# Patent

## Title
Electroless copper compositions

## Abstract

Electroless copper and copper alloys plating baths are disclosed. The electroless baths are formaldehyde free and are environmentally friendly. The electroless baths are stable and deposit a bright or copper alloy on substrates.

## Background
The present invention is directed to improved electroless copper compositions. More specifically, the present invention is directed to improved electroless copper compositions which are stable, provide uniform copper deposits and are environmentally friendly.
Electroless copper plating compositions, also known as baths, are in widespread use in metallization industries for depositing copper on various types of substrates. In the manufacture of printed wiring boards, for example, the electroless copper baths are used to deposit copper into through-holes and circuit paths as a base for subsequent electrolytic copper plating. Electroless copper plating also is used in the decorative plastics industry for deposition copper onto non-conductive surfaces as a base for further plating of copper, nickel, gold, silver and other metals as required. Typical baths which are in commercial use today contain divalent copper compounds, chelating agents or complexing agents for the divalent copper ions, formaldehyde reducing agents and various addition agents to make the bath more stable, adjust the plating rate and brighten the copper deposit. Although many of such baths are successful and are widely used, the metallization industry has been searching for alternative electroless copper plating baths that do not contain formaldehyde due to its toxic nature.
Formaldehyde is known as an eye, nose and upper respiratory tract irritant. Animal studies have shown that formaldehyde is an in vitro mutagen. According to a WATCH committee report (WATCH/2005/06—Working Group on Action to Control Chemicals—sub committee with UK Health and Safety Commission) over fifty epidemiological studies have conducted prior to 2000 suggested a link between formaldehyde and nasopharyngeal/nasal cancer but were not conclusive. However, more recent studies conducted by IARC (International Agency for Research on Cancer) in the U.S.A. showed that there was sufficient epidemiological evidence that formaldehyde causes nasopharyngeal cancer in humans. As a result the INRS, a French agency, has submitted a proposal to the European Community Classification and Labelling Work Group to reclassify formaldehyde from a category 3 to a category 1 carcinogen. This would make usage and handling of it more restricted, including in electroless copper formulations. Accordingly, there is a need in the metallization industry for a comparable or improved reducing agent to replace formaldehyde. Such a reducing agent must be compatible with existing electroless copper processes; provide desired capability and reliability and meet cost targets.
Hypophosphites have been suggested as a replacement for formaldehyde; however, plating rates of baths containing this compound are generally too slow. Boron containing compounds such as dimethylamine borane (DMAB) or sodium borohydride have also been tried with varying degrees of success but these compounds tend to be significantly more expensive and have associated health and safety issues, resultant borates have adverse effects on crops on release to the environment and DMAB is toxic.
U.S. Pat. No. 6,331,239 discloses an alkaline electroless copper bath which is free of formaldehyde. Saccharides such as grape sugar (glucose), glucose, sorbitol, cellulose, cane sugar, mannitol and gluconolactone are used as reducing agents. The electroless copper bath also includes hydantoin as a complexing agent. The disclosure alleges that the saccharide and hydantoin provide stability to the bath. However, plating and stability tests with the saccharides glucose and sorbitol, have demonstrated that these baths were too stable and no plating resulted. Accordingly, there is still a need for an electroless copper bath which is free of formaldehyde and is both stable and provides acceptable copper deposits.
In one aspect compositions include one or more sources of copper ions, one or more chelating agents chosen from hydantoin and hydantoin derivatives and one or more reducing agent chosen from fructose and fructose esters.
In another aspect, methods include a) providing a substrate; and b) electrolessly depositing copper on the substrate using an electroless copper composition including one or more sources of copper ions, one or more chelating agents chosen from hydantoin and hydantoin derivatives and one or more reducing agents chosen from fructose and fructose esters.
In a further aspect, methods include a) providing a printed wiring board having a plurality of through-holes; b) desmearing the through-holes; and c) depositing copper on walls of the through-holes using an electroless copper composition including one or more sources of copper ions, one or more chelating agents chosen from hydantoin and hydantoin derivatives and one or more reducing agents chosen from fructose and fructose esters.
In still another aspect, the electroless copper compositions may include one or more additional metal ions to deposit a copper alloy on a substrate. Such additional metal ions include tin, nickel, silver and gold.
The electroless copper baths are formaldehyde free thus they are environmentally friendly. The environmentally friendly electroless copper plating compositions are stable during storage as well as during copper deposition. Additionally, the environmentally friendly electroless copper baths provide uniform copper deposits which have a uniform pink and smooth appearance, and generally meet industry standards desired for commercially acceptable electroless copper baths. The electroless copper compositions also plate copper at commercially acceptable rates.
As used throughout this specification, the abbreviations given below have the following meanings, unless the context clearly indicates otherwise: g=gram; mg=milligram; ml=milliliter; L=liter; cm=centimeter; m=meter; mm=millimeter; μm=micron; 2.54 cm/inch; min.=minute; ppm=parts per million; ° C.=degrees Centigrade; M=molar; g/L=grams per liter; wt %=percent by weight; Tg=glass transition temperature; and dyne=1 g-cm/second2=(10−3 Kg)(10−2 m)/second2=10−5 Newtons.
The terms “printed circuit board” and “printed wiring board” are used interchangeably throughout this specification. The terms “plating” and “deposition” are used interchangeably throughout this specification. A dyne is a unit of force. All amounts are percent by weight, unless otherwise noted. All numerical ranges are inclusive and combinable in any order except where it is logical that such numerical ranges are constrained to add up to 100%.
Electroless copper compositions are formaldehyde free and are environmentally friendly. They also are stable during storage and during electroless copper deposition. The compositions provide a uniform copper deposit with a uniform pink appearance. The compositions include one or more sources of copper ions, one or more chelating agents chosen from hydantoin and hydantoin derivatives and one or more reducing agents chosen from fructose and fructose esters.
Sources of copper ions include, but are not limited to, water soluble halides, nitrates, acetates, sulfates and other organic and inorganic salts of copper. Mixtures of one or more of such copper salts may be used to provide copper ions. Examples include copper sulfate, such as copper sulfate pentahydrate, copper chloride, copper nitrate, copper hydroxide and copper sulfamate. Conventional amounts of copper salts may be used in the compositions. Copper ion concentrations in the composition may range from 0.5 g/L to 30 g/L or such as from 1 g/L to 20 g/L or such as from 5 g/L to 10 g/L.
Chelating agents are compounds chosen from one or more of hydantoin and hydantoin derivatives. Hydantoin derivatives include, but are not limited to 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin and allantoin. Typically the chelating agents are chosen from hydantoin, 5,5-dimethylhydantoin and allantoin. More typically, the chelating agents are chosen from 5,5-dimethylhydantoin. Most typically the chelating agent is 5,5-dimethylhydantoin. Such chelating agents are included in the compositions in amounts of 20 g/l to 150 g/L or such as from 30 g/L to 100 g/L or such as 40 g/l to 80 g/L.
Reducing agents are chosen from one or more of fructose and fructose esters. Fructose esters include, but are not limited to, fructose hexanoate, fructose heptanoate and fructose pentanoate. Typically the reducing agent is fructose. Reducing agents are included in amounts of 10 g/L to 100 g/l or such as from 20 g/L to 80 g/L or such as from 30 g/l to 60 g/L.
Optionally, conventional additives for electroless compositions may be included in the electroless copper compositions. Conventional additives include, but are not limited to, one or more complexing agents, additional chelating agents, stabilizers (including those that adjust mechanical properties, provide rate control, refine grain structure and modify deposit stress), buffering agents and one or more sources of alloying metals.
Optional conventional additives include, but are not limited to, sulfur containing compounds such as mercaptosuccinic acid, dithiodisuccinic acid, mercaptopyridine, mercaptobenzothiazole, thiourea; compounds such as pyridine, purine, quinoline, indole, indazole, imidazole, pyrazine and their derivatives; alcohols such as alkyne alcohols, allyl alcohols, aryl alcohols and cyclic phenols; hydroxy substituted aromatic compounds such as methyl-3,4,5-trihydroxybenzoate, 2,5-dihydroxy-1,4-benzoquinone and 2,6-dihydroxynaphthalene; carboxylic acids, such as citric acid, tartaric acid, succinic acid, malic acid, malonic acid, lactic acid, acetic acid and salts thereof; amines; amino acids; aqueous soluble metal compounds such as metal chlorides and sulfates; silicon compounds such as silanes, siloxanes and low to intermediate molecular weight polysiloxanes; germanium and its oxides and hydrides; and polyalkylene glycols, cellulose compounds, alkylphenyl ethoxylates and polyoxyethylene compounds; and stabilizers such as pyridazine, methylpiperidine, 1,2-di-(2-pyridyl)ethylene, 1,2-di-(pyridyl)ethylene, 2,2′-dipyridylamine, 2,2′-bipyridyl, 2,2′-bipyrimidine, 6,6′-dimethyl-2,2′-dipyridyl, di-2-pyrylketone, N,N,N′,N′-tetraethylenediamine, naphthalene, 1,8-naphthyridine, 1,6-naphthyridine, tetrathiafurvalene, terpyridine, pththalic acid, isopththalic acid and 2,2′-dibenzoic acid. Such additives may be included in the electroless copper compositions in amounts of 0.01 ppm to 1000 ppm or such as from 0.05 ppm to 10 ppm.
Other optional additives include, but are not limited, to Rochelle salts, sodium salts of ethylenediamine tetraacetic acid, nitriloacetic acid and its alkali metal salts, triethanolamine, modified ethylene diamine tetraacetic acids such as N-hydroxyethylenediamine triacetate, hydroxyalkyl substituted dialkaline triamines such as pentahydroxy propyldiethylenetriamine and compounds such as N, N-dicarboxymethyl L-glutamic acid tetrasodium salt. Also s,s-ethylene diamine disuccinic acid and N,N,N′,N′-tetrakis (2-hydroxypropyl) ethytlenediamine (ethylenedinitrilo) tetra-2-propanol may be included. Such compounds are typically used as complexing agents to keep copper (II) in solution. Such compounds may be included in the compositions in conventional amounts. Typically, such compounds are included in amounts of from 1 g/L to 50 g/l or such as from 10 g/L to 40 g/L.
Surfactants also may be included in the compositions. Conventional surfactants may be included in the compositions. Such surfactants include ionic, non-ionic and amphoteric surfactants. Ionic surfactants include conventional anionic and cationic surfactants. Typically the surfactants are non-ionic. Examples of non-ionic surfactants are alkyl phenoxy polyethoxyethanols, polyoxyethylene polymers having from 20 to 150 repeating units and block copolymers of polyoxyethylene and polyoxypropylene. Surfactants may be used in conventional amounts. Typically surfactants are used in amounts of 0.5 g/L to 20 g/L or such as from 1 g/L to 10 g/L.
Alkaline compounds are included in the electroless copper plating compositions to maintain a pH of 9 and higher. A high pH is desirable because oxidation potentials for reducing agents are shifted to more negative values as the pH increases thus making the copper deposition thermodynamically favorable. Typically the electroless copper plating compositions have a pH from 10 to 14. More typically the electroless copper plating compositions have a pH from 11.5 to 13.5.
One or more compounds which provide an alkaline composition within the desired pH ranges may be used. Alkaline compounds include, but are not limited to, one or more alkaline hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide. Typically sodium hydroxide, potassium hydroxide or mixtures thereof are used. More typically sodium hydroxide is used. Such compounds may be included in amounts of 5 g/L to 100 g/L or such as from 10 g/L to 80 g/L.
One or more alloying metals also may be included in the electroless compositions to form binary or ternary alloys of copper. Such alloying metals include, but are not limited to, nickel and tin. Examples of copper alloys include copper/nickel and copper/tin. Typically the copper alloy is copper/nickel.
Sources of nickel ions may include one or more conventional water soluble salts of nickel. Sources of nickel ions include, but are not limited to, nickel sulfates and nickel halides. Sources of nickel ions may be included in the electroless alloying compositions in conventional amounts. Typically sources of nickel ions are included in amounts of 0.5 g/L to 10 g/L or such as from 1 g/l to 5 g/L.
Sources of tin ions may include one or more conventional water soluble salts of tin. Sources of tin ions include, but are not limited to, tin sulfates, tin halides and organic tin sulfonates. Sources of tin ions may be included in the electroless compositions in conventional amounts. Typically sources of tin ions are included in amounts of 0.5 g/L to 10 g/L or such as 1 g/L to 5 g/L.
The electroless copper and copper alloy compositions may be used to deposit a copper or copper alloy on both conductive and non-conductive substrates. The electroless compositions may be used in many conventional methods known in the art. Typically copper or copper alloy deposition is done at temperatures of 20° C. to 80° C. More typically the electroless compositions deposit copper or copper alloys at temperature of 30° C. to 60° C. The substrate to be plated with copper or copper alloy is immersed in the electroless composition or the electroless composition is sprayed onto the substrate. Conventional plating times may be used to deposit the copper or copper alloy onto the substrate. Deposition may be done for 5 seconds to 30 minutes; however, plating times may vary depending on the thickness of the copper or copper alloy desired on the substrate.
Copper and Copper alloy plating rates may range from 0.1 μm/20 minutes to 5 μm/20 minutes or such as from 0.25 μm/20 minutes to 4 μm/20 minutes. Typically copper and copper alloy plating rates may range from 0.5 μm/20 minutes to 3 μm/20 minutes.
Substrates include, but are not limited to, materials including inorganic and organic substances such as glass, ceramics, porcelain, resins, paper, cloth and combinations thereof. Metal-clad and unclad materials also are substrates which may be plated with the electroless copper and copper alloy compositions.
Substrates also include printed circuit boards. Such printed circuit boards include metal-clad and unclad with thermosetting resins, thermoplastic resins and combinations thereof, including fiber, such as fiberglass, and impregnated embodiments of the foregoing.
Thermoplastic resins include, but are not limited to, acetal resins, acrylics, such as methyl acrylate, cellulosic resins, such as ethyl acetate, cellulose propionate, cellulose acetate butyrate and cellulose nitrate, polyethers, nylon, polyethylene, polystyrene, styrene blends, such as acrylonitrile styrene and copolymers and acrylonitrile-butadiene styrene copolymers, polycarbonates, polychlorotrifluoroethylene, and vinylpolymers and copolymers, such as vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, vinyl chloride-acetate copolymer, vinylidene chloride and vinyl formal.
Thermosetting resins include, but are not limited to, allyl phthalate, furane, melamine-formaldehyde, phenol-formaldehyde and phenol-furfural copolymers, alone or compounded with butadiene acrylonitrile copolymers or acrylonitrile-butadiene-styrene copolymers, polyacrylic esters, silicones, urea formaldehydes, epoxy resins, allyl resins, glyceryl phthalates and polyesters.
Porous materials include, but are not limited to paper, wood, fiberglass, cloth and fibers, such as natural and synthetic fibers, such as cotton fibers and polyester fibers.
The electroless copper and copper alloy compositions may be used to plate both low and high Tg resins. Low Tg resins have a Tg below 160° C. and high Tg resins have a Tg of 160° C. and above. Typically high Tg resins have a Tg of 160° C. to 280°° C. or such as from 170° C. to 240° C. High Tg polymer resins include, but are not limited to, polytetrafluoroethylene (PTFE) and polytetrafluoroethylene blends. Such blends include, for example, PTFE with polypheneylene oxides and cyanate esters. Other classes of polymer resins which include resins with a high Tg include, but are not limited to, epoxy resins, such as difunctional and multifunctional epoxy resins, bimaleimide/triazine and epoxy resins (BT epoxy), epoxy/polyphenylene oxide resins, acrylonitrile butadienestyrene, polycarbonates (PC), polyphenylene oxides (PPO), polypheneylene ethers (PPE), polyphenylene sulfides (PPS), polysulfones (PS), polyamides, polyesters such as polyethyleneterephthalate (PET) and polybutyleneterephthalate (PBT), polyetherketones (PEEK), liquid crystal polymers, polyurethanes, polyetherimides, epoxies and composites thereof.
In one embodiment the electroless compositions may be used to deposit copper or copper alloys on the walls of through-holes or vias of printed circuit boards. The electroless compositions may be used in both horizontal and vertical processes of manufacturing printed circuit boards.
In one embodiment through-holes are formed in the printed circuit board by drilling or punching or any other method known in the art. After the formation of the through-holes, the boards are rinsed with water and a conventional organic solution to clean and degrease the board followed by desmearing the through-hole walls. Typically desmearing of the through-holes begins with application of a solvent swell.
Any conventional solvent swell may be used to desmear the through-holes. Solvent swells include, but are not limited to, glycol ethers and their associated ether acetates. Conventional amounts of glycol ethers and their associated ether acetates may be used. Such solvent swells are well known in the art. Commercially available solvent swells include, but are not limited to, CIRCUPOSIT CONDITIONERTM 3302, CIRCUPOSIT HOLE PREPTM 3303 and CIRCUPOSIT HOLE PREPTM 4120 (obtainable from Rohm and Haas Electronic Materials, Marlborough, Mass.).
Optionally, the through-holes are rinsed with water. A promoter is then applied to the through-holes. Conventional promoters may be used. Such promoters include sulfuric acid, chromic acid, alkaline permanganate or plasma etching. Typically alkaline permanganate is used as the promoter. An example of a commercially available promoter is CIRCUPOSIT PROMOTERTM 4130 available from Rohm and Haas Electronic Materials, Marlborough, Mass.
Optionally, the through-holes are rinsed again with water. A neutralizer is then applied to the through-holes to neutralize any residues left by the promoter. Conventional neutralizers may be used. Typically the neutralizer is an aqueous alkaline solution containing one or more amines or a solution of 3 wt % peroxide and 3 wt % sulfuric acid. Optionally, the through-holes are rinsed with water and the printed circuit boards are dried.
After desmearing an acid or alkaline conditioner may be applied to the through-holes. Conventional conditioners may be used. Such conditioners may include one or more cationic surfactants, non-ionic surfactants, complexing agents and pH adjusters or buffers. Commercially available acid conditioners include, but are not limited to, CIRCUPOSIT CONDITIONERTM 3320 and CIRCUPOSIT CONDITIONERTM 3327 available from Rohm and Haas Electronic Materials, Marlborough, Mass. Suitable alkaline conditioners include, but are not limited to, aqueous alkaline surfactant solutions containing one or more quaternary amines and polyamines. Commercially available alkaline surfactants include, but are not limited to, CIRCUPOSIT CONDITIONERTM 231, 3325, 813 and 860 available from Rohm and Haas Electronic Materials. Optionally, the through-holes are rinsed with water after conditioning.
Conditioning is followed by microetching the through-holes. Conventional microeteching compositions may be used. Microetching is designed to provide a micro-roughened copper surface on exposed copper (e.g. innerlayers and surface etch) to enhance subsequent adhesion of deposited electroless and electroplate. Microetches include, but are not limited to, 60 g/L to 120 g/L sodium persulfate or sodium or potassium oxymonopersulfate and sulfuric acid (2%) mixture, or generic sulfuric acid/hydrogen peroxide. An example of a commercially available microetching composition includes CIRCUPOSIT MICROETCHTM 3330 available from Rohm and Haas Electronic Materials. Optionally, the through-holes are rinsed with water.
A pre-dip is then applied to the microeteched through-holes. Examples of pre-dips include 2% to 5% hydrochloric acid or an acidic solution of 25 g/L to 75 g/L sodium chloride. Optionally, the through-holes are rinsed with cold water.
A catalyst is then applied to the through-holes. Any conventional catalyst may be used. The choice of catalyst depends on the type of metal to be deposited on the walls of the through-holes. Typically the catalysts are colloids of noble and non-noble metals. Such catalysts are well known in the art and many are commercially available or may be prepared from the literature. Examples of non-noble metal catalysts include copper, aluminum, cobalt, nickel, tin and iron. Typically noble metal catalysts are used. Suitable noble metal colloid catalysts include, for example, gold, silver, platinum, palladium, iridium, rhodium, ruthenium and osmium. More typically, noble metal catalysts of silver, platinum, gold and palladium are used. Most typically silver and palladium are used. Suitable commercially available catalysts include, for example, CIRCUPOSIT CATALYSTTM 3344 and CATAPOSITTM 44 available from Rohm and Hats Electronic Materials. The through-holes optionally may be rinsed with water after application of the catalysts.
The walls of the through-holes are then plated with copper or copper alloy with an electroless composition as described above. Typically copper is plated on the walls of the through-holes. Plating times and temperatures are also described above.
After the copper or copper alloy is deposited on the walls of the through-holes, the through-holes are optionally rinsed with water. Optionally, anti-tarnish compositions may be applied to the metal deposited on the walls of the through-holes. Conventional anti-tarnish compositions may be used. Examples of anti-tarnish compositions include ANTI TARNISHTM 7130 and CUPRATECTM 3 (obtainable from Rohm and Haas Electronic Materials). The through-holes may optionally be rinsed by a hot water rinse at temperatures exceeding 30° C. and then the boards may be dried.
In an alternative embodiment the through-holes may be treated with an alkaline hydroxide solution after desmear to prepare the through-holes for electroless deposition of copper or copper alloy. This alternative embodiment for plating through-holes or vias is typically used when preparing high Tg boards for plating. The alkaline hydroxide solution contacts the through-holes for 30 seconds to 120 seconds or such as from 60 seconds to 90 seconds. Application of the alkaline hydroxide composition between the desmearing and plating the through-holes provides for good coverage of the through-hole walls with the catalyst such that the copper or copper alloy covers the walls. The alkaline hydroxide solution is an aqueous solution of sodium hydroxide, potassium hydroxide or mixtures thereof. The hydroxides are included in amounts of 0.1 g/L to 100 g/L or such as from 5 g/L to 25 g/L. Typically the hydroxides are included in the solutions in amounts of 15 g/L to 20 g/l. Typically the alkaline hydroxide is sodium hydroxide. If the alkaline hydroxide solution is a mixture of sodium hydroxide and potassium hydroxide, the sodium hydroxide and potassium hydroxide are in a weight ratio of 4:1 to 1:1, or such as from 3:1 to 2:1.
Optionally one or more surfactants may be added to the alkaline hydroxide solution. Typically the surfactants are non-ionic surfactants. The surfactants reduce surface tension to enable proper wetting of the through-holes. Surface tension after application of the surfactant in the through-holes ranges from 25 dynes/cm to 50 dynes/cm, or such as from 30 dynes/cm to 40 dynes/cm. Typically the surfactants are included in the formulation when the alkaline hydroxide solution is used to treat small through-holes to prevent flaring. Small through-holes typically range in diameter of 0.2 mm to 0.5 mm. In contrast, large through-holes typically range in diameter of 0.5 mm to 1 mm. Aspect ratios of through-holes may range from 1:1 to 20:1.
Surfactants are included in the alkaline hydroxide solutions in amounts of 0.05 wt % to 5 wt %, or such as from 0.25 wt % to 1 wt %. Suitable non-ionic surfactants include, for example, aliphatic alcohols such as alkoxylates. Such aliphatic alcohols have ethylene oxide, propylene oxide, or combinations thereof, to produce a compound having a polyoxyethylene or polyoxypropylene chain within the molecule, i.e., a chain composed of recurring (—O—CH2—CH2—) groups, or chain composed of recurring (—O—CH2—CH—CH3) groups, or combinations thereof. Typically such alcohol alkoxylates are alcohol ethoxylates having carbon chains of 7 to 15 carbons, linear or branched, and 4 to 20 moles of ethoxylate, typically 5 to 40 moles of ethoxylate and more typically 5 to 15 moles of ethoxylate.
Many of such alcohol alkoxylates are commercially available. Examples of commercially available alcohol alkoxylates include, for example, linear primary alcohol ethoxylates such as NEODOL 91-6, NEODOL 91-9 (C9-C11 alcohols having an average of 6 to 9 moles of ethylene oxide per mole of linear alcohol ethoxylate) and NEODOL 1-73B (C11 alcohol with an average blend of 7 moles of ethylene oxide per mole of linear primary alcohol ethoxylate). Both are available from Shell Oil Company, Houston Tex.
After the through-holes are treated with the alkaline hydroxide solution, they may be treated with an acid or alkaline conditioner. The through-holes are then micro-etched and applied with a pre-dip followed by applying a catalyst. The through-holes are then electrolessly plated with copper or copper alloy.
After the through-holes are plated with copper or copper alloy, the substrates may undergo further processing. Further processing may include conventional processing by photoimaging and further metal deposition on the substrates such as electrolytic metal deposition of, for example, copper, copper alloys, tin and tin alloys.
While not being bound by theory, the hydantoin and hydantoin derivatives in combination with one or more of the fructose and fructose esters enable a controlled autocatalytic deposition of copper or copper alloys on substrates. The hydantoin and hydantoin derivatives in combination with one or more of the fructose and fructose esters prevent the formation of copper oxide (Cu2O) in the bath. Such copper oxide formation destabilizes the electroless copper and copper alloy compositions and compromises the deposition of copper and copper alloys on substrates. The inhibition of the copper oxide formation enables the autocatalytic process to operate at high pH ranges where copper and copper alloy deposition is thermodynamically favorable.
The electroless copper and copper alloy compositions are free of formaldehyde and are environmentally friendly. They are stable during storage and during electroless deposition. They deposit a uniform copper or copper alloy layer on a substrate which is bright and has a salmon pink appearance, which indicates a fine grain deposit.
The following examples are not intended to limit the scope of the invention but are intended to further illustrate it.


EXAMPLE 1
Six aqueous electroless copper compositions included fructose and 5,5-dimethylhydantoin. The electroless copper compositions were free of formaldehyde and were environmentally friendly. They were tested for their stability, plating rate and quality of their copper deposits. Each aqueous electroless composition included at least 7 g/L of copper chloride (CuCl22H2O), 47 g/L of fructose and 64 g/L of 5,5-dimethylhydantoin. In addition electroless copper compositions 2-6 included one or more conventional complexing or chelating agents in conventional amounts.
The temperature of the compositions was maintained at 55° C. and a pH of 13.2 during electroless copper deposition. Copper was deposited on substrates for 20 minutes. The substrates used were six unclad FR4 epoxy/glass laminates with dimensions 1.5 inches×1.5 inches (2.54 cm/inch). The printed circuit boards were obtained from Isola Laminate Systems Corp., LaCrosse Wis. The process was as follows:

    
    
        1. The surface of each laminate was immersed in an aqueous bath containing 5% of the aqueous acid conditioner CIRCUPOSIT CONDITIONERTM 3327 for 6 minutes at 50° C.
        2. Each laminate was then rinsed with cold water for 6 minutes.
        3. A pre-dip was then applied to each laminate for 1 minute at room temperature. The pre-dip was Pre-dipTM 3340 obtainable from Rohm and Haas Electronic Materials.
        4. The laminates were then primed for 6 minutes at 40° C. with a catalyst for electroless copper metallization. The laminates were primed by immersing each board in the catalyst. The catalyst was CIRCUPOSIT CATALYSTTM 3344
        5. The laminates were then rinsed with cold water for 5 minutes.
        6. Each laminate was then immersed in one of the electroless copper plating compositions described above for copper metal deposition. Copper metal deposition was done over 20 minutes. No red precipitate (Cu2O formation) was observed during copper plating.
        7. The copper plated laminates were then rinsed with cold water for 2 minutes.
        8. Each copper plated laminate was then rinsed with deionized water for one minute.
        9. Each copper plated laminate was then placed into a conventional convection oven and dried for 20 minutes at 105° C.
        10. After drying each copper plated laminate was placed in a conventional laboratory dessicator for 20 minutes or until it cooled to room temperature.
        11. After drying each copper plated laminate was observed for the quality of the copper deposit. All appeared to have a good or very good appearance (see Table below).
        12. Each copper plated laminate was then weighed and recorded on a standard laboratory balance.
        13. After weighing and recording the weight of each laminate, the copper deposit was etched from each laminate by immersion in a 3% sulfuric acid/3% hydrogen peroxide solution.
        14. Each laminate was then rinsed with cold water for 3 minutes.
        15. Each laminate was then put back in the oven for 20 minutes at 105° C.
        16. The laminates were then placed in a dessicator for 20 minutes or until it reached room temperature.
        17. The laminates were then weighed and the weight difference before etching and after etching was determined. The weight difference for each laminate is in the table below.
    
    












TABLE 2







RATE



COMPOSITION
STABILITY
(μm/20 minutes)
APPEARANCE







1
No precipitate
0.2080
Salmon pink


2
No precipitate
2.2440
Salmon pink


3
No precipitate
0.3360
Salmon pink


4
No precipitate
0.2200
Salmon pink


5
No precipitate
0.1400
Salmon pink


6
No precipitate
0.1080
Salmon pink









All of the electroless copper compositions were stable. There was no observable Cu2O precipitate. All of the copper deposits appeared salmon pink which indicated that the copper deposits were suitable for industrial application. No dark brown patchy deposits were observed, which are indicative of poor quality copper plating. In addition to composition stability and good copper deposition, the plating rates were acceptable for industrial application.
EXAMPLE 2
Six aqueous electroless copper compositions included fructose and hydantoin. They were tested for their stability, plating rate and quality of their copper deposits. Each aqueous electroless composition included at least 7 g/L of copper chloride (CuCl22H2O), 47 g/L of fructose and 50 g/L of 0.5M hydantoin. The electroless copper compositions were formaldehyde free and environmentally friendly. In addition electroless copper compositions 2-6 included one or more conventional complexing agent or chelating agent in conventional amounts.
The temperature of the compositions was maintained at 55° C. and a pH of 13.2 during electroless copper deposition. Copper was deposited on substrates for 20 minutes. The substrates used were six unclad FR4 epoxy/glass laminates with dimensions 1.5 inches× 1.5 inches. The laminates were obtained from Isola Laminate System Corp., Lacrosse Wis. The process was the same as described in Example 1 above. The results of the tests are in the table below.










TABLE 3







RATE



COMPOSITIONS
STABILITY
(μm/20 minutes)
APPEARANCE







1
No precipitate
0.2800
Salmon pink


2
No precipitate
0.3480
Salmon pink


3
No precipitate
0.1080
Dark brown


4
No precipitate
0.2080
Salmon pink


5
No precipitate
0.4200
Salmon pink


6
No precipitate
0.2160
Salmon pink









All of the electroless copper compositions were stable during copper deposition. No Cu2O precipitate was observed. All of the compositions, except composition 3, had copper deposits which were salmon pink in color indicating optimum copper plating performance. This may have been caused by oxidation or passivation of the deposit.
In addition to composition stability and over all good copper deposition, the plating rates for all of the electroless compositions were acceptable for industrial application.
EXAMPLE 3
Six aqueous electroless copper compositions included fructose and allantoin and were tested for their stability, plating rate and quality of their copper deposits. Each aqueous electroless composition included at least 7 g/L of copper chloride (CuCl22H2O), 47 g/L of fructose and 79 g/L of allantoin. In addition electroless copper compositions 2-6 included one or more complexing or chelating agents.
The temperature of the compositions was maintained at 55° C. and a pH of 13.2 during electroless copper deposition. Copper was deposited on substrates for 20 minutes. The substrates used were six unclad FR4 epoxy/glass laminates with dimensions 1.5 inches× 1.5 inches. The laminates were obtained from Isola Laminate Systems Corp., LaCrosse Wis. The process for testing the compositions was the same as in Examples 1 and 2 above. The results are in the table below.










TABLE 4







RATE



COMPOSITION
STABILITY
(μm/20 minutes)
APPEARANCE







1
No precipitate
0.2360
Salmon pink


2
No precipitate
0.2600
Salmon pink


3
No precipitate
0.1680
Salmon pink


4
No precipitate
0.1800
Salmon pink


5
No precipitate
0.2560
Salmon pink


6
No precipitate
0.2200
Salmon pink









All of the electroless compositions were stable. There were no visible signs of Cu2O in any of the compositions. All of the copper deposits were salmon pink which indicated that the copper deposits were suitable for industrial application. No dark brown patchy deposit were observed.
In addition to composition stability and good copper deposition, the plating rates were acceptable for industrial application.
EXAMPLE 4 (COMPARATIVE)
An aqueous electroless copper plating bath was prepared which included glucose as a reducing agent. The aqueous electroless copper plating bath had the following formula:










TABLE 5







COMPONENT
AMOUNT









Copper sulfate pentahydrate
 4 g/L



Glucose
20 g/L



Sodium hydroxide
40 g/L



Hydantoin
20 g/L










The pH of the electroless bath was 12.6 and the temperature of the bath was 40° C. during copper deposition. No evidence of Cu2O was initially observed after making the bath.
A conventional palladium spade electrode was immersed in the bath. The electrode was observed for copper deposition at 5, 10, 15, 30, 60 and 120 minutes. No copper plating was observed.
A second plating test was done using a catalyzed cotton cloth. The cloth was prepared for electroless copper deposition by immersing the cloth in colloidal palladium catalyst called CATALYST 3344, obtainable from Rohm and Haas Electronic Materials.
The cloth was then immersed in the electroless copper bath. The cloth was observed for copper plating after 5, 10, 15, 30, 60 and 120 minutes. No copper plating was observed, however after 5 minutes the cloth began to turn brown. As time progressed the brown color became more apparent. The brown color may have been due to passivation or oxidation of the copper deposit, which prevented any further plating. After a period of 24 hours, the bath crashed, i.e. the bath became unstable and a red precipitate of Cu2O formed.
In contrast, the electroless copper compositions of Examples 1-3 which included fructose as a reducing agent in combination with 5,5-dimethylhydantoin, hydantoin and allantoin were stable. All of the electroless copper compositions, except one, plated a salmon pink copper deposit which is indicative in the metal plating industry as industrially acceptable. The tests showed that including fructose in electroless copper plating baths was an improvement over electroless copper plating baths with glucose.
EXAMPLE 5 (COMPARATIVE)
An aqueous electroless copper plating bath was prepared which included sorbitol as a reducing agent. The aqueous electroless copper plating bath had the following formulation:










TABLE 7







COMPONENT
AMOUNT









Copper sulfate pentahydrate
 4 g/L



1-methylhydantoin
20 g/L



Sorbitol
15 g/L



Potassium hydroxide
45 g/L










A palladium spade electrode was immersed in the electroless copper plating bath. The electrode was removed and examined for copper plating after 5, 10, 15, 30, 60 and 120 minutes. No copper plating was observed.
A cotton cloth was soaked in a colloidal catalyst bath as described in Example 4 above. The cloth was immersed in the electroless copper plating bath of Table 7 for 5, 10, 15, 30, 60 and 120 minutes. No plating was observed. The bath remained stable for 24 hours and no precipitation was observed.
In contrast, the electroless copper compositions of Examples 1-3 which included fructose as a reducing agent in combination with 5,5-dimethylhydantoin, hydantoin and allantoin were also stable. However, all of the electroless copper composition, except one, plated a salmon pink copper deposit which is indicative in the metal plating industry as industrially acceptable. The tests showed that including fructose in electroless copper plating baths was an improvement over electroless copper plating baths with sorbitol.

## Claims

1. A composition comprising one or more sources of copper ions, one or more chelating agents selected from the group consisting of hydantoin and hydantoin derivatives and 20 g/L to 80 g/L of one or more reducing agents selected from the group consisting of fructose esters, the composition is formaldehyde free.

2. The composition of claim 1, wherein the chelating agents range from 20 g/L to 150 g/L.

3. The composition of claim 1, wherein the hydantoin derivatives are selected from the group consisting of 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin and allantoin.

4. The composition of claim 1, wherein the fructose esters are selected from the group consisting of fructose hexanoate, fructose heptanoate and fructose pentanoate.

5. The composition of claim 1, further comprising one or more additional additives.

6. A method comprising:
a) providing a substrate; and
b) electrolessly depositing copper on the substrate with an electroless copper composition comprising one or more sources of copper ions, one or more chelating agents selected from the group consisting of hydantoin and hydantoin derivatives and 20 g/L to 80 g/L of one or more reducing agents selected from the group consisting of fructose esters, the electroless copper composition is formaldehyde free.

7. A method comprising:
a) providing a printed wiring board comprising a plurality of through-holes;
b) desmearing the through-holes; and
c) depositing copper on walls of the through-holes with an electroless copper bath comprising one or more sources of copper ions, one or more chelating agents selected from the group consisting of hydantoin and hydantoin derivatives and 20 g/L to 80 g/L of one or more reducing agents selected from the group consisting of fructose esters, the electroless copper bath is formaldehyde free.

8. The method of claim 7, wherein the electroless copper composition further comprises one or more additional additives.