-1,2,4-triazole-3-thiol, 2-amino-6-purinethiol, 4-amino-5-(4′-pyridyl)-4H-1,2,4-triazole-3-thiol, diethyl heptadedecyl imidazolinium ethylsulfate, hexamethylenetetraamine, 1,3-bis(3-pyridylmethyl)-2-thiourea, 2,4-diamino-6-mercaptopyrimidine hemisulfate, dithiouracil, 4,5-diamino-2,6-dimercaptopyrimidine, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine hemisulfate hydrate, 4(5)-imidazoledithio-carboxylic acid, 2-mercapto-5-benzimidazolesulfonic acid, sodium salt dihydrate, 2-thiouracil, trithio cyanuric acid, (2-pyrimidylthio) acetic acid, 7-trifluoromethyl-4-quinlinethiol, 5-carbethoxy-2-thiouracil, 1H-1,2,4-triazole-3-thiol, 1-phenyl-1H-1,2,4-triazole-5-thiol, N,N′-ethylene-thiourea, and 2-mercapto benzothiazole. The most preferred one is thionicotinamide. [0019]
  • Representative examples of organic dyes include but are not limited to Bismarck Brown Y, Chicago Sky Blue 6B, and Acid Violet. [0020]
  • The organic additives are constantly consumed due to breakdown and oxidation in the electroplating process. The consumed additives are generally compensated for by a replenishing process to maintain constant bath chemistry. Numerous consumption/replenishment cycles may proceed before a complete replacement of the plating bath is necessary. As a result of this process, there is an accumulation of contaminants which can be a critical problem. The contaminants may interfere with the functioning of organic additives and may cause inconsistent plating that is unacceptable to the semiconductor industry. [0021]
  • It has been found that removal of organic additives can be accomplished with activated carbon such as type 4040 and DCL activated carbon from Barneby Scientific Corp. The bath can be filtered through an activated carbon bed and returned to the plating bath without the need for dumping and restocking the plating bath. The increased number of cycles without having to remake the bath improve effectiveness and economics of the plating process. [0022]
  • This consumption and breakdown of the plating bath additives will result in the need for replenishment of these additives. An accurate determination is needed in-situ and feedback provided fairly rapidly to enable efficient use of baths by semiconductor fabs. The criteria for this analysis include the ability to separate bath components, minimum detection limits, measurement time, accuracy and repeatability and the complexity and frequency of calibration and maintenance. Electrochemical analytical techniques such as cyclic voltammetric stripping (CVS), AC-cyclic voltammetry (AC-CV), AC impedance spectroscopy (AC-IS) and pulsed cyclic galvanostatic analysis (PCGA) have been employed. CVS is generally preferred as it provides relatively high measurement accuracy and fast test results while not generating waste. High performance liquid chromatography (HPLC) is also employed as it offers the advantage of allowing quantitative measurement of contaminants and determination of break-down additives. [0023]
  • The invention further comprises the use of molecules that combine brightener/carrier and carrier/leveler functionalities. The combination of brightener/carrier is typically a monomeric to polymeric protein chain where the chain is linked by sulfide and disulfide bridges. The combination of carrier/leveler can help improve the stability of the leveler while simplifying the bath by reducing the number of organic additives. Such materials can be poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited, and poly(melamine-co-formaldehyde), partially methylated. [0024]
  • The carrier of the present invention may be added in an amount ranging from about 2 to about 1000 parts per million parts water. The leveler may be added in an amount of about 2 parts to about 1000 parts per million parts of water in the electroplating solution. [0025]
  • The brightener may be added in an amount ranging from about 5 parts to about 100 parts per million parts water. When the combination carrier/brightener is employed, it is added in an amount ranging from about 5 to about 100 parts per million parts water. The combination carrier/leveler when employed may be added in an amount ranging from about 2 to about 1000 parts per million. [0026]
  • Other additives that are found in the baths include wetting agents such as carboxylic acids and antioxidants. Carboxylic acids such as citric acid improve wetting ability of the cathode and provide better adsorption of the organic additives to the cathode. Typically, these are added in a range of about 2 to about 1000 parts per million parts water in the bath. [0027]
  • Brighteners tend to be oxidized in the vicinity of the anode during and without plating. Oxidized brighteners lose their functionality and cause an inconsistent plating rate and poor quality of the as-plated object. The oxidizing agents near the cathode are typically hydrogen peroxide and oxygen. The present inventors have discovered that continuously purging the bath solution near the anode side with an inert gas will expel oxygen out of the solution. [0028]
  • The additive packages of the present invention may be added to the aqueous acid copper electroplating bath either individually or as combinations depending upon the type of substrate being plated. [0029]
  • The plating solutions of this invention are used in a conventional manner. They are preferably used at room temperature or higher temperature. During plating, the bath solution is preferably agitated by inert gas, air sparger or by mechanical means. The plating current density can range between 3 mA/cm[0030] 2 and 40 mA/cm2 depending on aspect ratio of trenches and vias. The wave form can be direct current (DC), pulse current (PC) or pulse reverse current (PRC).
  • In studies performed using 67 g/l of CuSO[0031] 4-5H2O, 170 g/l of H2SO4 and 45 g/l of C1− as the starting bath, good plating results were obtained using a current density of 3.2 mA/cm2 and 25.5 mA/cm2 with DC, PC or PRC wave form. The following additive combinations produced the best results regarding trench filling.
    Plating Solution Composition (PPM)
    1 C1(20) B1(12) L1 (15)
    2 C1(20) B1(12) L2 (25)
    3 C1(20) B1(12) L3 (25)
    4 C1(20) B1(12) L4 (25)
  • While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention. [0032]

Claims (23)

1-38 (cancelled)
39. A method for copper plating of advanced interconnects comprising immersing said interconnects in a copper plating bath comprising an aqueous solution of an acid and a copper salt and at least one of a carrier compound; a water-soluble, mercapto-containing organic brightener compound; and a leveler compound containing single and multiply charged centers; wherein said leveler compound is selected from the group consisting of poly(allylamine); poly(allylamine hydrochloride); polyaniline, sulfonated, 5 wt. % in water, 75 mole % sulfonated; poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited; poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine; polyacrylamide; poly(acrylamide-co-diallyldimethylammonium chloride); poly(diallyldimethylammonium chloride); poly(melamine-co-formaldehyde), partially methylated; poly(4-vinylpyridine), 25% cross-linked; and poly(1,2-dihydro-2,2,4-trimethylquinoline).
40. The method as claimed in claim 39 wherein said acid is sulfuric acid.
41. The method as claimed in claim 39 wherein said copper salt is selected from the group consisting of copper sulfate, copper acetate, copper fluoborate, cupric nitrate and copper pyrophosphate.
42. The method as claimed in claim 41 wherein said copper salt is copper sulfate.
43. The method as claimed in claim 39 wherein said carrier compound is selected from the group consisting of a polysaccharide compound, polyethylene glycol and poly(ethylene oxide).
44. The method as claimed in claim 43 wherein said polysaccharide carrier compound is selected from the group consisting of starch, cellulose, amylopectin and amylose.
45. The method as claimed in claim 39 wherein said water-soluble, mercapto-containing organic brightener is selected from the group consisting of N-methylallyl-N′-methylthiourea; tetramethylthiuram disulfide; ethylethylthiomethyl sulfoxide; ammonium diethyldithiocarbamate; dimethyl-2-thioxo-1,3-dithiole-4,5-dicarboxylate; 3-mercapto-1-propanesulfonic acid sodium salt; 3-mercapto-1-propanesulfonic acid; bis (2-mercaptoethyl) sulfide; ethylene trithio carbonate; ethanethiol; 2-mercaptoethanol; monothioglycerol (1-thioglycerol); 1,2-ethanedithiol; and thiodiethanol.
46. The method as claimed in claim 45 wherein said water-soluble, mercapto-containing organic brightener is selected from the group consisting of ammonium diethyldithiocarbamate, 3-mercapto-1-propanesulfonic acid sodium salt, and 3-mercapto-1-propanesulfonic acid.
47-48 (cancelled)
49. The method as claimed in claim 46 wherein said leveler compound is selected from the group consisting of poly[(bis(2-chloroethyl)ether-alt-1,2-bis[3(-dimethylamino)propyl]urea, quaternited, and poly(diallyl dimethylammonium chloride).
50-53 (cancelled)
54. The method as claimed in claim 39 further comprising a brightener/carrier molecule.
55. The method as claimed in claim 54 wherein said brightener/carrier molecule is polymeric protein.
56. The method as claimed in claim 39 further comprising a carrier/leveler molecule.
57. The method as claimed in claim 56 wherein said carrier/leveler molecule is selected from the group consisting of poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl] urea, quaternited, and poly(melamine-co-formaldehyde).
58. The method as claimed in claim 39 wherein said carrier is present in the composition in an amount ranging from about 2 to about 1000 parts per million parts water.
59. The method as claimed in claim 39 wherein said leveler is present in the composition in an amount ranging from about 2 to about 1000 parts per million parts water.
60. The method as claimed in claim 39 wherein said brightener is present in the composition in an amount ranging from about 5 to about 100 parts per million parts water.
61. The method as claimed in claim 39 wherein said carrier/brightener is present in an amount ranging from about 5 to about 1000 parts per million parts water and said carrier/leveler is present in an amount ranging from about 2 to about 1000 parts per million parts water.
62. The method as claimed in claim 39 wherein said compounds are added either individually or as combinations to said aqueous solution.
63. The method as claimed in claim 39 wherein a current between 3 mA/cm2 and 40 mA/cm2 is applied to said solution.
64. The method as claimed in claim 63 wherein the wave form of said current is selected from the group consisting of direct current, pulse current and pulse reverse current.
US10/823,982 1999-07-15 2004-04-14 Acid copper electroplating solutions Abandoned US20040187731A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/823,982 US20040187731A1 (en) 1999-07-15 2004-04-14 Acid copper electroplating solutions

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14415999P 1999-07-15 1999-07-15
US58359900A 2000-05-31 2000-05-31
US10/823,982 US20040187731A1 (en) 1999-07-15 2004-04-14 Acid copper electroplating solutions

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US58359900A Division 1999-07-15 2000-05-31

Publications (1)

Publication Number Publication Date
US20040187731A1 true US20040187731A1 (en) 2004-09-30

Family

ID=26841728

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/823,982 Abandoned US20040187731A1 (en) 1999-07-15 2004-04-14 Acid copper electroplating solutions

Country Status (4)

Country Link
US (1) US20040187731A1 (en)
EP (1) EP1069211A3 (en)
JP (1) JP2001073182A (en)
KR (1) KR20010015342A (en)

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040222104A1 (en) * 2003-02-19 2004-11-11 Rohm And Haas Electronic Materials, L.L.C Electroplating composition
US20050045486A1 (en) * 2003-07-09 2005-03-03 Tsuyoshi Sahoda Plating method and plating solution
US20050045488A1 (en) * 2002-03-05 2005-03-03 Enthone Inc. Copper electrodeposition in microelectronics
US20060134902A1 (en) * 2004-12-21 2006-06-22 Dubin Valery M Method for constructing contact formations
US20070084732A1 (en) * 2005-09-30 2007-04-19 Rohm And Haas Electronic Materials Llc Leveler compounds
US20070158199A1 (en) * 2005-12-30 2007-07-12 Haight Scott M Method to modulate the surface roughness of a plated deposit and create fine-grained flat bumps
US20080121527A1 (en) * 2002-03-05 2008-05-29 Enthone Inc. Defect reduction in electrodeposited copper for semiconductor applications
US20080181813A1 (en) * 2007-01-26 2008-07-31 Baker Hughes Incorporated Novel Mercaptan-Based Corrosion Inhibitors
US20090166213A1 (en) * 2005-10-31 2009-07-02 Mitsui Mining & Smelting Co., Ltd. Production method of electro-deposited copper foil, electro-deposited copper foil obtained by the production method, surface-treated copper foil obtained by using the electro-deposited copper foil and copper-clad laminate obtained by using the electro-deposited copper foil or the surface-treated copper foil
US20090188805A1 (en) * 2008-01-25 2009-07-30 Government Of The United States Of America, As Represented By The Superconformal electrodeposition of nickel iron and cobalt magnetic alloys
US20100089758A1 (en) * 2006-10-03 2010-04-15 Mitsui Mining & Smelting Co., Ltd. Method of preparing electrolytic copper solution acidified with sulfuric acid, sulfuric-acid-acidified electrolytic copper solution prepared by the preparation method, and electrodeposited copper film
US20100126872A1 (en) * 2008-11-26 2010-05-27 Enthone, Inc. Electrodeposition of copper in microelectronics with dipyridyl-based levelers
EP2199315A1 (en) 2008-12-19 2010-06-23 Basf Se Composition for metal electroplating comprising leveling agent
US20100219081A1 (en) * 2007-05-21 2010-09-02 C. Uyemura & Co., Ltd. Copper electroplating bath
US20100255269A1 (en) * 2009-04-03 2010-10-07 Osaka Prefecture University Public Corporation Copper filling-up method
CN101892501A (en) * 2009-05-18 2010-11-24 公立大学法人大阪府立大学 Copper filling-up method
WO2011064154A2 (en) 2009-11-27 2011-06-03 Basf Se Composition for metal electroplating comprising leveling agent
WO2011113908A1 (en) 2010-03-18 2011-09-22 Basf Se Composition for metal electroplating comprising leveling agent
US20120211369A1 (en) * 2011-02-18 2012-08-23 Myung-Beom Park Copper electroplating method
WO2012175249A1 (en) * 2011-06-22 2012-12-27 Atotech Deutschland Gmbh Method for copper plating
CN104854265A (en) * 2012-11-26 2015-08-19 德国艾托特克公司 Copper plating bath composition
US20160115618A1 (en) * 2014-10-27 2016-04-28 International Business Machines Corporation System for treating solution for use in electroplating application and method for treating solution for use in electroplating application
US9365943B2 (en) 2010-12-15 2016-06-14 Rohm And Haas Electronic Materials Llc Method of electroplating uniform copper layers
CN105899715A (en) * 2013-12-09 2016-08-24 阿文尼公司 Copper electrodeposition bath containing electrochemically inert cation
US20180112321A1 (en) * 2015-11-26 2018-04-26 Fine Feature Electrodeposition Research Institute, Inc. Acidic copper plating solution, acidic copper plated product, and method for producing semiconductor device
US9963797B2 (en) * 2013-10-22 2018-05-08 Atotech Deutschland Gmbh Copper electroplating method
US20180142369A1 (en) * 2015-06-26 2018-05-24 Sumitimo Metal Mining Co., Ltd. Electrically conductive substrate
US10221496B2 (en) 2008-11-26 2019-03-05 Macdermid Enthone Inc. Copper filling of through silicon vias
US10538850B2 (en) 2015-04-20 2020-01-21 Atotech Deutschland Gmbh Electrolytic copper plating bath compositions and a method for their use
US10767275B2 (en) 2015-08-31 2020-09-08 Atotech Deutschland Gmbh Aqueous copper plating baths and a method for deposition of copper or copper alloy onto a substrate
US10882842B2 (en) 2017-02-09 2021-01-05 Atotech Deutschland Gmbh Pyridinium compounds, a synthesis method therefor, metal or metal alloy plating baths containing said pyridinium compounds and a method for use of said metal or metal alloy plating baths
US10917966B2 (en) 2018-01-29 2021-02-09 Corning Incorporated Articles including metallized vias
US10932371B2 (en) 2014-11-05 2021-02-23 Corning Incorporated Bottom-up electrolytic via plating method
WO2021091743A1 (en) * 2019-11-05 2021-05-14 Macdermid Enthone Inc. Single step electrolytic method of filling through holes in printed circuit boards and other substrates
US11066553B2 (en) 2015-08-31 2021-07-20 Atotech Deutschland Gmbh Imidazoyl urea polymers and their use in metal or metal alloy plating bath compositions
CN113956479A (en) * 2021-11-26 2022-01-21 电子科技大学 Copper electroplating accelerator and synthesis method and application thereof
CN116751362A (en) * 2023-08-21 2023-09-15 广东腐蚀科学与技术创新研究院 Water-soluble diaminourea polymer and preparation method and application thereof

Families Citing this family (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7014679B2 (en) * 2001-02-07 2006-03-21 Mykrolis Corporation Process for degassing an aqueous plating solution
KR20020092444A (en) * 2001-02-23 2002-12-11 가부시키 가이샤 에바라 세이사꾸쇼 Copper-plating solution, plating method and plating apparatus
JP4793530B2 (en) * 2001-07-02 2011-10-12 上村工業株式会社 Copper sulfate plating bath
US6736954B2 (en) * 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
JP3789107B2 (en) 2002-07-23 2006-06-21 株式会社日鉱マテリアルズ Copper electrolytic solution containing amine compound and organic sulfur compound having specific skeleton as additive, and electrolytic copper foil produced thereby
JP4115240B2 (en) * 2002-10-21 2008-07-09 日鉱金属株式会社 Copper electrolytic solution containing quaternary amine compound having specific skeleton and organic sulfur compound as additive, and electrolytic copper foil produced thereby
JP4534460B2 (en) * 2002-11-11 2010-09-01 凸版印刷株式会社 Copper plating hardness maintenance agent, copper plating method, and gravure plate and lens mold using the same
JP4510369B2 (en) 2002-11-28 2010-07-21 日本リーロナール有限会社 Electrolytic copper plating method
CN1312323C (en) * 2002-12-25 2007-04-25 日矿金属株式会社 Copper electrolytic solution containing quaternary amine compound having specific skeleton and organic sulfur compound as additives, and electrolytic copper foil produced therefrom
US7128822B2 (en) 2003-06-04 2006-10-31 Shipley Company, L.L.C. Leveler compounds
US20050211564A1 (en) * 2004-03-29 2005-09-29 Taiwan Semiconductor Manufacturing Co., Ltd. Method and composition to enhance wetting of ECP electrolyte to copper seed
TW200613586A (en) 2004-07-22 2006-05-01 Rohm & Haas Elect Mat Leveler compounds
JPWO2006018872A1 (en) * 2004-08-18 2008-05-01 荏原ユージライト株式会社 Additive for copper plating and method for producing electronic circuit board using the same
JP4976725B2 (en) * 2005-03-31 2012-07-18 三井金属鉱業株式会社 Copper electrolyte and method for forming electrodeposited copper film using the copper electrolyte
US7662981B2 (en) 2005-07-16 2010-02-16 Rohm And Haas Electronic Materials Llc Leveler compounds
JP4816901B2 (en) * 2005-11-21 2011-11-16 上村工業株式会社 Electro copper plating bath
JP4895734B2 (en) * 2006-09-08 2012-03-14 荏原ユージライト株式会社 Leveling agent for plating, additive composition for acidic copper plating bath, acidic copper plating bath, and plating method using the plating bath
JP2008088524A (en) * 2006-10-04 2008-04-17 Ebara Udylite Kk Copper sulfate plating solution for printed board
EP2128903B1 (en) * 2008-05-30 2017-02-22 ATOTECH Deutschland GmbH Electroplating additive for the deposition of a metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)-group 13 (IIIA)-group 16 (VIA)
JP5525762B2 (en) * 2008-07-01 2014-06-18 上村工業株式会社 Electroless plating solution, electroless plating method using the same, and method for manufacturing wiring board
US9683302B2 (en) 2010-06-01 2017-06-20 Basf Se Composition for metal electroplating comprising leveling agent
EP2392692A1 (en) 2010-06-01 2011-12-07 Basf Se Composition for metal electroplating comprising leveling agent
JP5505153B2 (en) * 2010-07-16 2014-05-28 上村工業株式会社 Electro copper plating bath and electro copper plating method
GB201100447D0 (en) * 2011-01-12 2011-02-23 Johnson Matthey Plc Improvements in coating technology
US20140238868A1 (en) * 2013-02-25 2014-08-28 Dow Global Technologies Llc Electroplating bath
CN103469260A (en) * 2013-09-27 2013-12-25 昆山纯柏精密五金有限公司 Acid copper plating method of hardware
TWI710671B (en) * 2014-09-15 2020-11-21 美商麥德美樂思公司 Levelers for copper deposition in microelectronics
US9611560B2 (en) 2014-12-30 2017-04-04 Rohm And Haas Electronic Materials Llc Sulfonamide based polymers for copper electroplating
US9783905B2 (en) 2014-12-30 2017-10-10 Rohm and Haas Electronic Mateirals LLC Reaction products of amino acids and epoxies
US9725816B2 (en) 2014-12-30 2017-08-08 Rohm And Haas Electronic Materials Llc Amino sulfonic acid based polymers for copper electroplating
CN105239109A (en) * 2015-10-28 2016-01-13 福州瑞华印制线路板有限公司 Haring cell copper electroplating method
CN105200467B (en) * 2015-11-02 2019-01-29 江苏梦得新材料科技有限公司 A kind of Gravure hard copper additive and plating solution
ES2881029T3 (en) 2018-01-09 2021-11-26 Atotech Deutschland Gmbh Ureylene additive, its use and a method for its preparation
WO2020021965A1 (en) * 2018-07-27 2020-01-30 三菱マテリアル株式会社 Tin alloy plating solution
JP6645609B2 (en) 2018-07-27 2020-02-14 三菱マテリアル株式会社 Tin alloy plating solution
CN110938848B (en) * 2019-12-26 2021-05-11 江苏艾森半导体材料股份有限公司 Composition for electrolytic deposition of copper and acid copper electroplating solution
EP3933073B1 (en) 2020-06-29 2023-11-29 Atotech Deutschland GmbH & Co. KG Copper electroplating bath
CN112144083B (en) * 2020-09-22 2021-12-10 广州三孚新材料科技股份有限公司 Cyanide-free copper plating electroplating solution for solar cell and preparation method thereof
CN116710599A (en) * 2021-01-20 2023-09-05 富士胶片株式会社 Plating solution and method for producing metal-filled structure
EP4032930B1 (en) 2021-01-22 2023-08-30 Atotech Deutschland GmbH & Co. KG Biuret-based quaternized polymers and their use in metal or metal alloy plating baths
CN113430598B (en) * 2021-08-27 2021-11-16 深圳市板明科技股份有限公司 Circuit board blind hole filling electro-coppering solution and application thereof

Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954331A (en) * 1958-08-14 1960-09-27 Dayton Bright Copper Company Bright copper plating bath
US3267010A (en) * 1962-04-16 1966-08-16 Udylite Corp Electrodeposition of copper from acidic baths
US3328273A (en) * 1966-08-15 1967-06-27 Udylite Corp Electro-deposition of copper from acidic baths
US3615736A (en) * 1969-01-06 1971-10-26 Enthone Electroless copper plating bath
US3715289A (en) * 1971-02-08 1973-02-06 Stauffer Chemical Co Brightener composition for acid copper electroplating baths
US4004956A (en) * 1974-08-14 1977-01-25 Enthone, Incorporated Selectively stripping tin or tin-lead alloys from copper substrates
US4028161A (en) * 1969-08-19 1977-06-07 Kuraray Co., Ltd. Method of making sheet material
US4134803A (en) * 1977-12-21 1979-01-16 R. O. Hull & Company, Inc. Nitrogen and sulfur compositions and acid copper plating baths
US4304646A (en) * 1980-10-27 1981-12-08 Enthone, Incorporated Method for selective removal of copper contaminants from activator solutions containing palladium and tin
US4324623A (en) * 1980-01-12 1982-04-13 Koito Seisakusho Co. Ltd. Method and apparatus for replenishing an electroplating bath with metal to be deposited
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4384930A (en) * 1981-08-21 1983-05-24 Mcgean-Rohco, Inc. Electroplating baths, additives therefor and methods for the electrodeposition of metals
US4430173A (en) * 1981-07-24 1984-02-07 Rhone-Poulenc Specialties Chimiques Additive composition, bath and process for acid copper electroplating
US4490220A (en) * 1982-09-30 1984-12-25 Learonal, Inc. Electrolytic copper plating solutions
US4555315A (en) * 1984-05-29 1985-11-26 Omi International Corporation High speed copper electroplating process and bath therefor
US4717439A (en) * 1985-10-24 1988-01-05 Enthone, Incorporated Process for the treatment of copper oxide in the preparation of printed circuit boards
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4790912A (en) * 1985-06-06 1988-12-13 Techno-Instruments Investments Ltd. Selective plating process for the electrolytic coating of circuit boards without an electroless metal coating
US4808481A (en) * 1986-10-31 1989-02-28 American Cyanamid Company Injection molding granules comprising copper coated fibers
US4897165A (en) * 1988-08-23 1990-01-30 Shipley Company Inc. Electroplating composition and process for plating through holes in printed circuit boards
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US4954226A (en) * 1988-12-21 1990-09-04 International Business Machines Corporation Additive plating bath and process
US5051154A (en) * 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
US5147905A (en) * 1991-05-01 1992-09-15 The Dow Chemical Company Advanced and unadvanced compositions, nucleophilic derivatives thereof and curable and coating compositions thereof
US5151170A (en) * 1991-12-19 1992-09-29 Mcgean-Rohco, Inc. Acid copper electroplating bath containing brightening additive
US5174886A (en) * 1991-02-22 1992-12-29 Mcgean-Rohco, Inc. High-throw acid copper plating using inert electrolyte
US5215645A (en) * 1989-09-13 1993-06-01 Gould Inc. Electrodeposited foil with controlled properties for printed circuit board applications and procedures and electrolyte bath solutions for preparing the same
US5266212A (en) * 1992-10-13 1993-11-30 Enthone-Omi, Inc. Purification of cyanide-free copper plating baths
US5328589A (en) * 1992-12-23 1994-07-12 Enthone-Omi, Inc. Functional fluid additives for acid copper electroplating baths
US5402465A (en) * 1993-12-02 1995-03-28 Foltz; Jack D. Telephone trouble isolator
US5433840A (en) * 1991-08-07 1995-07-18 Atotech Deutschland Gmbh Acid bath for the galvanic deposition of copper, and the use of such a bath
US5630950A (en) * 1993-07-09 1997-05-20 Enthone-Omi, Inc. Copper brightening process and bath
US5730854A (en) * 1996-05-30 1998-03-24 Enthone-Omi, Inc. Alkoxylated dimercaptans as copper additives and de-polarizing additives
US5733429A (en) * 1996-09-10 1998-03-31 Enthone-Omi, Inc. Polyacrylic acid additives for copper electrorefining and electrowinning
US5750018A (en) * 1997-03-18 1998-05-12 Learonal, Inc. Cyanide-free monovalent copper electroplating solutions
US5849171A (en) * 1990-10-13 1998-12-15 Atotech Deutschland Gmbh Acid bath for copper plating and process with the use of this combination
US5863410A (en) * 1997-06-23 1999-01-26 Circuit Foil Usa, Inc. Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby
US6261433B1 (en) * 1998-04-21 2001-07-17 Applied Materials, Inc. Electro-chemical deposition system and method of electroplating on substrates

Patent Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954331A (en) * 1958-08-14 1960-09-27 Dayton Bright Copper Company Bright copper plating bath
US3267010A (en) * 1962-04-16 1966-08-16 Udylite Corp Electrodeposition of copper from acidic baths
US3328273A (en) * 1966-08-15 1967-06-27 Udylite Corp Electro-deposition of copper from acidic baths
US3615736A (en) * 1969-01-06 1971-10-26 Enthone Electroless copper plating bath
US4028161A (en) * 1969-08-19 1977-06-07 Kuraray Co., Ltd. Method of making sheet material
US3715289A (en) * 1971-02-08 1973-02-06 Stauffer Chemical Co Brightener composition for acid copper electroplating baths
US4004956A (en) * 1974-08-14 1977-01-25 Enthone, Incorporated Selectively stripping tin or tin-lead alloys from copper substrates
US4134803A (en) * 1977-12-21 1979-01-16 R. O. Hull & Company, Inc. Nitrogen and sulfur compositions and acid copper plating baths
US4324623A (en) * 1980-01-12 1982-04-13 Koito Seisakusho Co. Ltd. Method and apparatus for replenishing an electroplating bath with metal to be deposited
US4304646A (en) * 1980-10-27 1981-12-08 Enthone, Incorporated Method for selective removal of copper contaminants from activator solutions containing palladium and tin
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US4430173A (en) * 1981-07-24 1984-02-07 Rhone-Poulenc Specialties Chimiques Additive composition, bath and process for acid copper electroplating
US4384930A (en) * 1981-08-21 1983-05-24 Mcgean-Rohco, Inc. Electroplating baths, additives therefor and methods for the electrodeposition of metals
US4490220A (en) * 1982-09-30 1984-12-25 Learonal, Inc. Electrolytic copper plating solutions
US4555315A (en) * 1984-05-29 1985-11-26 Omi International Corporation High speed copper electroplating process and bath therefor
US4790912A (en) * 1985-06-06 1988-12-13 Techno-Instruments Investments Ltd. Selective plating process for the electrolytic coating of circuit boards without an electroless metal coating
US4717439A (en) * 1985-10-24 1988-01-05 Enthone, Incorporated Process for the treatment of copper oxide in the preparation of printed circuit boards
US4808481A (en) * 1986-10-31 1989-02-28 American Cyanamid Company Injection molding granules comprising copper coated fibers
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US4786746A (en) * 1987-09-18 1988-11-22 Pennsylvania Research Corporation Copper electroplating solutions and methods of making and using them
US4897165A (en) * 1988-08-23 1990-01-30 Shipley Company Inc. Electroplating composition and process for plating through holes in printed circuit boards
US5051154A (en) * 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
US4954226A (en) * 1988-12-21 1990-09-04 International Business Machines Corporation Additive plating bath and process
US5215645A (en) * 1989-09-13 1993-06-01 Gould Inc. Electrodeposited foil with controlled properties for printed circuit board applications and procedures and electrolyte bath solutions for preparing the same
US5849171A (en) * 1990-10-13 1998-12-15 Atotech Deutschland Gmbh Acid bath for copper plating and process with the use of this combination
US5174886A (en) * 1991-02-22 1992-12-29 Mcgean-Rohco, Inc. High-throw acid copper plating using inert electrolyte
US5147905A (en) * 1991-05-01 1992-09-15 The Dow Chemical Company Advanced and unadvanced compositions, nucleophilic derivatives thereof and curable and coating compositions thereof
US5433840A (en) * 1991-08-07 1995-07-18 Atotech Deutschland Gmbh Acid bath for the galvanic deposition of copper, and the use of such a bath
US5151170A (en) * 1991-12-19 1992-09-29 Mcgean-Rohco, Inc. Acid copper electroplating bath containing brightening additive
US5266212A (en) * 1992-10-13 1993-11-30 Enthone-Omi, Inc. Purification of cyanide-free copper plating baths
US5328589A (en) * 1992-12-23 1994-07-12 Enthone-Omi, Inc. Functional fluid additives for acid copper electroplating baths
US5630950A (en) * 1993-07-09 1997-05-20 Enthone-Omi, Inc. Copper brightening process and bath
US5402465A (en) * 1993-12-02 1995-03-28 Foltz; Jack D. Telephone trouble isolator
US5730854A (en) * 1996-05-30 1998-03-24 Enthone-Omi, Inc. Alkoxylated dimercaptans as copper additives and de-polarizing additives
US5733429A (en) * 1996-09-10 1998-03-31 Enthone-Omi, Inc. Polyacrylic acid additives for copper electrorefining and electrowinning
US5750018A (en) * 1997-03-18 1998-05-12 Learonal, Inc. Cyanide-free monovalent copper electroplating solutions
US5863410A (en) * 1997-06-23 1999-01-26 Circuit Foil Usa, Inc. Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby
US6261433B1 (en) * 1998-04-21 2001-07-17 Applied Materials, Inc. Electro-chemical deposition system and method of electroplating on substrates

Cited By (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050045488A1 (en) * 2002-03-05 2005-03-03 Enthone Inc. Copper electrodeposition in microelectronics
US20140102909A1 (en) * 2002-03-05 2014-04-17 Enthone Inc. Copper electrodeposition in microelectronics
US8608933B2 (en) * 2002-03-05 2013-12-17 Enthone Inc. Copper electrodeposition in microelectronics
US9222188B2 (en) * 2002-03-05 2015-12-29 Enthone Inc. Defect reduction in electrodeposited copper for semiconductor applications
US20080121527A1 (en) * 2002-03-05 2008-05-29 Enthone Inc. Defect reduction in electrodeposited copper for semiconductor applications
US9493884B2 (en) * 2002-03-05 2016-11-15 Enthone Inc. Copper electrodeposition in microelectronics
US8002962B2 (en) * 2002-03-05 2011-08-23 Enthone Inc. Copper electrodeposition in microelectronics
US20040222104A1 (en) * 2003-02-19 2004-11-11 Rohm And Haas Electronic Materials, L.L.C Electroplating composition
US20050045486A1 (en) * 2003-07-09 2005-03-03 Tsuyoshi Sahoda Plating method and plating solution
US7442634B2 (en) * 2004-12-21 2008-10-28 Intel Corporation Method for constructing contact formations
US20060134902A1 (en) * 2004-12-21 2006-06-22 Dubin Valery M Method for constructing contact formations
US20070084732A1 (en) * 2005-09-30 2007-04-19 Rohm And Haas Electronic Materials Llc Leveler compounds
US8506788B2 (en) 2005-09-30 2013-08-13 Rohm And Haas Electronic Materials Llc Leveler compounds
US8262891B2 (en) 2005-09-30 2012-09-11 Rohm And Haas Electronic Materials Llc Leveler compounds
US20090166213A1 (en) * 2005-10-31 2009-07-02 Mitsui Mining & Smelting Co., Ltd. Production method of electro-deposited copper foil, electro-deposited copper foil obtained by the production method, surface-treated copper foil obtained by using the electro-deposited copper foil and copper-clad laminate obtained by using the electro-deposited copper foil or the surface-treated copper foil
US20070158199A1 (en) * 2005-12-30 2007-07-12 Haight Scott M Method to modulate the surface roughness of a plated deposit and create fine-grained flat bumps
US20100089758A1 (en) * 2006-10-03 2010-04-15 Mitsui Mining & Smelting Co., Ltd. Method of preparing electrolytic copper solution acidified with sulfuric acid, sulfuric-acid-acidified electrolytic copper solution prepared by the preparation method, and electrodeposited copper film
US8419920B2 (en) * 2006-10-03 2013-04-16 Mitsui Mining & Smelting Co., Ltd. Method of preparing electrolytic copper solution acidified with sulfuric acid, sulfuric-acid-acidified electrolytic copper solution prepared by the preparation method, and electrodeposited copper film
US20080181813A1 (en) * 2007-01-26 2008-07-31 Baker Hughes Incorporated Novel Mercaptan-Based Corrosion Inhibitors
AU2007345192B2 (en) * 2007-01-26 2012-11-22 Baker Hughes Incorporated Novel mercaptan-based corrosion inhibitors
US20110040126A1 (en) * 2007-01-26 2011-02-17 Baker Hughes Incorporated Novel mercaptan-based corrosion inhibitors
US8679317B2 (en) * 2007-05-21 2014-03-25 C. Uyemura & Co., Ltd. Copper electroplating bath
US20100219081A1 (en) * 2007-05-21 2010-09-02 C. Uyemura & Co., Ltd. Copper electroplating bath
US20090188805A1 (en) * 2008-01-25 2009-07-30 Government Of The United States Of America, As Represented By The Superconformal electrodeposition of nickel iron and cobalt magnetic alloys
US8388824B2 (en) 2008-11-26 2013-03-05 Enthone Inc. Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers
US10221496B2 (en) 2008-11-26 2019-03-05 Macdermid Enthone Inc. Copper filling of through silicon vias
US8771495B2 (en) 2008-11-26 2014-07-08 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
US20100126872A1 (en) * 2008-11-26 2010-05-27 Enthone, Inc. Electrodeposition of copper in microelectronics with dipyridyl-based levelers
US9011666B2 (en) 2008-12-19 2015-04-21 Basf Se Composition for metal electroplating comprising leveling agent
EP2199315A1 (en) 2008-12-19 2010-06-23 Basf Se Composition for metal electroplating comprising leveling agent
US8273232B2 (en) * 2009-04-03 2012-09-25 Osaka Prefecture University Public Corporation Copper filling-up method
CN101925265A (en) * 2009-04-03 2010-12-22 公立大学法人大阪府立大学 Copper filling-up method
US20100255269A1 (en) * 2009-04-03 2010-10-07 Osaka Prefecture University Public Corporation Copper filling-up method
CN101892501A (en) * 2009-05-18 2010-11-24 公立大学法人大阪府立大学 Copper filling-up method
US20100307925A1 (en) * 2009-05-18 2010-12-09 Osaka Prefecture University Public Corporation Copper filling-up method
US9512534B2 (en) 2009-05-18 2016-12-06 Osaka Prefecture University Public Corporation Copper filling-up method
WO2011064154A2 (en) 2009-11-27 2011-06-03 Basf Se Composition for metal electroplating comprising leveling agent
US9598540B2 (en) 2009-11-27 2017-03-21 Basf Se Composition for metal electroplating comprising leveling agent
EP3848417A1 (en) 2009-11-27 2021-07-14 Basf Se Composition for copper electroplating comprising leveling agent
WO2011113908A1 (en) 2010-03-18 2011-09-22 Basf Se Composition for metal electroplating comprising leveling agent
US9834677B2 (en) 2010-03-18 2017-12-05 Basf Se Composition for metal electroplating comprising leveling agent
US9365943B2 (en) 2010-12-15 2016-06-14 Rohm And Haas Electronic Materials Llc Method of electroplating uniform copper layers
US8795505B2 (en) * 2011-02-18 2014-08-05 Samsung Electronics Co., Ltd. Copper electroplating method
US20120211369A1 (en) * 2011-02-18 2012-08-23 Myung-Beom Park Copper electroplating method
US9506158B2 (en) 2011-06-22 2016-11-29 Atotech Deutschland Gmbh Method for copper plating
WO2012175249A1 (en) * 2011-06-22 2012-12-27 Atotech Deutschland Gmbh Method for copper plating
JP2016503461A (en) * 2012-11-26 2016-02-04 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ Copper plating bath composition
US9551080B2 (en) * 2012-11-26 2017-01-24 Atotech Deutschland Gmbh Copper plating bath composition
US20150299883A1 (en) * 2012-11-26 2015-10-22 Atotech Deutschland Gmbh Copper plating bath composition
TWI600802B (en) * 2012-11-26 2017-10-01 德國艾托特克公司 Copper plating bath composition
CN104854265A (en) * 2012-11-26 2015-08-19 德国艾托特克公司 Copper plating bath composition
US9963797B2 (en) * 2013-10-22 2018-05-08 Atotech Deutschland Gmbh Copper electroplating method
CN105899715A (en) * 2013-12-09 2016-08-24 阿文尼公司 Copper electrodeposition bath containing electrochemically inert cation
US20160115618A1 (en) * 2014-10-27 2016-04-28 International Business Machines Corporation System for treating solution for use in electroplating application and method for treating solution for use in electroplating application
US10450667B2 (en) * 2014-10-27 2019-10-22 International Business Machines Corporation System for treating solution for use in electroplating application and method for treating solution for use in electroplating application
US11053604B2 (en) 2014-10-27 2021-07-06 International Business Machines Corporation System for treating solution for use in electroplating application and method for treating solution for use in electroplating application
US10932371B2 (en) 2014-11-05 2021-02-23 Corning Incorporated Bottom-up electrolytic via plating method
US10538850B2 (en) 2015-04-20 2020-01-21 Atotech Deutschland Gmbh Electrolytic copper plating bath compositions and a method for their use
US20180142369A1 (en) * 2015-06-26 2018-05-24 Sumitimo Metal Mining Co., Ltd. Electrically conductive substrate
US10767275B2 (en) 2015-08-31 2020-09-08 Atotech Deutschland Gmbh Aqueous copper plating baths and a method for deposition of copper or copper alloy onto a substrate
US11066553B2 (en) 2015-08-31 2021-07-20 Atotech Deutschland Gmbh Imidazoyl urea polymers and their use in metal or metal alloy plating bath compositions
US20180112321A1 (en) * 2015-11-26 2018-04-26 Fine Feature Electrodeposition Research Institute, Inc. Acidic copper plating solution, acidic copper plated product, and method for producing semiconductor device
US10882842B2 (en) 2017-02-09 2021-01-05 Atotech Deutschland Gmbh Pyridinium compounds, a synthesis method therefor, metal or metal alloy plating baths containing said pyridinium compounds and a method for use of said metal or metal alloy plating baths
US10917966B2 (en) 2018-01-29 2021-02-09 Corning Incorporated Articles including metallized vias
WO2021091743A1 (en) * 2019-11-05 2021-05-14 Macdermid Enthone Inc. Single step electrolytic method of filling through holes in printed circuit boards and other substrates
US11746433B2 (en) 2019-11-05 2023-09-05 Macdermid Enthone Inc. Single step electrolytic method of filling through holes in printed circuit boards and other substrates
CN113956479A (en) * 2021-11-26 2022-01-21 电子科技大学 Copper electroplating accelerator and synthesis method and application thereof
CN116751362A (en) * 2023-08-21 2023-09-15 广东腐蚀科学与技术创新研究院 Water-soluble diaminourea polymer and preparation method and application thereof

Also Published As

Publication number Publication date
KR20010015342A (en) 2001-02-26
EP1069211A2 (en) 2001-01-17
EP1069211A3 (en) 2003-12-17
JP2001073182A (en) 2001-03-21

Similar Documents

Publication Publication Date Title
US20040187731A1 (en) Acid copper electroplating solutions
JP4342294B2 (en) Reverse pulse plating composition and reverse pulse plating method
JP4651906B2 (en) Plating bath and method for depositing a metal layer on a substrate
US6610192B1 (en) Copper electroplating
EP2723921B1 (en) Method for copper plating
JP3285886B2 (en) Electroplating solution composition
US6113771A (en) Electro deposition chemistry
US20040045832A1 (en) Electrolytic copper plating solutions
KR20070006612A (en) Plating method
JP2003113491A (en) Plating bath and method for depositing metal layer on substrate
EP1092790B1 (en) Electroplating of copper from alkanesulfonate electrolytes
US9783903B2 (en) Additives for electroplating baths
KR102127642B1 (en) Copper electroplating bath containing the reaction product of amine, polyacrylamide and bisepoxide
EP1148156A2 (en) Copper Electroplating
TWI659131B (en) Copper electroplating baths containing compounds of reaction products of amines and polyacrylamides
TWI609101B (en) Copper electroplating baths containing compounds of reaction products of amines, polyacrylamides and sultones
KR102125237B1 (en) Copper electroplating bath containing compound of reaction product of amine and quinone
KR100711426B1 (en) Acid copper electroplating composition for plating through holes in printed circuit boards

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION