KR101663841B1 - Electrolyte and method for deposition of matte metal layer - Google Patents

Abstract

The present invention relates to an electrolyte as well as an electrolyte for depositing a matte metal layer on the surface of a substrate, wherein the matte metal layer is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Potassium, aluminum, magnesium or boron in order to facilitate the deposition of a smooth, uniform layer with a much lower deposition metal requirement, There is a halogenide, sulfate or sulfonate of the element selected from the group consisting of

Description

ELECTROLYTE AND METHOD FOR DEPOSITION OF MATTE METAL LAYER FIELD OF THE INVENTION [0001]

The present invention relates to an electrolyte and a method for depositing a matte metal layer on a substrate surface. Specifically, the present invention relates to an electrolyte having a low concentration of deposited metal and a method for depositing a matte metal layer using such an electrolyte.

In general, it is an object to obtain a conventional glossy metal layer on the substrate surface when depositing the metal layer on the substrate surface. The deposited metal layer may retain the functional properties to optimize the substrate surface for future planning, or a decorative effect may be obtained. According to the intended use of the substrate, it is sometimes desirable that the metal layer is a non-glossy, matte or so-called purple metal layer at the substrate surface. This intention may on the one hand be based on the optical appearance of the deposit and on the other hand it may also have the property that a matte or so-called colloidal deposit becomes a special technical property, such as no-scintillation, May be desirable for decorative purposes. The applications of such matte or purplish metal layers are, for example, the jewelery industry, the accessories industry, the automotive industry, as well as the optical industry or the precision machinery industry. In particular, no-scintillation metal layers are needed in these fields. In the jewelry industry, deposition of a matte or purplish metal layer of non-allergenic or low-allergic metal is required. Likewise, the application of matte or purplish metal layers is also required in kitchen appliances and kitchen tools.

In the optical or precision machine industry, the deposition of a matte or purplish metal layer of various metals is beneficial because of the many features that derive from various metals, so that the substrate surface can be adapted for future technical applications. In this context, for example, ductility, hardness, corrosion resistance or similar mechanical properties of the substrate surface can be optimized.

International patent application WO 2007/076898 discloses a method for forming a matte metal layer, in particular a metal layer, such as metal vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tellurium, , Gold, thallium, bismuth or an alloy thereof. To deposit these metals on the surface of the substrate, WO 2007/076898 (for reference) forms emulsions and / or dispersions in the electrolyte by adding emulsifiers and / or dispersants, or wetting agents.

A disadvantage of electrolytes and methods known in the art is that it is sometimes difficult to obtain uniform deposits on the substrate surface. Accordingly, it is an object of the present invention to optimize electrolytes and methods known in the art.

In one aspect, the present invention provides an electrolyte composition for depositing a matte layer of a metal or an alloy on a surface of a substrate. The electrolyte composition includes V, Cr, Mn, Fe, Co, Ni, Cu, A deposit metal ion selected from the group consisting of Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, Pt, Au, Tl, Bi and combinations thereof; At least one halogenide, sulfate or sulfonate of an element selected from the group consisting of sodium, potassium, aluminum, magnesium or boron; And substituted and unsubstituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines or polyalkylene oxides And a quaternary amine. The present invention also relates to an electrolyte composition containing at least one dispersing agent selected from the group consisting of quaternary amines.

In another aspect, the present invention provides an electrolyte composition for depositing a matte layer of a metal or an alloy on a surface of a substrate. The electrolyte composition includes V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, A deposition metal ion selected from the group consisting of Rh, Pd, Ag, In, Sn, Sb, Te, Re, Pt, Au, Tl, Bi and combinations thereof; At least one halogenide, sulfate or sulfonate of an element selected from the group consisting of sodium, potassium, aluminum, magnesium or boron; Substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines or polyalkylene oxides At least one dispersing agent selected from the group consisting of amine; And surface active wetting agents selected from the group consisting of alkyl sulfates, sulfo-succinic acids and betaines.

The present invention also relates to a method for manufacturing a semiconductor device, comprising the steps of: exposing a substrate surface to the above-described electrolyte plating composition; And depositing a matte layer on the substrate surface by conducting a current between the substrate and the anode to deposit a matte layer on the substrate surface.

Another aspect of the present invention provides a method of depositing a matte nickel layer on a surface of a substrate in a more specific manner wherein the surface of the substrate is selected from the group consisting of at least about 10 g / L nickel ion and sodium, potassium, magnesium, aluminum, boron, To an electrolyte nickel plating composition comprising an auxiliary metal ion, wherein the weight ratio of the auxiliary metal ion to the nickel metal ion is at least about 0.8: 1; And conducting a current between the substrate and the anode to deposit a matte nickel layer on the substrate surface.

In another aspect, the present invention provides a method of depositing a matte nickel layer on a surface of a substrate, wherein the surface of the substrate is selected from the group consisting of at least about 40 g / L nickel ion and sodium, potassium, magnesium, aluminum, boron or combinations thereof To an electrolyte nickel plating composition containing an auxiliary metal ion, wherein the weight ratio of the auxiliary metal ion to the nickel metal ion is at least about 0.2: 1; And conducting a current between the substrate and the anode to deposit a matte nickel layer on the substrate surface.

The present invention also provides a method of depositing a matte cobalt-tin alloy layer on a surface of a substrate, wherein the surface of the substrate is coated with at least about 10 g / L cobalt ion, at least about 10 g / L tin ion and sodium, potassium, magnesium, Boron, or a combination thereof, wherein the total weight ratio of the auxiliary metal ion to the cobalt metal ion and the tin metal ion is at least about 0.2: 1, wherein the step of exposing the electrolyte cobalt- ; And conducting a current between the substrate and the anode to deposit a matte cobalt-tin alloy layer on the substrate surface.

Other objects and features will be in part apparent and some will be described below.

This application claims priority to European patent application 08012262.5, filed July 8, 2008, the disclosure of which is incorporated herein by reference in its entirety.

The present invention relates to a method of manufacturing a semiconductor device, comprising the steps of: (a) forming a metal layer on a surface of a substrate by using a metal material selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, On a substrate surface, a matte metal layer of a metal selected from the group consisting of any of the following alloys. Therefore, the electrolyte of the present invention can be used as a positive electrode active material of the present invention, which includes at least one of vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, ruthenium ion, rhodium ion, A metal ion for a plating metal selected from the group consisting of an ion, a tellurium ion, a rhenium ion, a platinum ion, a gold ion, a thallium ion, a bismuth ion and any compound ions listed.

In some embodiments, the source of the metal ions for plating is selected from the group consisting of vanadium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, ruthenium ions, rhodium ions, palladium ions, silver ions, Antimony ions, tellurium ions, rhenium ions, platinum ions, gold ions, thallium ions, bismuth ions, and any of the compound ions listed. Thus, the electrolyte can be any alloy of any of these metals, such as V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, Pt, Au, Is deposited on the surface of the substrate.

In some embodiments, the source of metal ions for plating is selected from the group consisting of iron ions, cobalt ions, nickel ions, copper ions, zinc ions, tin ions, silver ions and any of the compound ions listed. Thus, the electrolyte is suitable for depositing a matte metal layer of a metal selected from the group consisting of Fe, Co, Ni, Cu, Zn, Sn, Ag or alloys of any of these metals on the substrate surface. In a particular preferred embodiment, the source of metal ions for plating is selected from the group consisting of iron ions, cobalt ions, nickel ions, copper ions, tin ions, silver ions and any of the enumerated ions listed. Thus, the electrolyte is suitable for depositing a matte metal layer of a metal selected from the group consisting of Fe, Co, Ni, Cu, Sn, Ag or any alloy of these metals.

In each of the above-described aspects, the term "alloy" refers to three distinct aspects: an alloy of one of the listed metals with another of the listed metals; An alloy of one or more metals not listed with one of the listed metals; And alloys of one or more of the listed metals with one or more of the listed metals, with one of the listed metals. Thus, with respect to metal ions, in some embodiments the composition comprises only one or more of the listed ions; In other embodiments, it is combined with ions that are not selectively listed. That is, other metal ions not specifically listed in some embodiments are specifically excluded, and in other embodiments they are not excluded.

The electrolyte of the present invention is characterized in that it contains a relatively low concentration of metal ion for plating as compared with the electrolyte for the matte layer plating in the related art. If everything else for these electrolytes is the same, low concentrations of metal ions for plating result in electrolytes with low density. Generally speaking, such low density compositions tend not to reliably deposit a matte or purplish metal layer. Rather, this layer tends to be glossy or semi-glossy. Thus, the electrolyte of the present invention further comprises at least one halogenide, sulfate or sulfonate of an element selected from the group consisting of sodium, potassium, aluminum, magnesium or boron. By the addition of a halogenide, sulfate or sulfonate salt of sodium, potassium, aluminum, magnesium or boron, the density of the electrolyte is formed at or near the density of a conventional electrolyte containing a much higher concentration of plating metal ions.

In some embodiments, the additive that is partially used in place of the metal ion for plating (as compared to a conventional matte electrolyte) and maintains the density of the electrolyte at or near the density of the conventional electrolyte having a high metal ion concentration for plating may be sodium, potassium, Methane sulfonate of magnesium and hydrates thereof. They are sometimes referred to as density increasing compounds in that they, when incorporated into the electrolyte, result in higher densities than would otherwise be used. In some embodiments, aluminum sulphate and hydrates thereof are preferred. In some embodiments, sodium sulfate and its hydrates are preferred. In some embodiments, magnesium sulfate and its hydrates are preferred. In some embodiments, boron tetrafluoride is used. In some embodiments, a combination of aluminum sulfate and its hydrate and boron tetrafluoride is used.

In a preferred embodiment, the density increasing compounds present in the electrolyte of the present invention are sodium sulfate and its hydrates, magnesium sulfate and its hydrates, aluminum sulphate and its hydrates or combinations of these three salts.

Surprisingly, the addition of soluble compounds of heavy cations, in particular of alkaline or alkaline earth halides, alkaline sulphates or alkaline earth sulphates or alkaline sulphonates or alkaline earth sulphonates as well as of aluminum sulphates, aluminum chlorides or boron tetrafluorides The disadvantages can be overcome by solely adding or compounding them, overcoming the disadvantages known in the art, and specifically plating a matte or purplish metal layer from an electrolyte having a relatively low concentration of plating metal ions.

According to the present invention, the electrolyte contains a salt that maintains the density of the electrolyte of the present invention at a concentration such that the cation of the salt present in the electrolyte of the present invention is in the range of 10 to 100% by weight of the concentration of the metal to be deposited. The salt is preferably added to the electrolyte of the present invention at such a concentration that the cation of the salt is present in a range of 20 to 60% by weight of the concentration of the metal to be deposited.

Generally, the concentration of the salt of the auxiliary metal ion is such that the weight ratio of the auxiliary metal ion to the plating metal ion is at least about 0.2: 1, at least about 0.4: 1, at least about 0.6: 1, or even at least about 0.8: There is enough to exist. In some embodiments, the auxiliary metal ion is present in a weight ratio of the auxiliary metal ion to the plating metal ion of between about 0.10: 1 and 1.3: 1, such as between about 0.10: 1 and 1: 1, preferably between about 0.2: 1 and about 0.6 : 1. Means an amount of metal which is reduced or not substantially reduced to a metal and which is therefore an amount less than a trace amount, that is, less than or equal to 1 atomic%, less than or equal to 0.5 atomic%, preferably less than or equal to 0.1 atomic% Ionic species such as sodium, potassium, aluminum, magnesium or boron which are not incorporated into the layer. The auxiliary metal ions are used to substantially maintain the density of the solution as compared to conventional electrolytes, which generally contain a high concentration of metal ions for plating, which enables deposition of a matte or a purplish layer on the electrolytes having a relatively low concentration of plating metal ions Are incorporated into the electrolyte of the present invention.

For example, in an electrolytic nickel plating bath, such as a Watts bath, the weight ratio of auxiliary metal ion to nickel ion is at least about 0.2: 1, such as at least about 0.4: 1, at least about 0.6: 1, 0.8: 1, such as about 0.9: 1, about 1: 1, about 1.1: 1, about 1.2: 1, or even about 1.3: 1. In this regard, the weight ratio of the auxiliary metal ion to the nickel ion may range from about 0.2: 1 to about 1.3: 1, such as from about 0.6: 1 to about 1.2: 1. When incorporating auxiliary metal ions such as sodium, potassium, aluminum, magnesium, or boron, more preferably magnesium, into the electrolytic nickel plating bath, the concentration of nickel ions is lower than that of conventional electrolytic matte nickel plating baths.

As a general proposition, in some preferred embodiments, the nickel concentration is generally at least about 10 g / L, at least about 15 g / L, at least about 20 g / L, at least about 30 g / L, at least about 40 g / Even at least about 45 g / L. The nickel concentration is generally about 80 g / L or less, about 75 g / L or less, or about 60 g / L or less. In some embodiments, the nickel ion concentration is between about 10 g / L and about 80 g / L, between about 10 g / L and about 70 g / L, between about 10 g / L and about 60 g / L, g / L to about 50 g / L. Generally, the auxiliary metal ion concentration is at least about 10 g / L, at least about 15 g / L, at least about 20 g / L, or even at least about 25 g / L. In some embodiments, the nickel ion concentration is at least about 10 g / L and the weight ratio of the auxiliary metal ion to the nickel ion is at least about 0.8: 1, at least about 1: 1, or at least about 1.2: 1. In some embodiments, the nickel ion concentration is at least about 40 g / L and the weight ratio of the auxiliary metal ion to the nickel ion is at least about 0.2: 1, at least about 0.4: 1, or at least about 0.6: 1. It has been found that the electrolytic nickel plating composition having a sufficient concentration of auxiliary metal ions and a nickel ion concentration within the above range to yield the above-described weight ratio deposits a matte and purplish nickel layer.

In another embodiment, the electrolytic cobalt-tin alloy plating bath has a weight ratio of auxiliary metal ions to total plating ions (i.e., the sum of cobalt ions and tin ions) of at least about 0.2: 1, such as at least about 0.4: 1, or even at least about 0.8: 1, such as about 0.9: 1, about 1: 1, about 1.1: 1, about 1.2: 1, or even about 1.3: 1. In this regard, the total weight ratio of auxiliary metal ions to cobalt ions and tin ions may range from about 0.2: 1 to about 1: 1, such as from about 0.2: 1 to about 0.8: 1.

The incorporation of an auxiliary metal ion such as sodium, potassium, aluminum, magnesium or boron, more preferably aluminum, sodium or a combination of both in the electrolytic cobalt-tin alloy plating bath, the concentration of the cobalt ion and the tin ion, Cobalt-tin alloy plating bath. The cobalt concentration is generally at least about 80 g / L, at least about 75 g / L, or at least about 60 g / L, and most preferably at least about 10 g / / L or less. The cobalt ion concentration may be between about 20 g / L and about 70 g / L, or between about 30 g / L and about 60 g / L. The tin concentration is generally at least about 60 g / L, at most about 50 g / L or even at least about 40 g / L, and most preferably at least about 10 g / L, L or less. The tin ion concentration may be between about 10 g / L and about 40 g / L, or between about 15 g / L and about 30 g / L. It has been found that the electrolyteic cobalt-tin alloy plating composition having a sufficient concentration of auxiliary metal ions to yield the cobalt ion and tin ion concentrations within the aforementioned ranges and the above-described weight ratios, deposits a matte purple cobalt-tin alloy layer .

The concentration of Ni, Co and / or Sn may be selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Pd, Ag, In, Sn, Sb, , Bi, and alloys thereof. The present invention is also applicable to the plating composition of the present invention.

Increasing the density of the electrolyte increases the cloud point, which should be avoided in general electrolytic electrolytes, but here it results in the desired matte effect of the deposited metal layer. The addition of the aforementioned inert compounds (i.e., Na, K, Al, Mg and / or B compounds, or so-called density increasing compounds), which do not include any depositable metal cation, And increases the density to such an extent that the matte metal layer is deposited. The density is preferably similar to conventional solutions for depositing matte or purplish layers. Thus, although the density of the electrolyte of the present invention is preferably between about 85% and about 115% of the electrolyte density of conventional plating metal ion concentrations, even though the electrolyte of the present invention has a much lower concentration of plating metal ions . In other words, the inert metal salt contributes to the density to achieve the desired density without the need for a high concentration of plating metal. The density is preferably between about 95% and about 105% of the conventional electrolyte. Higher densities generally contribute to lower haze. The electrolyte of the present invention exceeds the cloud point, which is useful for achieving an emulsion or dispersion to achieve a matte or purple appearance of the final coating layer.

In other words, the incorporation of an inert metal salt of Na, K, Al, Mg or B produces a composition which is generally below the operating temperature of the electrolyte composition. If the cloud point is exceeded in this way at the working temperature, it is useful to achieve an emulsion or dispersion, and thus a matte or purplish appearance of the final plating layer according to the present invention is achieved.

The electrolytes of the present invention can also be used in combination with substituted or unsubstituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, quaternary ammonium compounds substituted with fluorinated or perfluorinated wetting agents or polyalkylene oxides The dispersion or the emulsion forming material to be selected. These materials are suitable for forming emulsions and / or dispersions in the electrolyte.

The dispersion or emulsion forming materials suitable for use in the electrolyte of the present invention include substituted or unsubstituted polyalkylene oxides and derivatives of substituted or unsubstituted polyalkylene oxides. Useful polyalkylene oxide type surfactants include polyethylene glycol having an average molecular weight in the range of 5000 to 100,000 g / mol. Commercially available polyethylene glycols are sold under the tradename Pluriol® from BASF. Other polyalkylene oxide type surfactants include polypropylene glycols having an average molecular weight in the range of 500 to 20,000 g / mol. Commercially available polypropylene glycols are sold under the trade name Pluriol® from BASF. Also useful are polypropylene glycol / polyethylene glycol copolymers such as Pluronic (R) PE and RPE available from BASF. Their molecular weight is generally in the range of 1000 to 5000 g / mol. The substituted or unsubstituted polyalkylene oxide and derivatives thereof may be added to the electrolyte in a concentration range of 0.1 mg / L to 10 g / L.

The dispersion or emulsion forming material also includes quaternary amines substituted with quaternary amines and polyalkylene oxides. Quaternary amines substituted with polyalkylene oxides include those sold under the tradename Ethoquad® type available from Akzo Nobel. Quaternary amine surfactants sold under the trade names Hyamine and Barquat are also useful. Barquat® quaternary amines include Barquat® MB-50 and Barquat® MB-80 available from Lonza Chemical. The quaternary amine dispersions or emulsion forming materials substituted with quaternary amine and polyalkylene oxide are added to the electrolyte of the present invention at a concentration of 0.1 mg / L to 1 g / L, preferably 1 mg / L to 100 mg / L Lt; / RTI >

The dispersion or emulsion forming additive may be incorporated into the electrolyte as a commercial package of additives such as PEARLBRITE 占 available from Enthorn Inc. The PEARLBRITE® package may include dispersing or emulsion forming additives as well as transport additives and uniformity enhancing additives known in the art. The transport additive may be present in the electrolyte at about 1 g / L to about 15 g / L, such as 2 g / L to about 10 g / L, such as about 5 g / L. One such transport additive is sodium saccharinate. Additives for enhancing the uniformity of deposits are generally complex formulations added to shift the reference reduction potentials of the various metals to similar ranges. The complexing agent is generally added to the electrolyte in a concentration range of 50 to 200 g / L, such as 70 to 140 g / L. Complexing agents include gluconates, cyanides, citric acid, and other complexing agents known in the art.

It has also been found that a surface active wetting agent can be added to the electrolyte of the present invention. The addition of the surface active wetting agent also supports uniform deposition of the metal layer. The addition of surface active wetting agents to electrolytes known in the art was not possible because these surfactant wetting agents affected the emulsion and / or dispersion formation of the electrolyte and affected the matte or purple effect of the electrolyte. When a surface active wetting agent is added to an electrolyte known in the art, the deposited metal layer has changed to lustrous instead of biphasic.

In the electrolyte of the present invention, the addition of the surface active wetting agent is possible without affecting the matte effect of the electrolyte.

The surface active wetting agent that may be added to the electrolyte of the present invention may be a wetting agent selected from the group consisting of alkyl sulphate, sulfosuccinic acid and betaine. Alkyl sulfates generally have a hydrocarbon chain of from 8 to about 20 carbon atoms, usually 12 to 14 carbon atoms (e.g., decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate and octadecyl sulfate) , Potassium ions, magnesium ions, and ammonium ions. Sulphosuccinates useful for electrolytes are of the type available from Akzo Nobel. Sulphosuccinates generally have 7 to 20 carbon atoms, typically 8 to 12 carbon atoms, which can form esters and / or maintain a charge balance with sodium ions, potassium ions, magnesium ions and ammonium ions, .

The surface active wetting agent may be included in the electrolyte of the present invention at a concentration of between 0.01 mol / L and 100 mol / L, preferably between 0.1 mol / L and 10 mol / L.

In a method aspect, an object of the present invention is to provide a method of depositing a matte metal layer on a surface of a substrate, on which a matt metal layer is deposited from an emulsion and / or a dispersion forming electrolyte, by conducting a current between the cathode- Wherein 10 to 50% by weight of the metal to be deposited contained in the electrolyte is selected from the group consisting of halogens of an element selected from the group consisting of sodium, potassium, aluminum, magnesium or boron, , ≪ / RTI > sulfate or sulfonate. The current density may range from 0.1 to 100 A / dm < ² >. The current density depends on the experimental conditions, such as the plating metal ion. Plating occurs when the substrate surface, which serves as the cathode, is connected to a power supply and an anode, suitably an insoluble anode, is connected to the power supply and current is passed between the cathode (substrate) and the anode. In some embodiments, the electrolyte of the present invention is useful for depositing a matte nickel layer at a current density between about 2 and about 7 A / dm 2. Generally, deposition continues until the thickness of the plated metal layer is generally between about 2 micrometers and about 20 micrometers, although thinner or thicker plated metal layers are also within the scope of the invention.

The idea of the present invention is to replace some concentration of the metal to be deposited in the electrolyte with a density enhancing compound to reduce the concentration of the metal to be deposited and increase the density of the electrolyte.

By doing so, on the one hand, the amount of metal to be deposited in the electrolyte is reduced, and an economical advantage is obtained because fewer deposited metals must be used to prepare the electrolyte. On the other hand, due to the addition of alkaline compounds and / or alkaline earth compounds, the density of the electrolyte increases and this results in a more uniform deposition of the metal on the substrate surface. Moreover, it has also been found that, due to the increased density of the electrolyte, the addition of a surface active wetting agent is possible without unintentionally affecting the matte appearance of the deposited metal layer.

Having thus described the invention in detail, it will be appreciated that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

Example

The following non-limiting examples are intended to further illustrate the present invention.

Example  One

A Watts type electrolyte of the present invention containing the following was prepared:

Nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) 190 g / L

Boric acid 40 g / L

Nickel chloride hexahydrate _{(NiCl 2 · 6H 2 O)} 30 g / L

5 g / L sodium saccharinate, and

Magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O) 300 g / L

PEG 10000 3 mg / L

The electrolyte of the present invention has a density of about 1.322 g / cm 3. The nickel ion concentration of the electrolyte of the present invention was about 49.83 g / L. The magnesium ion concentration was about 29.59 g / L. Thus, the weight ratio of magnesium ion to nickel ion was about 0.6: 1.

The matte nickel layer was deposited from the electrolyte within 10 minutes at a temperature of 52 캜 and a current density of 5 A / dm 2. The pH value of the electrolyte was about 4.2. The substrate to be plated was moved through the electrolyte at a rate of 2 m / min. The structure of the deposited matte nickel layer was the same as that of the matte nickel layer containing 3 mg / L of polyethylene glycol having an average molecular weight of 10,000 g / mol and deposited from a comparative electrolyte comprising the following components:

Nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) 440 g / L

Boric acid 40 g / L

Nickel chloride hexahydrate _{(NiCl 2 · 6H 2 O)} 30 g / L

5 g / L sodium saccharinate, and

PEG 10000 3 mg / L

The density of the comparative electrolyte was about 1.322 g / cm3. The nickel ion concentration of the comparative electrolyte was about 105.65 g / L.

Example  2

A Watts type electrolyte of the present invention containing the following was prepared:

Nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) 190 g / L

Boric acid 40 g / L

Nickel chloride hexahydrate _{(NiCl 2 · 6H 2 O)} 30 g / L

5 g / L sodium saccharinate, and

Magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O) 300 g / L

BARQUAT® MB-80 6mg / L

The electrolyte of the present invention had a density of about 1.322 g / cm 3. The nickel ion concentration of the electrolyte of the present invention was about 49.83 g / L. The magnesium ion concentration was about 29.59 g / L. Thus, the weight ratio of magnesium ion to nickel ion present in the electrolyte of the present invention was about 0.6: 1.

The matte nickel layer was deposited from the electrolyte within 10 minutes at a temperature of 52 캜 and a current density of 5 A / dm 2. The pH value of the electrolyte was about 4.2. The substrate to be plated was moved through the electrolyte at a rate of 2 m / min. The structure of the deposited matte nickel layer was identical to that of a matte nickel layer containing 6 mg / L BARQUAT® MB-80 and deposited from a comparative electrolyte comprising the following components:

Nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) 440 g / L

Boric acid 40 g / L

Nickel chloride hexahydrate _{(NiCl 2 · 6H 2 O)} 30 g / L

5 g / L sodium saccharinate, and

BARQUAT® MB-80 6 mg / L

The density of the comparative electrolyte was about 1.322 g / cm 3, and the nickel ion concentration was about 105.65 g / L.

Example  3

An electrolyte of the present invention for depositing a tin-cobalt alloy containing:

Sodium gluconate 120 g / L

Cobalt (II) sulfate heptahydrate (CoSO ₄ · 7H ₂ O) 50 g / L

Tin (II) sulfate (SnSO ₄ ) 25 g / L

260 g / L of sodium sulfate 10 hydrate (Na ₂ SO ₄ .10H ₂ O), and

PEG 35000 1 mg / L

The electrolyte of the present invention had a density of about 1.288 g / cm 3. In the electrolyte of the present invention, the cobalt ion concentration was about 10.48 g / L and the tin ion concentration was about 13.82 g / L. The sodium ion concentration was about 18.55 g / L. Thus, the weight ratio of sodium ions to plated metal ions (total of cobalt ions and tin ions) was about 0.76: 1.

A very good matte tin-cobalt layer was deposited from the electrolyte within 5 minutes at a temperature of 45 캜 and a current density of 0.5 A / dm 2. The pH value of the electrolyte was about 8.4, and the substrate to be plated was moved through the electrolyte at a rate of 2 m / min. A very good matte layer deposited from the electrolyte was the same as the layer deposited from the comparative electrolyte comprising the following components:

Sodium gluconate 120 g / L

Cobalt (II) sulfate heptahydrate (CoSO ₄ .7H ₂ O) 100 g / L

Tin (II) sulfate (SnSO ₄ ) 50 g / L

PEG 35000 1 mg / L

The density of the comparative electrolyte was about 1.225 g / cm3. The cobalt ion concentration in the comparative electrolyte was about 20.96 g / L and the tin ion concentration was about 27.64 g / L.

The above Examples 1, 2 and 3 show that the addition of the alkaline compound or alkaline earth compound of the present invention to the electrolyte composition known in the art enables the use of a low plating metal concentration in the electrolyte without affecting the plating result It shows clearly. This enables a plating electrolyte to hold a very low concentration of plating metal, which provides significant economic benefits.

Example  4

An electrolyte of the present invention was prepared for depositing a nickel layer containing:

Nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) 225 g / L

Nickel chloride hexahydrate _{(NiCl 2 · 6H 2 O)} 50 g / L

Boric acid 40 g / L

Magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O) 225 g / L

Sodium benzoate sulfonimide 2.6 g / L

1.5 mg / L of polyethylene glycol-methyl ether, and

theba-2-propene-sulfonate 1.8 mg / L

The electrolyte of the present invention had a density of about 1.303 g / cm 3. The nickel ion concentration in the electrolyte of the present invention was about 50.21 g / L. The magnesium ion concentration was about 22.19 g / L. Thus, the weight ratio of magnesium ion to nickel ion present in the electrolyte of the present invention was about 0.4: 1.

A matte nickel layer was deposited on the substrate surface from the electrolyte within a period of 10 minutes at a temperature of 55 캜 and a current density of 5 A / dm 2, which under the same conditions contained 450 g / L nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O) and did not contain magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O). The density of the comparative electrolyte was 1.326 g / cm 3 and the nickel ion concentration was about 112.82 g / L.

Example  5

An electrolyte of the present invention was prepared for depositing a tin-cobalt alloy containing the following components:

Sodium gluconate 120 g / L

Cobalt (II) sulfate heptahydrate (CoSO ₄ · 7H ₂ O) 50 g / L

Tin (II) sulfate (SnSO ₄ ) 25 g / L

Sodium sulfate 10 hydrate (Na ₂ SO ₄ .10H ₂ O) 120 g / L

_{(Al 2 (SO 4) 3} · 18H 2 O) and

PEG 35000 1 mg / L

The electrolyte of the present invention had a density of about 1.235 g / cm 3. In the electrolyte of the present invention, the cobalt ion concentration was about 10.48 g / L and the tin ion concentration was about 13.82 g / L. The aluminum ion concentration was about 4.86 g / L. Therefore, the weight ratio of aluminum ion to plated metal ion (total of cobalt ion and tin ion) was about 0.2: 1.

A very good matte tin-cobalt layer was deposited from the electrolyte within 5 minutes at a temperature of 45 캜 and a current density of 0.5 A / dm 2. The pH value of the electrolyte was about 8.4, and the substrate to be plated was moved through the electrolyte at a rate of 2 m / min. A very good matte layer deposited from the electrolyte was the same as the layer deposited from the comparative electrolyte comprising the following components:

Sodium gluconate 120 g / L

Cobalt (II) sulfate heptahydrate (CoSO ₄ .7H ₂ O) 100 g / L

Tin (II) sulfate (SnSO ₄ ) 50 g / L

PEG 35000 1 mg / L

The density of the comparative electrolyte was about 1.225 g / cm3. The cobalt ion concentration in the comparative electrolyte was about 20.96 g / L and the tin ion concentration was about 27.64 g / L.

These embodiments clearly show that the addition of the density increasing compounds of the present invention to the electrolyte compositions known in the art makes it possible to reduce the plating metal concentration in the electrolyte without affecting the plating results. This enables a plating electrolyte to hold a very low concentration of plating metal, which provides significant economic benefits.

When introducing elements of the invention or the preferred embodiment (s) thereof, the singular expressions and "above " mean that there are one or more of the elements. The terms "comprising," " including, "and" possessing "are open terms and mean that there may be additional components other than the listed components.

From the foregoing, it will be seen that various objects of the invention are achieved and other advantageous results obtained.

It should be understood that all of the constituent elements included in the above description are to be construed as illustrative and not restrictive, since various changes may be made in the above compositions and methods without departing from the scope of the present invention.

Claims (36)

An electrolyte composition for depositing a matte layer of a metal or alloy on a surface of a substrate,
The electrolyte composition comprises
i) a metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, And a combination thereof;
ii) at least one halogenide, sulfate or sulfonate of an auxiliary metal element selected from the group consisting of sodium, potassium, aluminum, magnesium and boron; And
iii) at least one member selected from the group consisting of unsubstituted polyalkylene oxides, substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides At least one dispersing agent selected from the group consisting of substituted quaternary amines
≪ / RTI >
The concentration of the deposited metal ions is 10 g / L to 80 g / L,
Wherein the sodium, potassium, aluminum, magnesium and / or boron ions of the halogenide, sulfate or sulfonate are present in the range of 10 to 100% by weight of the deposited metal ion concentration,
Electrolyte composition. An electrolyte composition for depositing a matte layer of a metal or alloy on a surface of a substrate,
The electrolyte composition comprises
(i) at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, Pt, Au, A metal ion selected from the group consisting of combinations thereof;
ii) at least one halogenide, sulfate or sulfonate of an auxiliary metal element selected from the group consisting of sodium, potassium, aluminum, magnesium and boron;
iii) at least one member selected from the group consisting of unsubstituted polyalkylene oxides, substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides At least one dispersing agent selected from the group consisting of substituted quaternary amines; And
iv) at least one surface active wetting agent selected from the group consisting of alkyl sulphate, sulfo-succinic acid and betaine;
Lt; / RTI >
The concentration of the deposited metal ions is 10 g / L to 80 g / L,
The sodium, potassium, aluminum, magnesium and / or boron ions of the halogenide, sulfate or sulfonate are present in a concentration ranging from 10 to 100% by weight of the deposited metal ion concentration,
Wherein the surface active wetting agent is present in a concentration from 0.1 mol / L to 10 mol / L,
Electrolyte composition. 3. The electrolyte composition according to claim 1 or 2, wherein the deposited metal ion is selected from the group consisting of Fe, Co, Ni, Cu, Sn, Ag and combinations thereof. 3. The process according to claim 1 or 2, wherein at least one halogenide, sulfate or sulfonate of an element selected from the group consisting of sodium, potassium, aluminum, magnesium and boron is sodium methanesulfonate and its hydrate, Wherein the electrolyte composition is at least one compound selected from the group consisting of sodium carbonate, magnesium carbonate, magnesium carbonate, magnesium carbonate, magnesium carbonate, magnesium carbonate, magnesium carbonate, magnesium carbonate and magnesium carbonate. The process according to claim 1 or 2, wherein at least one halogenide, sulfate or sulfonate of an element selected from the group consisting of sodium, potassium, aluminum, magnesium and boron is selected from the group consisting of aluminum sulfate and its hydrates, sodium sulfate and its hydrates , And magnesium sulfate and hydrates thereof, and any combination thereof. 3. The electrolyte composition according to claim 1 or 2, wherein the halogenide, sulfate or sulfonate comprises sodium sulfate and / or magnesium sulfate. The electrolyte composition of claim 1, further comprising at least one surface active wetting agent. 8. The electrolyte composition of claim 7, wherein the surface active wetting agent is selected from the group consisting of alkyl sulphate, sulfo-succinic acid and betaine. 9. The electrolyte composition of claim 8, wherein the surface active wetting agent has a concentration ranging from 0.01 mol / L to 100 mol / L. 9. The electrolyte composition of claim 8, wherein the surface active wetting agent has a concentration in the range of from 0.1 mol / L to 10 mol / L. The electrolyte composition according to claim 2 or 9, wherein sodium, potassium, aluminum, magnesium and / or boron ions are present in a concentration ranging from 20% to 60% by weight of the deposited metal ion concentration. The method of claim 1 or 2, wherein the concentration of sodium, potassium, aluminum, magnesium and / or boron is such that the weight ratio of sodium, potassium, aluminum, magnesium and / ≪ / RTI > 3. A process according to claim 1 or 2, wherein the concentration of sodium, potassium, aluminum, magnesium and / or boron is such that the weight ratio of sodium, potassium, aluminum, magnesium and / ≪ / RTI > 3. A process according to claim 1 or 2, wherein the concentration of sodium, potassium, aluminum, magnesium and / or boron is such that the weight ratio of sodium, potassium, aluminum, magnesium and / ≪ / RTI > 3. The method of claim 1 or 2, wherein the sodium, potassium, aluminum, magnesium and / or boron have a concentration such that the weight ratio of sodium, potassium, aluminum, magnesium and / ≪ / RTI > 3. The method according to claim 1 or 2, wherein the deposited metal ions contain nickel ions,
Wherein the sodium, potassium, aluminum, magnesium and / or boron are present in a concentration such that the weight ratio of sodium, potassium, aluminum, magnesium and / or boron ion to nickel ion is at least 0.4: 1. 3. The method of claim 1 or 2, wherein the deposited metal ions contain cobalt ions and tin ions,
Wherein the sodium, potassium, aluminum, magnesium and / or boron are present in a concentration such that the weight ratio of sodium, potassium, aluminum, magnesium and / or boron ions to total cobalt and tin ions is at least 0.4: 1. 3. The electrolyte composition of claim 2, wherein the deposited metal ion is selected from the group consisting of Fe, Co, Ni, Cu, Zn, Sn, Ag and combinations thereof. 8. The method according to claim 2 or 7,
A concentration of sodium, potassium, aluminum, magnesium or boron ions of 10 g / L or more;
Wherein the dispersing agent is selected from unsubstituted polyalkylene oxides, substituted polyalkylene oxides, and derivatives of substituted or unsubstituted polyalkylene oxides,
Wherein the concentration of the dispersing agent is 0.1 mg / L to 10 g / L,
Wherein the concentration of the surface active wetting agent is from 0.01 mol / L to 100 mol / L. 8. The method according to claim 2 or 7,
A concentration of sodium, potassium, aluminum, magnesium or boron ions of 10 g / L or more;
The dispersing agent is a quaternary amine having a concentration of 0.1 mg / L to 1 g / L and substituted with a quaternary amine or a polyalkylene oxide;
Wherein the concentration of the surface active wetting agent is from 0.01 mol / L to 100 mol / L. Exposing the substrate surface to an electrolyte composition, and
Depositing a matte layer on the substrate surface by conducting a current between the substrate and the anode
A method for depositing a matte layer on a surface of a substrate,
The electrolyte composition comprises
i) a group consisting of a combination of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Re, Pt, Au, Selected deposition metal ions;
Ii) at least one halogenide, sulfate or sulphonate selected from the group consisting of sodium, potassium, aluminum, magnesium and boron; And
iii) at least one member selected from the group consisting of unsubstituted polyalkylene oxides, substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides At least one dispersing agent selected from the group consisting of substituted quaternary amines
≪ / RTI >
The concentration of the deposited metal ions is 10 g / L to 80 g / L,
Wherein the sodium, potassium, aluminum, magnesium and / or boron ions of the halogenide, sulfate or sulphonate are present in a concentration ranging from 10 to 100% by weight of the deposited metal ion concentration,
A method for depositing a matte layer on a surface of a substrate. Exposing the surface of the substrate to the electrolyte composition according to any one of claims 1, 2, 7, 8, 9, 10 and 18; And
Depositing a matte layer on the substrate surface by conducting a current between the substrate and the anode
And depositing a matte layer on the surface of the substrate. 22. The method of claim 21, wherein the concentration of the deposited metal ions is from 10 g / L to 80 g / L. An electrolyte composition according to claim 1, wherein the substrate surface comprises an auxiliary metal ion selected from the group consisting of nickel ions of 10 g / L or more and sodium, potassium, magnesium, aluminum, boron and combinations thereof, To an electrolyte composition wherein the weight ratio of the nickel metal ion is greater than 0.8: 1; And
Conducting a current between the substrate and the anode to deposit a matte nickel layer on the substrate surface
And depositing a matte layer on the surface of the substrate. 25. The method of claim 24, wherein the weight ratio of the auxiliary metal ion to the nickel ion is 1: 1 or greater. 25. The method of claim 24, wherein the weight ratio of the auxiliary metal ion to the nickel ion is 1.2: 1 or greater. The surface of the substrate contains an auxiliary metal ion selected from the group consisting of nickel ions of 40 g / L or more and sodium, potassium, magnesium, aluminum, boron and combinations thereof as the electrolyte composition of claim 1, To an electrolyte nickel plating composition wherein the weight ratio of metal ions is at least 0.2: 1; And
Conducting a current between the substrate and the anode to deposit a matte nickel layer on the substrate surface
And depositing a matte nickel layer on the surface of the substrate. 28. The process of claim 27, wherein the weight ratio of the auxiliary metal ion to the nickel ion is at least 0.4: 1. 29. The method of claim 28, wherein the weight ratio of auxiliary metal ion to nickel ion is greater than or equal to 0.6: 1. The substrate surface is formed by the steps of: adding an auxiliary metal ion selected from the group consisting of cobalt ions of 10 g / L or more, tin ions of 10 g / L or more and sodium, potassium, magnesium, aluminum, boron, To an electrolyte cobalt-tin alloy plating composition wherein the total weight ratio of auxiliary metal ion to cobalt metal ion to tin metal ion is at least 0.2: 1; And
Depositing a matte cobalt-tin alloy layer on the substrate surface by conducting a current between the substrate and the anode
And depositing a matte cobalt-tin alloy layer on the surface of the substrate. 31. The method of claim 30, wherein the total weight ratio of auxiliary metal ions to cobalt metal ions and tin metal ions is at least 0.4: 1. 31. The method of claim 30, wherein the total weight ratio of auxiliary metal ions to cobalt metal ions and tin metal ions is at least 0.6: 1. The electrolyte composition according to claim 1, wherein the electrolyte composition comprises
i) water;
ii) nickel-deposited metal ions;
iii) at least one inert halogenide, sulfate or sulfonate of an auxiliary metal selected from the group consisting of sodium, potassium, aluminum, magnesium and boron; And
iv) at least one member selected from the group consisting of unsubstituted polyalkylene oxides, substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides At least one dispersing agent selected from the group consisting of substituted quaternary amines
≪ / RTI >
Wherein the sodium, potassium, aluminum, magnesium and / or boron ions of the halogenide, sulfate or sulfonate are present in the range of 10 to 100% by weight of the deposited metal ion concentration,
Electrolyte composition. The electrolyte composition according to claim 1, wherein the electrolyte composition comprises
Nickel-deposited metal ions;
At least one magnesium halogenide, sulfate or sulfonate; And
Substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides. At least one dispersing agent selected from the group consisting of quaternary amines
≪ / RTI >
Wherein the magnesium ion of the magnesium halogenide, sulfate or sulfonate is present in the range of 10 to 100% by weight of the concentration of the deposited metal ion.
Electrolyte composition. Exposing the substrate surface to an electrolyte plating composition; And
Conducting a current between the substrate and the anode to deposit a matte nickel layer on the substrate surface
A method for depositing a matte nickel layer on a surface of a substrate,
The electrolyte composition comprises
i) a deposited metal ion;
ii) at least one inert halogenide, sulfate or sulfonate of an auxiliary metal selected from the group consisting of sodium, potassium, aluminum, magnesium and boron; And
iii) at least one member selected from the group consisting of unsubstituted polyalkylene oxides, substituted polyalkylene oxides, derivatives of substituted or unsubstituted polyalkylene oxides, fluorinated wetting agents, perfluorinated wetting agents, quaternary amines, and polyalkylene oxides At least one dispersing agent selected from the group consisting of substituted quaternary amines
≪ / RTI >
The concentration of the deposited metal ions is 10 g / L to 80 g / L,
Wherein the matte layer contains at most 1 atomic percent of an auxiliary metal,
Wherein the deposition metal ion in the electrolyte composition comprises nickel < RTI ID = 0.0 >
A method for depositing a matte nickel layer on a surface of a substrate. delete