EP3272911B1 - Indium-elektroplattierungszusammensetzungen mit 2-imidazolidinethion-verbindungen und indium-elektroplattierungsverfahren - Google Patents

Indium-elektroplattierungszusammensetzungen mit 2-imidazolidinethion-verbindungen und indium-elektroplattierungsverfahren Download PDF

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EP3272911B1
EP3272911B1 EP17181754.7A EP17181754A EP3272911B1 EP 3272911 B1 EP3272911 B1 EP 3272911B1 EP 17181754 A EP17181754 A EP 17181754A EP 3272911 B1 EP3272911 B1 EP 3272911B1
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Prior art keywords
indium
imidazolidinethione
alkyl
electroplating
branched
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French (fr)
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EP3272911A1 (de
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Yi Qin
Kristen Flajslik
Mark Lefebvre
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer

Definitions

  • the present invention is directed to indium electroplating compositions containing 2-imidazolidinethione compounds for use in methods for electroplating indium metal on metal layers. More specifically, the present invention is directed to indium electroplating compositions containing 2-imidazolidinethione compounds for use in methods of electroplating indium metal on metal layers where the indium metal deposit is uniform, substantially void-free and has a smooth surface morphology.
  • Indium reduction occurs at potentials more negative than that of proton reduction, and significant hydrogen bubbling at the cathode causes increased surface roughness.
  • Indium (1 + ) ions stabilized due to the inert pair effect, formed in the process of indium deposition catalyze proton reduction and participate in disproportionation reactions to regenerate Indium (3 + ) ions. In the absence of a complexing agent, indium ions begin to precipitate from solutions above pH > 3.
  • conventional indium electroplating baths have not been able to electroplate an indium deposit which is compatible with multiple under bump metals (UBM) such as nickel, copper, gold and tin. More importantly, conventional indium electroplating baths have not been able to electroplate indium with high coplanarity and high surface planarity on substrates which include nickel.
  • Indium is a highly desirable metal in numerous industries because of its unique physical properties. For example, it is sufficiently soft such that it readily deforms and fills in microstructures between two mating parts, has a low melting temperature (156° C) and a high thermal conductivity ( ⁇ 82 W/m°K), good electrical conductivity, good ability to alloy and form intermetallic compounds with other metals in a stack.
  • solder bump material It may be used as low temperature solder bump material, a desired process for 3D stack assembly to reduce damage on assembled chips by the thermal stress induced during reflow processing.
  • Such properties enable indium for various uses in the electronics and related industries including in semiconductors and polycrystalline thin film solar cells.
  • TIMs are critical to protect electronic devices such as integrated circuits (IC) and active semiconductor devices, for example, microprocessors, from exceeding their operational temperature limit. They enable bonding of the heat generating device (e.g. a silicon semiconductor) to a heat sink or a heat spreader (e.g. copper and aluminum components) without creating an excessive thermal barrier.
  • the TIM may also be used in assembly of other components of the heat sink or the heat spreader stack that composes the overall thermal impedance path.
  • TIMs for example, thermal greases, thermal gels, adhesives, elastomers, thermal pads, and phase change materials.
  • thermal greases for example, thermal greases, thermal gels, adhesives, elastomers, thermal pads, and phase change materials.
  • thermal conductivity of many current TIMs does not exceed 5 W/m°K and many are less than 1 W/m°K.
  • TIMs that form thermal interfaces with effective thermal conductivities exceeding 15 W/m°K are presently needed.
  • EP1978051 discloses metal plating compositions which provide good leveling performance and throwing power.
  • EP1300486 discloses a metal plating bath and metal plating process that contains aldehyde compounds that prevent or reduce the consumption of metal plating bath additives.
  • US2005/173255 discloses methods of electroplating a quaternary alloy containing nickel, cobalt, and at least two metal alloys involving providing an electroplating bath comprising ionic nickel, ionic cobalt, at least two ionic alloy metals, and at least one brightener; and applying a current to the electroplating bath whereby a quaternary alloy forms.
  • indium is a highly desirable metal for electronic devices, and there is a need for an improved indium composition for electroplating indium metal on metal substrates.
  • compositions which include one or more sources of indium ions, one or more 2-imidazolidinethione compounds and citric acid, salts thereof or mixtures thereof.
  • a method includes providing a substrate including a nickel layer; contacting the substrate with an indium electroplating composition including one or more sources of indium ions, one or more 2-imidazolidinethione compounds and citric acid, salts thereof or mixtures thereof, wherein the indium electroplating composition is free of alloying metals; and electroplating an indium metal layer on the nickel layer of the substrate with the indium electroplating composition.
  • the indium electroplating compositions can provide a deposit of indium metal on a metal layer which is substantially void-free, uniform and has smooth morphology.
  • the ability to reproducibly plate a void-free uniform indium of target thickness, and smooth surface morphology enables the expanded use of indium in the electronics industry, including in semiconductors and polycrystalline thin film solar cells.
  • the indium deposited from the electroplating composition of the present invention can be used as a low temperature solder material which is desired for 3D stack assembly to reduce damage on assembled chips by the thermal stress induced during reflow processing.
  • the indium can also be used as thermal interface materials to protect electronic devices such as microprocessors and integrated circuits.
  • the present invention addresses a number of problems of the prior inability to electroplate an indium layer of sufficient properties to meet requirements for applications in advanced electronic devices.
  • plating plating
  • electroplating electroplating
  • electroroplating electrolymer
  • copolymer is a compound composed of two or more different mers.
  • dendrite means branching spike-like metal crystals.
  • all plating baths are aqueous solvent based, i.e. water based, plating baths. All amounts are percent by weight and all ratios are by moles, 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%.
  • the compositions include one or more sources of indium ions which are soluble in an aqueous environment.
  • the indium compositions are free of alloying metals.
  • sources include, but are not limited to, indium salts of alkane sulfonic acids and aromatic sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, butane sulfonic acid, benzenesulfonic acid and toluenesulfonic acid, indium salts of sulfamic acid, sulfate salts of indium, chloride and bromide salts of indium, nitrate salts, hydroxide salts, indium oxides, fluoroborate salts, indium salts of carboxylic acids, such as citric acid, acetoacetic acid, glyoxylic acid, pyruvic acid, glycolic acid, malonic acid, hydroxamic acid, iminodiacetic acid, salicylic acid, glyceric
  • the source of indium ions is one or more indium salts of sulfuric acid, sulfamic acid, alkane sulfonic acids, aromatic sulfonic acids and carboxylic acids. More typically, the source of indium ions is one or more indium salts of sulfuric acid and sulfamic acid.
  • the water-soluble salts of indium are included in the compositions in sufficient amounts to provide an indium deposit of the desired thickness.
  • the water-soluble indium salts are included in the compositions to provide indium (3 + ) ions in the compositions in amounts of 2 g/L to 70 g/L, more preferably from 2 g/L to 60 g/L, most preferably from 2 g/L to 30 g/L.
  • One or more 2-imidazolidinethione compounds are included in the indium compositions.
  • the one or more 2-imidazolidinethione compounds are included in the indium compositions in amounts of 0.005 g/l to 5 g/L, preferably from 0.01 g/L to 3 g/L, more preferably from 0.01 g/L to 1.5 g/L.
  • 2-imidazolidinethione compounds include, but are not limited to those compounds having a formula: where R 1 and R 2 are independently chosen from hydrogen, linear or branched (C 1 -C 12 )alkyl, linear or branched hydroxy(C 1 -C 12 )alkyl, linear or branched (C 1 -C 12 )alkoxy, linear or branched (C 3 -C 12 )allyl, amino, primary, secondary or tertiary amino (C 1 -C 12 )alkyl, acetyl and substituted or unsubstituted aryl(C 1 -C 12 )alkyl; R 3 , R 4 , R 5 and R 6 are independently chosen from hydrogen, linear or branched (C 1 -C 12 )alkyl, hydroxyl, linear or branched hydroxy(C 1 -C 12 )alkyl, primary, secondary or tertiary amino, aryl, linear or branched (C 1 -C 12 )
  • Substituent groups on the aryl include, but are not limited to linear or branched (C 1 -C 5 )alkyl, hydroxyl, hydroxy(C 1 -C 5 )alkyl, (C 1 -C 3 )alkoxy and primary, secondary and tertiary amino(C 1 -C 5 )alkyl.
  • the substituents replacing the hydrogens of the secondary and tertiary amino groups include, but are not limited to linear or branched (C 1 -C 5 )alkyl, substituted or unsubstituted phenyl, linear or branched hydroxyl(C 1 -C 5 )alkyl and (C 4 -C 8 )alicyclic.
  • R 1 and R 2 are independently chosen from hydrogen, linear or branched (C 1 -C 5 )alkyl, linear or branched hydroxy(C 1 -C 5 )alkyl, (C 1 -C 3 )alkoxy, amino, primary or secondary amino(C 1 -C 5 )alkyl and acetyl.
  • R 3 , R 4 , R 5 and R 6 are independently chosen from hydrogen, linear or branched (C 1 -C 5 )alkyl, hydroxyl, linear or branched hydroxy(C 1 -C 5 )alkyl and substituted or unsubstituted phenyl.
  • R 1 and R 2 are independently chosen from hydrogen, (C 1 -C 2 )alkyl, hydroxy(C 1 -C 3 )alkyl, primary amino(C 1 -C 3 )alkyl and acetyl. More preferably R 3 , R 4 , R 5 and R 6 are independently chosen from hydrogen, (C 1 -C 4 )alkyl, hydroxyl and phenyl.
  • 2-imidazolidinethione compounds examples include 2-imidazolidinethione, 1,3-dimethyl-2-imidazolidinethione, 1-methyl-5-phenyl-2-imidazolidinethione, 1,3-diethyl-2-imidazolidinethione, 1-methyl-2-imidazolidinethione, 4,4-dimethyl-2-imidazolidinethione, 4,5-dimethyl-2-imidazolidinethione, (4S)-4-methyl-2-imidazolidinethione, 1-dodecyl-2-imidazolidinethione, 1-butyl-5-(1-methylethyl)-2- imidazolidinethione, 1,3- diallyl-2-imidazolidinethione, 1-acetyl-3-allyl-2-imidazolidinethione, 1-(2-aminoethyl)-2-imidazolidinethione, 1-acetyl-2-imidazolidinethione, 4,5-dihydroxy-1-methyl-2
  • Citric acid, salts thereof or mixtures thereof is included in the indium compositions.
  • Citric acid salts include, but are not limited to sodium citrate dihydrate, monosodium citrate, potassium citrate and diammonium citrate.
  • Citric acid, salts thereof or mixtures thereof can be included in amounts of 5 g/L to 300 g/L, preferably from 50 g/L to 200 g/L.
  • Preferably a mixture of citric acid and its salts are included in the indium compositions in the foregoing amounts.
  • one or more sources of chloride ions are included in the indium electroplating compositions.
  • Sources of chloride ions include, but are not limited to sodium chloride, potassium chloride, hydrogen chloride or mixtures thereof.
  • the source of chloride ions is sodium chloride, potassium chloride or mixtures thereof. More preferably the source of chloride ions is sodium chloride.
  • One or more sources of chloride ions are included in the indium compositions such that a molar ratio of chloride ions to indium ions is at least 2:1, preferably from 2:1 to 7:1, more preferably from 4:1 to 6:1.
  • one or more additional buffers can be included in the indium compositions to provide a pH of 1-4, preferably from 2-3.
  • the buffer includes an acid and the salt of its conjugate base.
  • Acids include amino acids, carboxylic acids, glyoxylic acid, pyruvic acid, hydroxamic acid, iminodiacetic acid, salicylic acid, succinic acid, hydroxybutyric acid, acetic acid, acetoacetic acid, tartaric acid, phosphoric acid, oxalic acid, carbonic acid, ascorbic acid, boric acid, butanoic acid, thioacetic acid, glycolic acid, malic acid, formic acid, heptanoic acid, hexanoic acid, hydrofluoric acid, lactic acid, nitrous acid, octanoic acid, pentanoic acid, uric acid, nonanoic acid, decanoic acid, sulfurous acid, sulfuric acid, al
  • one or more surfactants can be included in the indium compositions.
  • surfactants include, but are not limited to amine surfactants such as quaternary amines, commercially available as TOMAMINE®-Q-C-15 surfactant, amine oxides, commercially available as TOMAMINE®-AO-455 surfactant, both available from Air Products; hydrophilic polyether monoamine commercially available as SURFONAMINE® L-207 amine surfactant from Huntsman; polyethyleneglycol octyl (3-sulfopropyl) diether commercially available as RALUFON® EA 15-90 surfactant; [(3-sulfopropoxy)-polyalkoxy]- ⁇ -naphthyl ether, potassium salt, commercially available as RALUFON® NAPE 14-90 surfactant, octaethyleneglycol octyl ether, commercially available as RALUFON® EN 16-80 surfactant, polyethyleneglycol
  • the indium compositions can include one or more grain refiners.
  • grain refiners include, but are not limited to 2-picolinic acid, Sodium 2-naphthol-7-sulfonate, 3-(benzothiazol-2-ylthio)propane-1-sulfonic acid (ZPS), 3-(carbamimidoylthio)propane-1-sulfonic acid (UPS), bis(sulfopropyl)disulfide (SPS), mercaptopropane sulfonic acid (MPS), 3- N , N -dimethylaminodithiocarbamoyl-1-propane sulfonic acid (DPS), and (O-ethyldithiocarbonato)-S-(3-sulfopropyl)-ester (OPX).
  • grain refiners are included in the indium compositions in amounts of 0.1 ppm to 5 g/L, more preferably from 0.5
  • the one or more suppressors can be included in the indium compositions.
  • Suppressors include, but are not limited to, phenanthroline and its derivatives, such as 1,10-phenantroline, triethanolamine and its derivatives, such as triethanolamine lauryl sulfate, sodium lauryl sulfate and ethoxylated ammonium lauryl sulfate, polyethyleneimine and its derivatives, such as hydroxypropylpolyeneimine (HPPEI-200), and alkoxylated polymers.
  • Such suppressors are included in the indium compositions in conventional amounts. Typically, suppressors are included in amounts of 1 ppm to 5 g/L.
  • Levelers include, but are not limited to, polyalkylene glycol ethers. Such ethers include, but are not limited to, dimethyl polyethylene glycol ether, di-tertiary butyl polyethylene glycol ether, polyethylene/polypropylene dimethyl ether (mixed or block copolymers), and octyl monomethyl polyalkylene ether (mixed or block copolymer). Such levelers are included in conventional amounts. In general, such levelers are included in amounts of 100 ppb to 500 ppb.
  • one or more hydrogen suppressors can included in the indium compositions to suppress hydrogen gas formation during indium metal electroplating.
  • Hydrogen suppressors include epihalohydrin copolymers.
  • Epihalohydrins include epichlorohydrin and epibromohydrin.
  • copolymers of epichlorohydrin are used.
  • Such copolymers are water-soluble polymerization products of epichlorohydrin or epibromohydrin and one or more organic compounds which includes nitrogen, sulfur, oxygen atoms or combinations thereof.
  • Nitrogen-containing organic compounds copolymerizable with epihalohydrins include, but are not limited to:
  • Aliphatic chain amines include, but are not limited to, dimethylamine, ethylamine, methylamine, diethylamine, triethyl amine, ethylene diamine, diethylenetriamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, isooctylamine, nonylamine, isononylamine, decylamine, undecylamine, dodecylaminetridecylamine and alkanol amines.
  • Unsubstituted heterocyclic nitrogen compounds having at least two reactive nitrogen sites include, but are not limited to, imidazole, imidazoline, pyrazole, 1,2,3-triazole, tetrazole, pyradazine, 1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-thiadiazole and 1,3,4-thiadiazole.
  • Substituted heterocyclic nitrogen compounds having at least two reactive nitrogen sites and having 1-2 substitutions groups include, but are not limited to, benzimidazole, 1-methylimidazole, 2-methylimidazole, 1,3-diemthylimidazole, 4-hydroxy-2-amino imidazole, 5-ethyl-4-hydroxyimidazole, 2-phenylimidazoline and 2-tolylimidazoline.
  • one or more compounds chosen from imidazole, pyrazole, imidazoline, 1,2,3-triazole, tetrazole, pyridazine, 1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-thiadiazole and 1,3,4-thiadiazole and derivatives thereof which incorporate 1 or 2 substituents chosen from methyl, ethyl, phenyl and amino groups are used to form the epihalohydrin copolymer.
  • epihalohydrin copolymers are commercially available such as from Raschig GmbH, Ludwigshafen Germany and from BASF, Wyandotte, MI, USA, or may be made by methods disclosed in the literature.
  • An example of a commercially available imidazole/epichlorohydrin copolymer is LUGALVAN® IZE copolymer, obtainable from BASF.
  • Epihalohydrin copolymers can be formed by reacting epihalohydrins with the nitrogen, sulfur or oxygen containing compounds described above under any suitable reaction conditions.
  • both materials are dissolved in suitable concentrations in a body of mutual solvent and reacted therein at, for example, 45 to 240 minutes.
  • the aqueous solution chemical product of the reaction is isolated by distilling off the solvent and then is added to the body of water which serves as the electroplating solution, once the indium salt is dissolved.
  • these two materials are placed in water and heated to 60° C with constant vigorous stirring until they dissolve in the water as they react.
  • a wide range of ratios of the reaction compound to epihalohydrin can be used, such as from 0.5:1 to 2:1 moles.
  • the molar ratio is from 0.6:1 to 2:1 moles, more typically the molar ratio is 0.7 to 1:1, most typically the molar ratio is 1:1.
  • reaction product may be further reacted with one or more reagents before the electroplating composition is completed by the addition of indium salt.
  • the described product may be further reacted with a reagent which is at least one of ammonia, aliphatic amine, polyamine and polyimine.
  • the reagent is at least one of ammonia, ethylenediamine, tetraethylene pentamine and a polyethyleneimine having a molecular weight of at least 150, although other species meeting the definitions set forth herein may be used.
  • the reaction can take place in water with stirring.
  • reaction between the reaction product of epichlorohydrin and a nitrogen-containing organic compound as described above and a reagent chosen from one or more of ammonia, aliphatic amine, and arylamine or polyimine can take place and can be carried out at a temperature of, for example, 30° C to 60° C for, example, 45 to 240 minutes.
  • the molar ratio between the reaction product of the nitrogen containing compound-epichlorohydrin reaction and the reagent is typically 1:0.3-1.
  • the epihalohydrin copolymers are included in the compositions in amounts of 0.01 g/L to 100 g/L. preferably, epihalohydrin copolymers are included in amounts of 0.1 g/L to 80 g/L, more preferably, they are included in amounts of 0.1 g/L to 50 g/L, most preferably in amounts of 1 g/L to 30 g/L.
  • the indium compositions may be used to deposit substantially uniform, void-free, indium metal layers on metal layers of various substrates.
  • the indium layers are also substantially dendrite-free.
  • the indium layers preferably range in thickness from 10 nm to 100 ⁇ m, more preferably from 100 nm to 75 ⁇ m.
  • Apparatus used to deposit indium metal on metal layers is conventional.
  • conventional soluble indium electrodes are used as the anode.
  • Any suitable reference electrode may be used.
  • the reference electrode is a silver chloride/silver electrode.
  • Current densities may range from 0.1 ASD to 10 ASD, preferably from 0.1 to 5 ASD, more preferably from 1 to 4 ASD.
  • the temperatures of the indium compositions during indium metal electroplating can range from room temperature to 80 °C. Preferably, the temperatures range from room temperature to 65 °C, more preferably from room temperature to 60 °C. Most preferably the temperature is room temperature.
  • the indium compositions may be used to electroplate indium metal on nickel layers of various substrates, including components for electronic devices, for magnetic field devices and superconductivity MRIs.
  • the metal layers preferably range from 10 nm to 100 ⁇ m, more preferably from 100 nm to 75 ⁇ m.
  • the indium compositions may also be used with conventional photoimaging methods to electroplate indium metal small diameter solder bumps on various substrates such as silicon wafers. Small diameter bumps preferably have diameters of 1 ⁇ m to 100 ⁇ m, more preferably from 2 ⁇ m to 50 ⁇ m, with aspect ratios of 1 to 3.
  • the indium compositions may be used to electroplate indium metal on a component for an electrical device to function as a TIM, such as for, but not limited to, ICs, microprocessors of semiconductor devices, MEMS and components for optoelectronic devices.
  • a component for an electrical device such as for, but not limited to, ICs, microprocessors of semiconductor devices, MEMS and components for optoelectronic devices.
  • electronic components may be included in printed wiring boards and hermetically sealed chip-scale and wafer-level packages.
  • packages typically include an enclosed volume which is hermetically sealed, formed between a base substrate and lid, with the electronic device being disposed in the enclosed volume. The packages provide for containment and protection of the enclosed device from contamination and water vapor in the atmosphere outside the package.
  • the presence of contamination and water vapor in the package can give rise to problems such as corrosion of metal parts as well as optical losses in the case of optoelectronic devices and other optical components.
  • the low melting temperature (156° C) and high thermal conductivity ( ⁇ 82 W/m°K) are properties which make indium metal highly desirable for use as a TIM.
  • the indium compositions may be used to electroplate underlayers on substrates to prevent whisker formation in electronic devices.
  • the substrates include, but are not limited to, electrical or electronic components or parts such as film carriers for mounting semiconductor chips, printed circuit boards, lead frames, contacting elements such as contacts or terminals and plated structural members which demand good appearance and high operation reliability.
  • Photoresist patterned silicon wafers from Silicon Valley Microelectronics, Inc. with a plurality of vias having a diameter of 75 ⁇ m and copper seed layer at the base of each via were electroplated with a nickel layer using NIKALTM BP nickel electroplating bath available from Dow Advanced Materials. Nickel electroplating was done at 55 °C, with a cathode current density of 1 ASD for 120 seconds. A conventional rectifier supplied the current. The anode was a soluble nickel electrode. After plating the silicon wafer was removed from the plating bath, the photoresist was stripped from the wafers with SHIPLEY BPRTM Photostripper available from Dow Advanced Materials and rinsed with water. The nickel deposits appeared substantially smooth and without any observable dendrites on the surface.
  • Figure 1A is an optical image of one of the nickel plated copper seed layers taken with a LEICATM optical microscope.
  • the foregoing nickel layer electroplating process was repeated on another set of photoresist patterned wafers except that after electroplating the nickel layer, the nickel plated silicon wafers were immersed in the indium electroplating composition and indium metal was electroplated on the nickel.
  • Indium electroplating was done at 25 °C at a current density of 4ASD for 30 seconds.
  • the pH of the indium electroplating composition was 2.4.
  • the anode was an indium soluble electrode. After the indium was plated on the nickel, the photoresist was stripped from the wafers and the morphology of the indium deposits was observed. All of the indium deposits appeared rough.
  • Figure 1B is an optical image of one of the indium metal deposits electroplated on the nickel layer.
  • the indium deposit was very rough in contrast to the nickel deposit as shown in Figure 1A .
  • Example 2 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1-(2-hydroxyethyl)-2-imidazolidinethione 0.25 g/L
  • the nickel plated silicon wafers were immersed in the indium electroplating composition and indium metal was electroplated on the nickel.
  • Indium electroplating was done at 25 °C at a current density of 4ASD for 30 seconds.
  • the pH of the composition was 2.4.
  • the anode was an indium soluble electrode. After indium was electroplated on the nickel layers, the photoresist was stripped from the wafers and the indium morphology was observed. All of the indium deposits appeared uniform and smooth.
  • Figure 2 is an optical microscope image of one of the indium metal deposits electroplated on the nickel layer. The indium deposit appeared smooth in contrast to the indium deposit of Figure 1B .
  • Example 3 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1-(2-hydroxyethyl)-2-imidazolidinethione 1.25 g/L
  • the nickel plated silicon wafers were immersed in the indium electroplating composition and indium metal was electroplated on the nickel.
  • Indium electroplating was done at 25 °C at a current density of 4ASD for 30 seconds.
  • the pH of the composition was 2.4.
  • the photoresist was stripped from the wafers and the indium morphology was observed. All of the indium deposits appeared uniform and smooth.
  • Figure 3 is an optical microscope image of one of the indium metal deposits electroplated on the nickel layer. The indium deposit appeared smooth in contrast to the indium deposit of Figure 1B .
  • Example 4 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1-(2-hydroxyethyl)-2-imidazolidinethione 0.01 g/L
  • the nickel plated silicon wafers were immersed in the indium electroplating composition and indium metal was electroplated on the nickel.
  • Indium electroplating was done at 25 °C at a current density of 4ASD for 30 seconds.
  • the pH of the composition was 2.4.
  • the anode was an indium soluble electrode. After indium was electroplated on the nickel layers, the photoresist was stripped from the wafers and the indium morphology was observed. All of the indium deposits appeared uniform and smooth.
  • Figure 4 is an optical microscope image of one of the indium metal deposits electroplated on the nickel layer. The indium deposit appeared smooth in contrast to the indium deposit of Figure 1B .
  • Example 2 The method described in Example 2 above was repeated except that the indium electroplating composition included the following components: Table 5 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1-(2-hydroxyethyl)-2-imidazolidinethione 0.1 g/L
  • the nickel plated silicon wafers were immersed in the indium electroplating composition and indium metal was electroplated on the nickel.
  • Indium electroplating was done at 25 °C at a current density of 4ASD for 30 seconds.
  • the pH of the composition was 2.4.
  • the anode was an indium soluble electrode. After indium was electroplated on the nickel layers, the photoresist was stripped from the wafers and the indium morphology was observed. All of the indium deposits appeared uniform and smooth.
  • Figure 5 is an optical microscope image of one of the indium metal deposits electroplated on the nickel layer. The indium deposit appeared smooth in contrast to the indium deposit of Figure 1B .
  • the indium electroplating composition includes the following components: Table 6 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1-(2-aminoethyl)-2-imidazolidinethione 0.25 g/L Quaternary amine surfactant 2 5 ppm 2 TOMAMINE® QC-15 surfactant available from Air Products
  • the pH of the bath during electroplating is 2.4.
  • the nickel plated silicon wafers are immersed in the indium electroplating composition and indium metal is electroplated on the nickel.
  • Indium electroplating is done at 25 °C at a current density of 4ASD for 11 seconds.
  • the photoresist is stripped from the wafers and the indium morphology is observed. All of the indium deposits are expected to appear uniform and smooth substantially the same as shown in Figures 2-5 .
  • An indium electroplating composition which includes the following components is prepared: Table 7 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 4,5-dihydroxy-1-methyl-2-imidazolidinethione 0.5 g/L Polyethyleneglycol octyl (3-sulfopropyl) diether 3 10 ppm 3 RALUFON® EA 15-90 surfactant available from Raschig
  • the pH of the bath during electroplating is 2.4.
  • the nickel plated silicon wafers are immersed in the indium electroplating composition and indium metal is electroplated on the nickel.
  • Indium electroplating is done at 25 °C at a current density of 4ASD for 11 seconds.
  • the photoresist is stripped from the wafers and the indium morphology is observed. All of the indium deposits are expected to appear uniform and smooth substantially the same as shown in Figures 2-5 .
  • An indium electroplating composition which includes the following components is prepared: Table 8 COMPONENT AMOUNT Indium sulfate 45 g/L Citric acid 96 g/L Sodium citrate dihydrate 59 g/L 1,3-dimethyl-2-imidazolidinethione 0.25 g/L Quaternary amine surfactant 4 5 ppm Sodium 2-naphthol-7-sulfonate 0.1 g/L 4 TOMAMINE® QC-15 surfactant available from Air Products
  • the pH of the bath during electroplating is 2.4.
  • the nickel plated silicon wafers are immersed in the indium electroplating composition and indium metal is electroplated on the nickel.
  • Indium electroplating is done at 25 °C at a current density of 4ASD for 11 seconds.
  • the photoresist is stripped from the wafers and the indium morphology is observed. All of the indium deposits are expected to appear uniform and smooth substantially the same as shown in Figures 2-5 .
  • FIG. 6 is an optical microscope image of the indium electroplated from the bath of Table 9. As shown in Figure 6 the indium deposit was uniform and smooth.

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Claims (11)

  1. Ein Verfahren, das Folgendes beinhaltet:
    a) Bereitstellen eines Substrats, das eine Nickelschicht beinhaltet;
    b) In-Kontakt-Bringen des Substrats mit einer Indiumelektroplattierungszusammensetzung, die eine oder mehrere Quellen von Indiumionen, eine oder mehrere 2-Imidazolidinthionverbindungen und Zitronensäure, Salz von Zitronensäure oder Mischungen davon beinhaltet, wobei die Indium elektroplattierende Zusammensetzung frei von Zusatzmetallen ist; und
    c) Elektroplattieren einer Indiummetallschicht auf der Nickelschicht des Substrats mit der Indium elektroplattierenden Zusammensetzung.
  2. Verfahren gemäß Anspruch 1, wobei die eine oder die mehreren 2-Imidazolidinthionverbindungen die folgende Formel aufweisen:
    Figure imgb0003
     wobei R1 und R2 unabhängig ausgewählt sind aus Wasserstoff, linearem oder verzweigtem (C1-C12)Alkyl, linearem oder verzweigtem Hydroxy(C1-C12)alkyl, linearem oder verzweigtem (C1-C12)Alkoxy, linearem oder verzweigtem (C3-C12)Allyl, Amino, primärem, sekundärem oder tertiärem Amino(C1-C12)alkyl, Acetyl und substituiertem oder nicht substituiertem Aryl(C1-C12)Alkyl; R3, R4, R5 und R6 unabhängig ausgewählt sind aus Wasserstoff, linearem oder verzweigtem (C1-C12)Alkyl, Hydroxyl, linearem oder verzweigtem Hydroxy(C1-C12)alkyl, primärem, sekundärem oder tertiärem Amino, Aryl, linearem oder verzweigtem (C1-C12)Alkoxy, primärem, sekundärem oder tertiärem Amino(C1-C12)alkyl und Acetyl, wobei Substituentengruppen auf dem Aryl lineares oder verzweigtes (C1-C5)Alkyl, Hydroxyl, Hydroxy(C1-C5)alkyl, (C1-C3)Alkoxy und primäres, sekundäres und tertiäres Amino(C1-C5)alkyl umfassen, aber nicht darauf beschränkt sind.
  3. Verfahren gemäß Anspruch 2, wobei die eine oder die mehreren 2-Imidazolidinthionverbindungen ausgewählt sind aus 2-Imidazolidinthion, 1,3-Dimethyl-2-imidazolidinthion, 1-Methyl-5-phenyl-2-imidazolidinthion, 1,3-Diethyl-2-imidazolidinthion, 1-Methyl-2-imidazolidinthion, 4,4-Dimethyl-2-imidazolidinthion, 4,5-Dimethyl-2-imidazolidinthion, (4S)-4-Methyl-2-imidazolidinthion, 1-Dodecyl-2-imidazolidinthion, 1-Butyl-5-(1-methylethyl)-2-imidazolidinthion, 1,3-Diallyl-2-imidazolidinthion, 1-Acetyl-3-allyl-2-imidazolidinthion, 1-(2-Aminoethyl)-2-imidazolidinthion, 1-Acetyl-2-imidazolidinthion, 4,5-Dihydroxy-1-methyl-2-imidazolidinthion, 1-(2-Hydroxyethyl)-2-imidazolidinthion, 1,3-Bis(hydroxymethyl)-2-imidazolidinthion, 1-Ethyl-5-(4-methoxyphenyl)-2-imidazolidinthion, 1,3-Diethyl-4,5-dihydroxy-4,5-diphenyl-2-imidazolidinthion und 1,3 Bis[(cyclohexylamino)methyl]-2-imidazolidinthion.
  4. Verfahren gemäß Anspruch 1, wobei die Indium elektroplattierende Zusammensetzung ferner ein oder mehrere Tenside, ausgewählt aus Amintensiden, ethoxylierten Naphtholen, sulfonierten Naphtholpolyethern, (Alkyl)phenolethoxylaten, sulfonierten Alkylalkoxylaten, Alkylenglycolalkylethern und sulfopropylierten polyalkoxylierten beta-Naphtholalkalisalzen, beinhaltet.
  5. Verfahren gemäß Anspruch 1, wobei die Indium elektroplattierende Zusammensetzung ferner ein oder mehrere Copolymere eines Reaktionsprodukts von Epihalohydrin und einer oder mehreren Stickstoff enhaltenden organischen Verbindungen beinhaltet.
  6. Verfahren gemäß Anspruch 1, wobei die eine oder die mehreren 2-Imidazolidinthionverbindungen in der Indium elektroplattierenden Zusammensetzung in Mengen von 0,005 g/l bis 5 g/l eingeschlossen sind.
  7. Verfahren gemäß Anspruch 1, wobei die Indium elektroplattierende Zusammensetzung ferner eine oder mehrere Quellen von Chloridionen beinhaltet, wobei ein Molverhältnis der Chloridionen zu den Indiumionen 2 : 1 oder mehr beträgt.
  8. Verfahren gemäß Anspruch 7, wobei das Molverhältnis von Chloridionen zu Indiumionen 2 : 1 bis 7 : 1 beträgt.
  9. Verfahren gemäß Anspruch 8, wobei das Molverhältnis von Chloridionen zu Indiumionen 4 : 1 bis 6 : 1 beträgt.
  10. Verfahren gemäß Anspruch 1, wobei die Nickelschicht 10 nm bis 100 µm dick ist.
  11. Verfahren gemäß Anspruch 1, wobei die Indiummetallschicht 10 nm bis 100 µm dick ist.
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