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    • 专利摘要:
    PLATING BATH FOR ELECTRODE-FREE DEPOSITION OF NICKEL LAYERS AND ITS METHOD. The present invention relates to aqueous plating bath compositions for the deposition of nickel and alloys that utilize novel stabilizing agents that have a carbon-carbon triple bond and a functional group to enhance the performance of the bath.
    公开号:BR112014028715B1
    申请号:R112014028715-5
    申请日:2013-05-31
    公开日:2022-01-25
    发明作者:Heiko Brunner；Jan Picalek；Iulia Bejan；Carsten Krause；Holger BERA；Sven Rückbrod
    申请人:Atotech Deutschland Gmbh；
    IPC主号:
    专利说明:

    field of invention
    [001] The present invention relates to aqueous plating bath compositions for electrodeless deposition of nickel and nickel alloys. Nickel coatings obtained by means of the present invention show high uniformity and high hardness, good wear resistance and corrosion resistance. Such coatings are suitable as a functional coating in the aerospace, automotive, electrical and electrodeless industries. The metal layers deposited from such plating baths are also useful as barrier layers and in semiconductor devices, printed circuit boards, IC substrates and the like. Background of the Invention
    [002] Barrier layers are used in electronic devices such as semiconductor devices, printed circuit boards, IC substrates and the like to separate layers of different composition and in this way prevent unwanted diffusion between these layers of different composition.
    [003] Typical barrier layer materials are binary nickel alloys, such as Ni-P alloys, which are typically deposited by non-electrical plating onto a first layer of a first composition, followed by depositing a second layer of a second composition on the barrier layer. This first layer may consist of copper or aluminium.
    [004] Another application of barrier layer materials in electronic devices is as a cover layer which is for example deposited over copper to prevent copper corrosion.
    [005] Another application of nickel deposits and nickel alloys is corrosion protection for various substrates.
    [006] Compositions for electrodeless nickel plating solutions are known in the art. For example, US patent 2,658,841 teaches the use of soluble organic acid salts as buffers for electrodeless nickel plating solutions. US patent 2,658,842 teaches the use of short chain dicarboxylic acids as EN bath enhancers. US Patent 2,762,723 teaches the use of sulfide and sulfur support additives for an electrodeless nickel plating bath to improve the stability of the bath.
    [007] US Patent 2,847,327 introduced other means of stabilizing an electrodeless nickel plating solution. These include the use of higher purity starting materials; more effective stabilizers from the heavy metals class such as Pb, Sb, Bi, Cu and SE; inorganic compounds such as iodates, and thio compounds; organic compounds such as alkenes and unsaturated alkynes and others. Purpose of the Invention
    [008] It is an object of the present invention to provide an electrodeless nickel plating bath for the deposition of nickel and nickel alloys, which has a high stability against unwanted decomposition and provides uniform coatings. Summary of the Invention
    [009] This objective is solved through an aqueous plating bath composition for electrodeless deposition of nickel and nickel alloys, the plating bath comprising: (i) a source of nickel ions, (ii) at least a complexing agent, (iii) at least one reducing agent, (iv) a stabilizing agent according to formula (1):

    [0010] where X is selected from O and NR4, n ranges from 1 to 6, m ranges from 1 to 8; R1, R2, R3 and R4 are independently selected from hydrogen and C1 to C4; Y is selected from -SO3R5, -CO2R5 and -PO3R52, and R5 is selected from hydrogen, C1-C4 alkyl and a suitable counterion.
    [0011] The present invention further relates to a method for deposition of nickel and nickel alloys by immersing the substrate to be plated in the above-described plating solution. Brief Description of Drawings
    [0012] Figure 1 shows a test substrate with copper wafers for deposition without nickel electrode.
    [0013] Figure 2 shows the stability of electrodeless nickel deposition baths, containing a stabilizing agent of the present invention (samples 1 to 3) or a comparison compound (example 6), during storage time, also called of downtime. Detailed Description of the Invention
    [0014] Electrodeless nickel plating compositions for the application of nickel coatings are well known in the art and the plating processes and compositions are described in various publications, such as US Patent Nos. 2,935,425; 3,338,726; 3,597,266; 3,717,482; 3,915,716; 4,467,067; 4466233 and 4780342. Electrodeless plating generally describes methods that do not utilize external current sources for the reduction of metal ions. The latter are commonly described as electrolytic or galvanic plating methods. In electrodeless plating, chemical solutions reducing hypophosphite-type reducing agents, boranes or formaldehyde are used to reduce metal ions to their metallic form and thus form a deposit on the substrate.
    [0015] A commonly used nickel alloy deposit is nickel phosphorus alloy (NPI). In general, NiP deposition solutions comprise at least four ingredients dissolved in a solvent, typically water. These are: (1) a source of nickel ions, (2) a reducing agent, (3) an acidic or hydroxide pH regulator to obtain the desired pH, and (4) a complexing agent for sufficient metal ions. to prevent its precipitation in the solution. A large number of complexing agents suitable for NiP solutions are described in the publications referred to above. If hypophosphite is used as the reducing agent, the deposit will contain nickel and phosphorus. Likewise, if a borane amine is employed, the deposit contains nickel and boron as shown in US Patent No. 3953654.
    [0016] The nickel ion can be supplied by using any soluble salt, such as nickel sulfate, nickel chloride, nickel acetate, nickel methyl sulfonate and mixtures thereof. The nickel concentration in the solution can vary widely and is about 0.1 to 60 g/l, preferably about 2 to 50 g/l, for example 4 to 10 g/l.
    [0017] The reducing agent is normally and preferably the hypophosphite ion to supply the bath by means of any suitable source, such as sodium, potassium, ammonium and nickel hypophosphite. Other reducing agents, such as boranes, borohydrides, hydrazine and derivatives thereof, and formaldehyde may also suitably be employed. The concentration of the reducing agent is generally in molar excess of the amount sufficient to reduce the nickel in the bath. The concentration of the reducing agent generally varies between 0.05 and 0.35 mol/l.
    [0018] The baths can be acidic, neutral or alkaline and the acidic or alkaline pH adjusters can be selected from a wide range of materials such as hydroxide, sodium hydroxide, hydrochloric acid and the like. The pH of the bath can range from about 2 to 12, with acid baths being preferred. A slightly acidic pH range, preferably from about 3.5 to 7, more preferably from about 4 to 6.5, is recommended.
    [0019] A complexing agent (sometimes also referred to as a chelating agent) or a mixture of complexing agents is included in the composition of the nickel-nickel alloy plating bath.
    [0020] In one embodiment, the carboxylic acids, hydroxyl carboxylic acids, aminocarboxylic acids, and the above-mentioned salts or mixtures thereof, can be employed as complexing agents. Useful carboxylic acids include mono-, di-, tri- and tetracarboxylic acids. The carboxylic acids can be substituted with various substituent moieties, such as hydroxy or amino groups, and the acids can be introduced into the plating bath as their sodium, potassium or ammonium salts. Some complexing agents, such as acetic acid, for example, can also act as a pH buffering agent, and the appropriate concentration of such additive components can be optimized for any plating bath, in consideration of their dual functionality.
    [0021] Examples of such carboxylic acids that are useful as complexing or chelating agents in the plating bath of the present invention include: monocarboxylic acids such as acetic acid, hydroxyacetic acid (glycolic acid), aminoacetic acid (glycine), 2-amino acid propanoic (alanine); 2-hydroxy propanoic acid (lactic acid); dicarboxylic acids such as succinic acid, amino succinic acid (aspartic acid), hydroxy succinic acid (malic acid), propanedioic acid (malonic acid), tartaric acid; tricarboxylic acids such as 2-hydroxy-1,2,3-propane tricarboxylic acid (citric acid); and tetracarboxylic acids such as tetradiamine ethylene acetic acid (EDTA). In one embodiment, mixtures of two or more of the above complexing/chelating agents are used in the plating bath in accordance with the present invention.
    [0022] Alkylamines can also be used as complexing agents, for example mono-, di- and trialkylamines. C1 -C3 alkyl amines, for example triethanolamine are preferred.
    [0023] The concentration of the complexing agent or, in case more than one complexing agent is used, the concentration of all the complexing agents together preferably ranges from 0.01 to 3.0 mol/l, plus preferably from 0.1 to 1.0 mol/l, and even more preferably from 0.2-0.6 mol/l.
    [0024] In case a hypophosphite compound is used as a reducing agent, a Ni-P alloy deposit is obtained. A borane-based compound as the reducing agent leads to a deposition of Ni-B alloy and a mixture of hypophosphite and borane-based compounds as the reducing agents leads to a ternary deposition of the Ni-BP alloy. A nitrogen-based reducing agent such as hydrazine and derivatives thereof, as well as formaldehyde as a reducing agent leads to nickel deposits.
    [0025] Additional metal ions may be present in the nickel plating solution in the event that the respective nickel alloy is obtained in the form of a deposit.
    [0026] A suitable plating composition can be formed by dissolving the ingredients in water and adjusting the pH to the desired range.
    [0027] The part to be made of nickel or nickel alloy can be coated for the Thickness and the amount of deposits desired by immersing the part in the nickel plating bath, which is maintained over a temperature range from about 20 to 100°C, preferably 70 to 95°C or 90°C. A deposit thickness of up to 60 µm or higher may be employed, depending on the application.
    [0028] For corrosion resistant coatings, in general, a greater thickness of between 30 to 60 uM is desirable, while for electronic applications a thickness of between 5 to 14 uM is generally applied.
    [0029] It will be appreciated by those skilled in the art that the rate of metallization can be influenced by a number of factors, including (1) the pH of the plating solution, (2) the concentration of the reducing agent, (3) ) the temperature of the plating bath, (4) the concentration of soluble nickel, (5) the ratio of bath volume to plated surface area, and (6) the method of creating and stirring solution, and that the above parameters are provided only to give general directions for the practice of the present invention.
    [0030] A highly phosphorous NiP alloy is defined in the present invention as a metallic coating that contains less than 90% by weight of Ni and equal to or greater than 10% by weight of P, for example, 10.5% by weight. . High phosphorous alloys generally contain up to 15% P by weight. A highly phosphorous alloy (NiP) that contains more than about 10.5% phosphorus is known as a highly phosphorous NiP coating and is paramagnetic (non- magnetic) as plated.
    [0031] A mildly phosphorous NiP alloy is defined, in the present invention, as a metallic coating that contains between 5 to 9% by weight of P.
    [0032] The electrodeless plating bath of the present invention is suitable for providing nickel-phosphorus alloy coatings with a wide range of P content of between about 5 to 15% P by weight.
    [0033] Generally, the thickness of NiP deposits can vary between 5 to 60 µm. The thickness depends on the technical application and may be higher or lower for certain applications. For example, if the NiP layer is deposited to provide a corrosion resistant coating, generally a thickness of between 30 to 60 µM is desired.
    [0034] In addition, the plating bath composition contains a stabilizing agent according to formula (1):

    [0035] wherein X is selected from O and NR 4, n ranges from 1 to 6, m ranges from 1 to 8; R1, R2, R3 and R4 are independently selected from hydrogen and C1 to C4; Y is selected from -SO3R5, -CO2R5 and -PO3R52, and R5 is selected from hydrogen, C1-C4 alkyl and a suitable counterion.
    [0036] If R5 is a suitable counterion, it can for example be selected from alkali metals such as sodium and potassium, or nickel and ammonium. If R5 is selected from the group consisting of C1 to C4 alkyl, it is preferably methyl and ethyl.
    [0037] Compounds according to formula (1) wherein n = 1 or 2 are particularly preferred. Compounds according to formula (1) wherein X = O, NH or NCH3 are particularly preferred. Compounds according to formula (1) wherein R1 , R2 , R3 are independently selected from hydrogen CH3 and are particularly preferred. Compounds according to formula (1) wherein m = 1, 2, 3 or 4 are particularly preferred. Compounds according to formula (1) wherein Y is selected from SO3H, -SO3Na, -SO3K, CO2H, -CO2Na and -CO2K are particularly preferred.
    [0038] For example, the following compounds can be used in a plating bath composition according to the present invention:
    [0039] 4-(But-3-ynoxy)-butane-1-sulfonate-sodium salt; 3-(prop-2-ynyloxy)-propyl-1-sulfonate-sodium salt; 3-(prop-2-ynylamino-propane-1-sulfonic acid; 2-(prop-2-ynyloxy)-acetate sodium salt; 2-(prop-2-ynyloxy)-propanoate sodium salt; salt of 4 -(prop-2-ynyloxy)-butane-1-sulfonate-sodium.
    [0040] The concentration of the stabilizing agent according to formula (1) preferably ranges from 0.02 to 5.0 mmols/l, more preferably from 0.05 to 3.0 mmols/l, even more preferably from 0 .1 and 2.0 mmols/l, even more preferably from 0.1 to 5.0 mmols/l, even more preferably from 0.3 to 5.0 mmols/l, and even more preferably from 0.5 to 5 .0 mmol/l.
    [0041] The stabilizing agents of the present invention provide high stability to electrodeless nickel deposition baths against spontaneous, unwanted, off-plating nickel deposition. Stabilizing agents according to the present invention are also suitable for providing stability of the high plating bath over a long period of time and that effect is obtained even if the bath is heated.
    [0042] Furthermore, the stabilizing agents of the present invention do not have a negative influence on the deposition rate of the electrodeless nickel deposition bath and the corrosion resistance of the nickel alloy or deposited nickel layer.
    [0043] The stabilizing agents of the present invention further have the advantage of being less toxic than other compounds containing a carbon-carbon triple bond and known to be used in electrodeless nickel deposition baths, such as propargyl alcohol. or propargyl alcohol ethoxylate.
    [0044] Other materials may be included in the plating bath according to the present invention, such as pH buffers, wetting agents, accelerators, bleaches, additional stabilizing agents, etc. These materials are known in the art.
    [0045] The aqueous electrodeless plating bath may further comprise a water-soluble metal salt of a non-nickel alloy M metal. The optional metal alloy M metal ions are preferably selected from the group consisting of titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, copper, silver, gold, aluminum, iron, cobalt, palladium, ruthenium, rhodium, osmium, iridium, platinum, zinc, cadmium, gallium, indium, tin, antimony, thallium, lead and bismuth.
    [0046] More preferably, the optional metal alloy M metal ions are selected from the group consisting of molybdenum, tungsten, copper, silver, gold, aluminum, zinc and tin.
    [0047] The concentration of metal ions of the optional metal alloy M preferably ranges from 10-4 to 0.2 mol/l, more preferably from 10-2 to 0.1 mol/l.
    [0048] When there is the addition of metal ions of a metal alloy M to the plating bath without aqueous electrode (depending on the type of reducing agent present) the ternary or quaternary alloys of Ni-MP, Ni-MB, and Ni- MBP are deposited.
    [0049] In another embodiment of the present invention, a water-soluble salt of a metal alloy M and a water-soluble salt of a second metal alloy M* are added to the aqueous electrodeless plating bath. In this case, nickel alloy deposits comprising the alloy metals M and M * are obtained.
    [0050] The aqueous electrodeless plating bath may further comprise the particles, preferably in the size range of 0.01 to 150 µm, more preferably 0.1 to 10 µm. These particles are insoluble or poorly soluble in the plating bath.
    [0051] The particles are preferably suspended in the aqueous electrodeless plating bath during the deposition process, and are co-deposited with the nickel alloy during plating. Co-deposited particles can serve functionalities such as lubricity, wear and abrasion resistance, corrosion protection and their combinations.
    [0052] The particles are selected from the group comprising ceramics, such as silica and alumina, glass, talc, plastic materials such as polytetrafluoroethylene (Teflon), diamond (polycrystalline and monocrystalline types), graphite, carbon nanotubes, oxides, carbonates, silicides, carbides (such as silicon carbide and tungsten carbide), sulphides, phosphates, silicates, borides, nitrides, oxylates, nitrides, fluorides of various metals, as well as metals and boron, tantalum, stainless steel, chromium, molybdenum, vanadium, zirconium, titanium and tungsten alloys.
    [0053] The concentration of optional particles in the plating bath without aqueous electrode, preferably varies from 0.01 to 0.5% by weight.
    [0054] The electrodeless plating bath of the present invention is particularly suitable for the deposition of nickel, phosphorus alloys, for example the mildly and highly NiP alloys as defined above. Hypophosphite-based reducing agents are applied through the deposition of NiP alloys. Such reducing agents provide the source of phosphorus in the deposited alloy.
    [0055] Highly NiP Alloys are particularly preferred. Such alloys are obtained when the coating process is carried out at a coating rate of between 4-14 µm/hour, more preferred 6-11 µm/hour. The person skilled in the art can determine the plating parameters to obtain such a plating rate by adjusting the plating parameters (temperature, concentrations, etc.) with routine experiments.
    [0056] The highly NiP alloys obtained by means of the electrodeless plating bath according to the present invention result in alloys with compressive stress. Voltage values, for example, range from -10 to -40 N / mm2. Such deposits exhibit high corrosion resistance and good adhesion to the underlying substrate, for example copper substrates, which are plated.
    [0057] The electrodeless plating bath may also contain metal stabilizers, such as PB, Cu, Se, Bi or Sb ions. Pb ions are generally less desirable because of their toxicity. The concentration of metal ions can vary and, for example, range between 1 - 50 mg/l, preferably between 3-10 mg/l. In addition, iodates can be added as additional stabilizers.
    [0058] The present invention further relates to a method for the electrodeless deposition of nickel and nickel alloys, comprising the steps of (i) supplying a substrate, (ii) immersing the substrate in the plating bath. without an aqueous electrode according to the present invention, (iii) and thereby depositing a nickel or nickel alloy on the substrate.
    [0059] In one embodiment, the method of the present invention utilizes the electrodeless plating bath of the present invention containing hypophosphite as the at least one reducing agent.
    [0060] In another embodiment the plating rate of the method according to the present invention ranges from 4-14 µm/hour to obtain a phosphorus content comprised between 10 to 15% by weight.
    [0061] The substrates to be coated with a nickel or nickel alloy layer from the plating bath according to the present invention are cleaned (pretreated) prior to deposition of metal. The type of pretreatment depends on the coating substrate material to be coated and is known in the art.
    [0062] Copper or copper alloy surfaces are treated with a corrosion cleaning method which is normally carried out in oxidizing, acidic solutions, eg a solution of sulfuric acid and hydrogen peroxide. Preferably, this is combined with another cleaning method in an acidic solution, such as, for example, a sulfuric acid solution, which is used either before or after corrosion cleaning.
    [0063] For a pre-treatment of aluminum and aluminum alloys of different zincs, for example the Xenolyte® ACA, Xenolyte® Etch MA, Xenolyte® CFA or Xenolyte® CF cleaner (all available from Atotech Deutschland GmbH) are available. meet cyanide-free chemical industry standards. Such pretreatment methods for aluminum and aluminum alloys are, for example, described in US 7223299 B2.
    [0064] The following non-limiting examples further illustrate the present invention. Examples
    [0065] The examples refer to the preparation for the synthesis of the stabilizing agent used in the plating baths of the present invention. Preparation Example 1
    [0066] Preparation of 4-(but-3-ynyloxy)-butane-1-sulfonate-sodium salt
    [0067] In 85 ml of THF, 2.0 g (49.9 mmols) of sodium hydride is suspended in argon. To this reaction mixture, 3.5 g (49.9 mmol) of but-3-yn-1-ol is added dropwise at room temperature.
    [0068] After completion of hydrogen evolution, 6.87 g (49.9 mmol) of 1,2-oxathian-2,2-dioxide dissolved in 20 ml of THF is added dropwise at room temperature. After the addition, the reaction mixture was stirred for an additional 12 hours, and the THF was removed in vacuo.
    [0069] The solid residue was extracted with ethyl acetate and filtered. The solid was dried under vacuum.
    [0070] 10.2 g (44.7 mmol) of a yellowish solid were obtained (89% yield). Preparation Example 2
    [0071] Preparation of 3-(prop-2-ynyloxy)propyl-1-sulfonate-sodium salt
    [0072] In 70 ml of THF, 1.997 g (49.9 mmol) of sodium hydride is suspended in argon. To this reaction mixture, 2.830 g (49.9 mmol) prop-2-in-1-ol is added dropwise at room temperature.
    [0073] After completion of hydrogen evolution, 6.1 g (49.9 mmol) of 1,2-oxathiolane-2,2-dioxide dissolved in 15 ml of THF is added dropwise at room temperature. After the addition, the reaction mixture was stirred for an additional 12 hours, and the THF was removed in vacuo.
    [0074] The solid residue was extracted with ethyl acetate and filtered. The solid was dried under vacuum.
    [0075] 9.0 g (44.9 mmol) of a yellowish solid were obtained (90% yield). Preparation Example 3
    [0076] Preparation of 3-(prop-2-ynylamino)-propane-1-sulfonic acid
    [0077] 4 g (71.2 mmol) of prop-2-yn-1-amine was dissolved in 75 ml of THF and cooled to 0°C. To this mixture, 8.87 g (71.2 mmol) of 1,2-oxathiolane 2,2,-dioxide dissolved in 25 ml of THF was added dropwise at 0° to 5°C. After the addition the reaction mixture was warmed to room temperature and stirred for 12 hours.
    [0078] The beige crystals that occur were filtered and washed with 10 ml of THF and 10 ml of ethanol. The solid was dried under vacuum.
    [0079] 10.2 g (57.6 mmol) of a beige solid were obtained (81% yield). Preparation Example 4
    [0080] Preparation of 2-(prop-2-ynyloxy)-acetate sodium salt
    [0081] 1.8 g (44 mmol) of sodium hydride was suspended in 18.88 g of DMF at room temperature. To this suspension, 3.5 g (37 mmol) of 2-chloroacetic acid are dosed within 10 min at room temperature.
    [0082] In a second flask, 1.8 g (44 mmol) of sodium hydride was suspended in 56.6 g of DMF. To this suspension, 2.08 g (36.74 mmol) prop-2-in-1-ol is given at room temperature.
    [0083] After completion of hydrogen evolution, the 2-chloroacetic acid sodium salt solution is added dropwise to the sodium prop-2-in-1-olate solution at room temperature within 6 minutes. After the addition, the reaction mixture was stirred for a further 25 hours at room temperature and heated at 50 °C for an additional 10 hours.
    [0084] The reaction mixture was cooled to room temperature and hydrolyzed with 20 ml of water. The solvent was removed and the residue dissolved in 50 ml of methanol and filtered. The filtrate was evaporated and the solid residue was washed with 200 ml of diethyl ether.
    [0085] The resulting solid was dried under vacuum.
    [0086] 4.9 g (36 mmol) of a tan solid were obtained (98% yield). Preparation Example 5
    [0087] Preparation of sodium salt 2-(prop-2-ynyloxy)-propanoate
    [0088] 1.6 g (39.11 mmol) of sodium hydride was suspended in 18.88 g of DMF at room temperature. To this suspension, 3.8 g (33 mmol) of 2-chloropropanoic acid are dosed within 10 min at room temperature.
    [0089] In a second flask, 1.6 g (39.11 mmol) of sodium hydride was suspended in DMF at 56.64 g. To this suspension, 1886g (363.33 mmol) of prop-2-in-1-ol is given at room temperature.
    [0090] After completion of hydrogen evolution, a solution of the sodium salt of 2-chloropropanoic acid is added dropwise to the sodium prop-2-in-1-olate solution at room temperature within 6 minutes. After the addition, the reaction mixture was stirred for an additional 25 hours at room temperature and heated at 50°C for an additional 10 hours.
    [0091] The reaction mixture was cooled to room temperature and hydrolyzed with 20 ml of water. The solvent was removed and the residue dissolved in 50 ml of methanol and filtered. The filtrate was evaporated and the solid residue was washed with 200 ml of diethyl ether.
    [0092] The resulting solid was dried under vacuum.
    [0093] 4.79 g (32 mmol) of a tan solid were obtained (96% yield). Example 6
    [0094] Ethoxylated Propargyl alcohol is commercially available, for example, from BASF AG (Golpanol PME). Preparation Example 7
    [0095] Preparation of 4-(prop-2-ynyloxy)-butane-1-sulfonate-sodium salt
    [0096] In 45 mL of THF, 1.999 g (50 mmol) of sodium hydride is suspended in argon. To this reaction mixture, 2.830 g (50 mmol) prop-2-in-1-ol is added dropwise at room temperature.
    [0097] After completion of hydrogen evolution, 6.87 g (50 mmol) of 1,2-oxathian-2,2-dioxide dissolved in 20 ml of THF is added dropwise at room temperature. After the addition the reaction mixture was stirred for an additional 12 hours, and the THF was removed in vacuo.
    [0098] The solid residue was extracted with ethyl acetate and filtered. The solid was dried under vacuum.
    [0099] 8.4 g (39.2 mmol) of a yellowish solid were obtained (78% yield). Example 8: Determination of the stability number of electrodeless plating baths:
    [00100] The respective stabilizing agents of Examples 1 to 5 (according to the present invention) as well as 6 (comparative) were added to an aqueous plating bath stock solution comprising
    [00101] NISO4 • 6H2O 26.3 g / l of 0.1 mol / l
    [00102] Lactic acid (90% by weight) 24.0 g / l 0.27 mol / l
    [00103] Malic acid 19.8 g / l, 0.15 mol / l
    [00104] Sodium hypophosphite monohydrate 30 g / l, 0.22 mol / l
    [00105] 100 ml of the plating bath in question was heated to 80 ± 1°C in a 200 ml glass beaker with stirring. Then, 0.2 ml of a palladium test solution (125 mg/L palladium chloride in deionized water) was added every 60 s to the plating bath. The test is terminated when a gray precipitate associated with gas bubbles is formed in the plating bath, which indicates undesired decomposition of the plating bath.
    [00106] The stability number achieved by the plating bath under consideration corresponds to the number of palladium test solutions in 0.2 ml increments with a one-minute interval for the plating bath, until a precision is formed. - gray pith. The values shown correspond to a freshly prepared plating bath just after heating to a temperature of 80°C, after 120 minutes and after 240 minutes at 80°C.
    [00107] Entry 17 for Sample 1 (Table 1 in the Stability / Time No. column "0") for example corresponds to a 17-fold addition of 0.2 ml of palladium chloride solution from a bath of plating, which was heated to 80°C. After 3.4 ml (17 times 0.2 ml/l added at one minute intervals) and 17 minutes, a gray precipitate occurs. Stability numbers for the entries in Table 1 "120 minutes" (heating for 120 minutes at 80°C) and "240 minutes" (heating for 240 minutes at 80°C) result in stability numbers of 16 and 15, respectively. , indicating that the bath maintains its high stability even after prolonged heating.Table 1: Stability numbers for the different bath compositions


    [00108] As is evident from Table 1 and Figure 2, the stabilizing agents according to the present invention are suitable for providing high plating bath stability over a long period of time. In contrast, propargyl alcohol ethoxylate, a comparator compound with structural similarity to the stabilizing agents of the present invention, namely a carbon-carbon triple bond, has a lesser stabilizing effect on the electrodeless nickel deposition bath and does not act as a stabilizing agent for a long period of time. Example 9:
    [00109] Table 2 shows that the stabilizing agent does not negatively influence the plating rate.
    [00110] The plating experiments according to Table 2 were carried out in a one liter beaker using one liter of NISO4 ^6H2O solution (26.3 g/l) and triethanolamine as complexing agent, sodium hypophosphite monohydrate (30 g/l) and different concentrations of the additive at a temperature of 86°C (water bath) and a pH of 4.8.
    [00111] The deposition rate was measured using a stainless steel strip with a thickness of 0.1 mm, which was primed for one hour. The measurement was with a micrometer device. A Determination of plating ratio = 0.5 x (panel thickness after plating - panel thickness before plating in mm).
    [00112] The tension in the coating was measured using a tension strip finger. The test strips are made of chemically etched beryllium-copper alloy and have spring like properties. After plating the test strip is mounted on the Test Stand (Etension Analyzer Depot and Model No. 683 from Specialty & Development Tests Co., York, PA, USA), which measures the distance that the test strip legs scattered after plating. Distance L is included in a formula that calculates deposit voltage.
    [00113] Voltage = U / 3 * T * K
    [00114] L is the number of propagation increments, t is the deposit thickness, and K is the strip calibration constant.
    [00115] The thickness of the T deposit is determined using the weight gain method and determined according to the following formula: T = W / D * A, where W = weight in grams of deposit, D = density of deposited metal, expressed in grams per cm3, and A = surface area in cm2.
    [00116] It is recognized that each batch of test strips manufactured will respond with slight differences when used for depot stress testing. This degree of difference will be determined by the supplier when each batch of test strips is calibrated. The K value will be provided with each lot of test strips supplied by Specialty Testing & Development Co.
    [00117] Tension is also determined to be either compressive or tensile in nature. If the test strip legs are spread out on the side that has been plated, the deposit voltage is tensile in nature. If the test strip legs are distributed inward on the side that has been plated, the deposit stress is compressive in nature. Table 2: Deposition rate and coating stress by different concentrations of 3-(prop-2-ynyloxy)-propyl-1-sulfonate-sodium salt additive (Example 2)

    [00118] Table 2 also shows that the deposits obtained from the plating bath compositions according to the present invention have a compressive stress that is desired, since it positively influences the corrosion protection of the deposited nickel layer. . Example 10:
    [00119] Further experiments were carried out to test the nickel plating bath according to the present invention for the production of small structures as used in the semiconductor industry.
    [00120] An aqueous plating bath containing
    [00121] NISO4 • 6H2O 26.3 g / l of 0.1 mol / l
    [00122] Lactic acid (90% by weight) 24.0 g / l 0.27 mol / l
    [00123] Malic acid 19.8 g / l, 0.15 mol / l
    [00124] Sodium hypophosphite monohydrate 30 g / l, 0.22 mol / l
    [00125] Four different plating bath compositions were prepared by adding the following stabilizing agents to the bath matrix mentioned above.
    [00126] 3-(prop-2-ynylamino)-propane-1-sulfonic acid (Example 3), 35 mg/l
    [00127] 4-(prop-2-ynyloxy)-butane-1-sulfonate-sodium salt (Example 7) 100 mg/l
    [00128] 4-(But-3-ynyloxy)-butane-1-sulfonate-sodium salt (Example 1) 150 mg/l
    [00129] 3-(prop-2-ynyloxy)-propyl-1-sulfonate-sodium salt (Example 2) 120 mg/l.
    [00130] A comparative example was carried out using the aforementioned bath matrix without additive.
    [00131] The nickel deposition was copper on the pads of a test substrate as shown in Figure 1. Such substrates are used in plating experiments in the semiconductor industry. Figure 1 shows a number of 16 metallized copper pads. The numbers denote:
    [00132] 50 (diameter of copper pads in one),
    [00133] 75 (step (the distance between the center of two copper pads), in one).
    [00134] Coating was performed by dipping the substrate into the above-described plating composition (pH = 4.9, T = 85°C).
    [00135] Very good plating results can be obtained by applying plating bath compositions containing stabilizing agents according to the present invention: no overlap and very homogeneous thickness distribution of deposited nickel-phosphorus alloy are observed.
    [00136] Regarding the Comparative Example: Pads metallized from the free stabilizers of the nickel bath show homogeneous nickel deposits (with respect to the thickness distribution over the nickel surface) and small spots on the edges of the pads. Example 11: according to the present invention Determination of the stability number of electrodeless plating baths for different concentrations of stabilizing agents:
    [00137] The respective stabilizing agents of Examples 1 to 5 and 7 (according to the present invention) were added in different amounts with the aqueous plating bath stock solution of Example 8, and maintained at a temperature of 23°C. Shortly after reaching a constant temperature, the stability numbers were determined as described in Example 8. The concentrations of the stabilizing agents and the corresponding stability numbers are summarized in Table 3. Table 3: The stability numbers for various concentrations of stabilizing agents

    [00138] As is evident from Table 3, the stabilizing agents according to the present invention are suitable for providing high plating bath stability over a wide concentration range. Example 12: according to the invention Determining the number of electrodeless plating baths during the extended stability time:
    [00139] The respective Stabilizing Agents of Examples 2, 3 and 7 (according to the present invention) were added to the aqueous plating bath stock solution of Example 8 and heated to 86°C for the duration of the experiment. At certain times, 100 ml samples from the plating bath in question were transferred to a 200 ml glass beaker and heated to 80 ± 1°C while stirring. Stability numbers were determined as described in Example 8. Stabilizing agent concentrations, times and corresponding stability numbers are summarized in Table 4. Table 4: Stability of different numbers of bath compositions over an extended time

    [00140] As is evident from Table 4, the stabilizing agents according to the present invention are suitable for providing high stability of the plating bath over a long period of time even if the bath is heated. Example 13: Comparative example Determination of the number of electrodeless plating baths for different concentrations of stability stabilizing agents:
    [00141] The stabilizing agent of Example 2 (according to the present invention), as well as the comparative compounds of Propargyl Sulfonic Acid Sodium Salt (Sample 8), 3-hexyne-2,5-diol (Example 9 ) and 2-butyne-1-ol (sample 10) were added in different amounts to the aqueous plating bath stock solution of Example 8, and maintained at a temperature of 23°C. Shortly after reaching a constant temperature, the stability numbers were determined as described in Example 8. The concentrations of the stabilizing agent, the comparative compounds, and the corresponding stability numbers are summarized in Table 5. The sodium salt of sulfonic acid of propargyl is commercially available, for example, from BASF AG (Golpanol PS). 3-hexyne-2,5-diol and 2-butyne-1-ol are also commercially available. Table 5: Stability numbers for various concentrations of stabilizing agents and comparative compounds

    [00142] As is evident from Table 5, the stabilizing agents according to the present invention are suitable for providing high plating bath stability over a wide concentration range. In contrast, comparative compounds with structural similarity to the stabilizing agents of the present invention, namely a carbon-carbon triple bond, exhibit a significantly less stabilizing effect when added at the same concentration to a nickel deposition bath without electrode.
    权利要求:
    Claims (13)
    [0001]
    1. Aqueous plating bath composition for electrodeless deposition of nickel and nickel alloys, characterized in that the plating bath comprises (i) a source of nickel ions, (ii) at least one complexing agent selected from among the group consisting of amines, carboxylic acids, hydroxy carboxylic acids, amino carboxylic acids and salts thereof, (iii) at least one reducing agent selected from hypophosphite, borane amine, borohydrides, hydrazine and formaldehyde, (iv) a stabilizing agent according to formula (1):
    [0002]
    2. Aqueous electrodeless plating bath, according to claim 1, characterized in that R1, R2, R3 and R4 are selected from hydrogen, methyl and ethyl.
    [0003]
    3. Plating bath without aqueous electrode, according to claim 1 or 2, characterized in that R5 is selected from hydrogen, methyl, ethyl, sodium, potassium, nickel and ammonium.
    [0004]
    4. Plating bath without aqueous electrode, according to any one of claims 1 to 3, characterized in that Y represents SO3R5.
    [0005]
    5. An aqueous electrodeless plating bath according to any one of claims 1 to 4, characterized in that it further comprises at least one source of the alloy metal ion and wherein at least one alloy metal ion Alloy is selected from the group consisting of titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, copper, silver, gold, aluminum, iron, cobalt, palladium, ruthenium, rhodium , osmium, iridium, platinum, zinc, cadmium, gallium, indium, tin, antimony, thallium, lead and bismuth.
    [0006]
    6. Aqueous electrodeless plating bath, according to any one of claims 1 to 5, characterized in that the plating bath has a pH value of 3.5 to 7.
    [0007]
    7. Plating bath without aqueous electrode, according to any one of claims 1 to 6, characterized in that the concentration of nickel ions is from 0.1 to 60 g/L.
    [0008]
    8. An aqueous electrodeless plating bath, according to any one of claims 1 to 7, characterized in that the concentration of at least one complexing agent varies from 0.01 to 3.0 mol/L.
    [0009]
    9. An aqueous electrodeless plating bath, according to any one of claims 1 to 8, characterized in that the concentration of the at least one reducing agent varies from 0.01 to 3.0 mol/L.
    [0010]
    10. An aqueous electrodeless plating bath, according to any one of claims 1 to 9, characterized in that at least one reducing agent is a hypophosphite salt.
    [0011]
    11. Method for electrodeless deposition of nickel and nickel alloys, characterized in that it comprises the steps of: (i) supply of a substrate, (ii) immersion of the substrate in the plating bath without aqueous electrode, as defined in any one of claims 1 to 10, (iii) and thereby depositing a nickel or nickel alloy on the substrate.
    [0012]
    12. Method according to claim 11, characterized in that the electrodeless plating bath contains hypophosphite as the at least one reducing agent.
    [0013]
    13. Method according to claim 11 or 12, characterized by the fact that the plating rate varies from 4 to 14 μm/hour to obtain a phosphorus content between 10 to 15% by weight.
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    同族专利:
    公开号 | 公开日
    EP2671969A1|2013-12-11|
    TWI560316B|2016-12-01|
    JP2015524024A|2015-08-20|
    CA2875317C|2020-03-31|
    BR112014028715A2|2017-06-27|
    US9175399B2|2015-11-03|
    WO2013182489A2|2013-12-12|
    CN104321463A|2015-01-28|
    EP2855732B1|2018-07-18|
    CA2875317A1|2013-12-12|
    CN104321463B|2016-12-28|
    KR20150024317A|2015-03-06|
    MY168645A|2018-11-27|
    ES2688547T3|2018-11-05|
    TW201406992A|2014-02-16|
    EP2855732A2|2015-04-08|
    JP6161691B2|2017-07-12|
    KR101930585B1|2018-12-18|
    WO2013182489A3|2014-07-17|
    US20150110965A1|2015-04-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2658841A|1950-11-08|1953-11-10|Gen Am Transport|Process of chemical nickel plating and bath therefor|
    US2658842A|1951-01-04|1953-11-10|Gen Am Transport|Process of chemical nickel plating and bath therefor|
    US2762723A|1953-06-03|1956-09-11|Gen American Transporation Cor|Processes of chemical nickel plating and baths therefor|
    US2847327A|1954-10-25|1958-08-12|Gen Am Transport|Processes of chemical nickel plating and baths therefor|
    US2935425A|1954-12-29|1960-05-03|Gen Am Transport|Chemical nickel plating processes and baths therefor|
    US2841602A|1955-10-04|1958-07-01|Udylite Res Corp|Alkynoxy acids|
    US3338726A|1958-10-01|1967-08-29|Du Pont|Chemical reduction plating process and bath|
    US3457089A|1967-04-07|1969-07-22|Shipley Co|Electroless copperplating|
    US3597266A|1968-09-23|1971-08-03|Enthone|Electroless nickel plating|
    US3915716A|1969-04-17|1975-10-28|Schering Ag|Chemical nickel plating bath|
    US3649308A|1970-05-21|1972-03-14|Shipley Co|Stabilized electroless plating solutions|
    JPS504327B1|1970-06-03|1975-02-18|
    DE2028950B2|1970-06-12|1976-05-13|Shipley Co., Inc., Newton, Mass. |Aqueous solution for the electroless cutting of nickel, cobalt or its alloys|
    GB1315212A|1970-07-31|1973-05-02|Shipley Co|Electroless nickel and or cobalt plating solutions|
    US3953654A|1973-08-13|1976-04-27|Rca Corporation|Temperature-stable non-magnetic alloy|
    US4016051A|1975-05-02|1977-04-05|Starlite Chemicals, Inc.|Additives for bright plating nickel, cobalt and nickel-cobalt alloys|
    US4435254A|1978-11-01|1984-03-06|M&T Chemicals Inc.|Bright nickel electroplating|
    US4466233A|1982-09-30|1984-08-21|Thesman Industries, Inc.|Mower drive assembly|
    US4467067A|1982-12-27|1984-08-21|Shipley Company|Electroless nickel plating|
    US4600609A|1985-05-03|1986-07-15|Macdermid, Incorporated|Method and composition for electroless nickel deposition|
    US4699811A|1986-09-16|1987-10-13|Macdermid, Incorporated|Chromium mask for electroless nickel or copper plating|
    US4780342A|1987-07-20|1988-10-25|General Electric Company|Electroless nickel plating composition and method for its preparation and use|
    JP3115095B2|1992-04-20|2000-12-04|ディップソール株式会社|Electroless plating solution and plating method using the same|
    DE10327374B4|2003-06-18|2006-07-06|Raschig Gmbh|Use of propanesulfonated and 2-hydroxy-propanesulfonated Alkylaminaloxylaten as an aid for the electrolytic deposition of metallic layers and plating baths containing them|
    US7223299B2|2003-09-02|2007-05-29|Atotech Deutschland Gmbh|Composition and process for improving the adhesion of a siccative organic coating compositions to metal substrates|
    JP2005126734A|2003-10-21|2005-05-19|C Uyemura & Co Ltd|Electroless nickel plating bath, and plating method using the same|
    WO2005078163A1|2004-02-05|2005-08-25|Taskem, Inc.|Ternary and quaternary alloys to replace chromium|
    US20060283715A1|2005-06-20|2006-12-21|Pavco, Inc.|Zinc-nickel alloy electroplating system|
    JP5158320B2|2007-03-30|2013-03-06|上村工業株式会社|Electroless nickel plating method, link chain and manufacturing method thereof|
    JP2012508322A|2008-11-07|2012-04-05|エクスタリックコーポレイション|Electrodeposition bath, electrodeposition system, and electrodeposition method|
    EP2639335B1|2012-03-14|2015-09-16|Atotech Deutschland GmbH|Alkaline plating bath for electroless deposition of cobalt alloys|CN103952687B|2014-05-05|2017-02-15|广东东硕科技有限公司|Plating penetration prevention method for chemical nickel-plating of printed circuit board|
    US20150345027A1|2014-06-02|2015-12-03|Macdermid Acumen, Inc.|Aqueous Electroless Nickel Plating Bath and Method of Using the Same|
    US9708693B2|2014-06-03|2017-07-18|Macdermid Acumen, Inc.|High phosphorus electroless nickel|
    JP6352079B2|2014-07-03|2018-07-04|奥野製薬工業株式会社|Electroless plating solution, plating film, plating product and method for forming plating film|
    EP3026143A1|2014-11-26|2016-06-01|ATOTECH Deutschland GmbH|Plating bath and method for electroless deposition of nickel layers|
    EP3034650B1|2014-12-16|2017-06-21|ATOTECH Deutschland GmbH|Plating bath compositions for electroless plating of metals and metal alloys|
    JP6698685B2|2015-03-20|2020-05-27|アトテック ドイチェランド ゲーエムベーハー|How to activate a silicon substrate|
    TWI707061B|2015-11-27|2020-10-11|德商德國艾托特克公司|Plating bath composition and method for electroless plating of palladium|
    CN105624656B|2015-12-30|2018-05-01|大连大学|A kind of chemical Ni-P plating/Ni-Mo-P-PTFE composite structure platings and preparation method thereof|
    EP3190208B1|2016-01-06|2018-09-12|ATOTECH Deutschland GmbH|Electroless nickel plating baths comprising aminonitriles and a method for deposition of nickel and nickel alloys|
    EP3452635B1|2016-05-04|2020-02-26|ATOTECH Deutschland GmbH|Process for depositing a metal or metal alloy on a surface of a substrate including its activation|
    US10577692B2|2017-01-05|2020-03-03|International Business Machines Corporation|Pretreatment of iron-based substrates for electroless plating|
    CN107313034A|2017-06-27|2017-11-03|佛山科学技术学院|A kind of high phosphorus chemical plating nickel cobalt manganese phosphorus alloy solution for magnesium alloy and preparation method thereof|
    CN107475699A|2017-08-28|2017-12-15|中石化炼化工程（集团）股份有限公司|The corrosion-inhibiting coating of gas-liquid allotter, preparation method and applications|
    EP3456870A1|2017-09-13|2019-03-20|ATOTECH Deutschland GmbH|A bath and method for filling a vertical interconnect access or trench of a work piece with nickel or a nickel alloy|
    KR102036334B1|2017-09-20|2019-10-25|한국기계연구원|Electroless plating solution and electroless plating method|
    KR102036329B1|2017-09-20|2019-10-25|한국기계연구원|Electroless plating solution, electroless plating method and plating layer formed thereby|
    KR101932963B1|2018-02-20|2018-12-27|한국기계연구원|Composition for catalyst-free electroless plating and method for electroless plating using the same|
    CA3092257A1|2018-02-26|2019-08-29|Graphene Leaders CanadaInc.|Electroless plating of objects with carbon-based material|
    CN108607586B|2018-04-28|2021-02-05|重庆长安汽车股份有限公司|Nickel phosphide, preparation method thereof and method for producing hydrogen by electrolyzing water|
    KR102250500B1|2019-03-18|2021-05-12|엠에스씨|Electroless Ni plating solution for manufacturing automobile LDS parts used at neutral pH and medium temperature|
    CN110079794A|2019-05-08|2019-08-02|深圳市长裕环保有限公司|A kind of nanometer easily welds high hard wear-and corrosion-resistant fancy alloys catalytic liquid and preparation method thereof|
    WO2021225827A1|2020-05-08|2021-11-11|Lam Research Corporation|Electroplating cobalt, nickel, and alloys thereof|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-14| B06G| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]|
    2021-03-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-07-20| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-11-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12170693.1|2012-06-04|
    EP20120170693|EP2671969A1|2012-06-04|2012-06-04|Plating bath for electroless deposition of nickel layers|
    PCT/EP2013/061280|WO2013182489A2|2012-06-04|2013-05-31|Plating bath for electroless deposition of nickel layers|
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