CN111621773B - Application of dithiocarbamate compounds in chemical palladium plating and chemical palladium plating composition - Google Patents
Application of dithiocarbamate compounds in chemical palladium plating and chemical palladium plating composition Download PDFInfo
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- CN111621773B CN111621773B CN202010464309.1A CN202010464309A CN111621773B CN 111621773 B CN111621773 B CN 111621773B CN 202010464309 A CN202010464309 A CN 202010464309A CN 111621773 B CN111621773 B CN 111621773B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The invention relates to application of dithiocarbamate compounds in chemical palladium plating and a chemical palladium plating composition. The dithiocarbamic acid compound with the structure shown in the general formula (I) is used as a raw materialPreparing an electroless palladium plating composition, and then carrying out palladium plating treatment on a palladium part to be plated by using the electroless palladium plating composition. The dithiocarbamate compounds are applied to chemical palladium plating, so that the deposition speed of palladium ions can be effectively improved, the treatment time of chemical palladium plating is shortened, and the productivity is improved. In addition, the dithiocarbamate compound can stabilize the chemical palladium plating composition and reduce the risk of palladium ion precipitation in the composition, thereby improving the stability of the chemical palladium plating composition and ensuring the palladium plating effect.
Description
Technical Field
The invention relates to the technical field of chemical plating, in particular to application of dithiocarbamic acid compounds in chemical palladium plating and a chemical palladium plating composition.
Background
In the manufacturing process of printed circuit boards, integrated circuits or wafers, etc., since complicated circuit processing is involved, in order to improve the stability between circuits, it is often necessary to perform chemical palladium plating treatment on the circuit boards or wafers, etc. to improve the corrosion resistance, oxidation resistance, etc. of metals.
However, in the conventional electroless palladium plating process, the deposition rate of palladium ions is generally slow, and in the actual processing process, in order to obtain a thicker palladium layer, it is often necessary to prolong the processing time of electroless palladium plating or increase the temperature of the electroless palladium plating solution. Although the palladium layer with larger thickness can be obtained to a certain extent, the productivity of the production line is affected by prolonging the processing time of chemical palladium plating, and the improvement of the productivity is not facilitated; the deposition rate of palladium ions can be improved to a certain extent by increasing the temperature of the chemical palladium plating solution, but the increase of the temperature can cause instability of the chemical palladium plating solution, influence the performance of chemical palladium plating and further bring adverse effects to the effect of chemical palladium plating.
Disclosure of Invention
Based on the above, there is a need for an application of dithiocarbamate compounds in electroless palladium plating, which can effectively increase the deposition rate of palladium ions in the electroless palladium plating process.
In addition, it is also necessary to provide an electroless palladium plating composition, wherein the raw material of the electroless palladium plating composition comprises the dithiocarbamate compound, and the electroless palladium plating treatment of the palladium plating piece by the electroless palladium plating composition can effectively improve the deposition rate of palladium ions, and the electroless palladium plating composition has good stability.
In addition, it is necessary to provide an electroless palladium plating method, which can effectively increase the deposition rate of palladium ions by performing an electroless palladium plating treatment on a palladium to be plated with the electroless palladium plating composition.
The specific scheme for solving the technical problems is as follows:
one object of the present invention is to provide an application of dithiocarbamate compounds in electroless palladium plating, wherein the dithiocarbamate compounds have a structure shown in a general formula (I):
wherein R is 1 、R 2 Independently selected from hydrogen, phenyl, substituted or unsubstituted amine groups, or substituted or unsubstituted C1-C8 alkyl groups; when R is 1 、R 2 When the substituent group is independently selected from substituted amino, the substituent group on the amino is C1-C4 alkyl; when R is 1 、R 2 Independently selected from substituted C1-C8 alkyl, the substituent on the C1-C8 alkyl is hydroxyl, carboxyl, sulfonic group, aminoC1-C4 alkoxy or C1-C4 alkyl substituted amino;
R 3 selected from hydrogen, sodium ion, potassium ion, ammonium ion, cyano, or substituted or unsubstituted C1-C8 alkyl; when R is 3 When the substituent is selected from substituted C1-C8 alkyl, the substituent on the C1-C8 alkyl is hydroxyl, carboxyl, sulfonic acid group, amino, nitro or C1-C4 ester group.
In one embodiment, R 1 、R 2 Independently selected from hydrogen, phenyl, substituted or unsubstituted C1-C4 alkyl; when R is 1 、R 2 Independently selected from substituted C1-C4 alkyl, the substituent on the C1-C4 alkyl is hydroxyl, carboxyl, sulfonic group or amino;
R 3 selected from hydrogen, substituted or unsubstituted C1-C4 alkyl; when R is 3 When the substituent is selected from substituted C1-C4 alkyl, the substituent on the C1-C4 alkyl is hydroxyl, carboxyl, sulfonic group or amino.
Another object of the present invention is to provide an electroless palladium plating composition, wherein the raw material of the electroless palladium plating composition comprises a dithiocarbamate compound having a structure represented by general formula (I).
In one embodiment, the raw materials of the electroless palladium plating composition further comprise a palladium source, a complexing agent, a reducing agent, and a solvent.
In one embodiment, in the electroless palladium plating composition, the concentration of the dithiocarbamate compound is 0.1-20 mg/L, the concentration of palladium ions provided by the palladium source is 100-1500 mg/L, the concentration of the complexing agent is 5-200 g/L, and the concentration of the reducing agent is 1-30 g/L.
In one embodiment, the complexing agent is at least one of a fatty amine, a fatty acid salt, a nitrogen-containing fatty acid, and a nitrogen-containing fatty acid salt.
In one embodiment, the reducing agent is at least one of a hypophosphorous acid compound and a formic acid compound.
In addition to the above two objects, it is another object of the present invention to provide an electroless palladium plating method, comprising the steps of:
the chemical palladium plating treatment is carried out on the palladium piece to be plated by adopting the chemical palladium plating composition in any embodiment.
In one embodiment, the electroless palladium plating method further comprises the following steps: and before the chemical palladium plating treatment, adjusting the pH value of the chemical palladium plating composition to 4-9.
In one embodiment, the part to be plated with palladium is a printed circuit board, an integrated circuit board or a wafer.
The application of the dithiocarbamate compound in chemical palladium plating adopts the dithiocarbamate compound with the structure shown in the general formula (I) as a raw material to prepare a chemical palladium plating composition, and then the chemical palladium plating composition is adopted to carry out palladium plating treatment on a palladium part to be plated. The inventor of the invention finds in experiments that the application of the dithiocarbamate compound to the chemical palladium plating can effectively improve the deposition speed of palladium ions, shorten the treatment time of the chemical palladium plating and improve the productivity. In addition, the dithiocarbamate compound can stabilize the chemical palladium plating composition and reduce the risk of palladium ion precipitation in the composition, thereby improving the stability of the chemical palladium plating composition, ensuring the palladium plating effect, prolonging the service life of the chemical palladium plating composition and reducing the production cost of the chemical palladium plating.
The raw material of the chemical palladium plating composition comprises a dithiocarbamate compound with a structure shown in a general formula (I). The chemical palladium plating composition has good stability, palladium ions are not easy to be converted into palladium simple substances, and the service life is long. In the using process, the chemical palladium plating composition can ensure a stable and qualified palladium plating effect.
The chemical palladium plating method can effectively improve the deposition speed of palladium ions in the chemical palladium plating process, and is beneficial to improving the production efficiency.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the following detailed description, unless otherwise specified, all conventional methods are used; the raw materials, reagents, and the like used in the following embodiments are all commercially available products unless otherwise specified.
In describing the present invention, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity, and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
In the description of the present invention, a list of items connected by the term "at least one of", or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a alone, or B alone, or a and B. In still other examples, if items A, B and C are listed, the phrase "at least one of A, B and C" means all of a alone, or B alone, or C alone, or a and B (excluding C), or a and C (excluding B), or B and C (excluding a), or a and B and C. While item a may comprise a single unit or multiple units. Item B may comprise a single unit or multiple units. Item C may comprise a single unit or multiple units.
In the description of the present invention, in the numbers following the expression concerning the carbon number, i.e., the capital letter "C", such as "C1 to C8", "C1 to C4", etc., in "Numbers after C "such as" 1 "," 4 "or" 8 "indicate the number of carbons in a particular functional group. That is, the functional groups may include 1 to 8 carbon atoms and 1 to 4 carbon atoms, respectively. For example, "C1-C8 alkyl" refers to an alkyl group having 1-8 carbon atoms, such as CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、CH 3 CH 2 CH(CH 3 ) -or (CH) 3 ) 3 C-。
In the description of the present invention, the "alkyl group" is intended to be a straight-chain saturated hydrocarbon structure having 1 to 8 carbon atoms. "alkyl" is also contemplated to be a branched or cyclic hydrocarbon structure having 3 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 8 carbon atoms, an alkyl group having 3 to 7 carbon atoms, an alkyl group having 3 to 5 carbon atoms or an alkyl group having 3 to 4 carbon atoms. When an alkyl group having a particular carbon number is specified, all geometric isomers having that carbon number are intended to be encompassed. Thus, for example, "butyl" is meant to include n-butyl, sec-butyl, isobutyl, tert-butyl, and cyclobutyl. "propyl" is meant to include n-propyl, isopropyl and cyclopropyl. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, and the like. In addition, the alkyl group may be optionally substituted.
The dithiocarbamic acid compounds of the present invention can be purchased from commercial sources, such as Sigma-Aldrich (Sigma Aldrich), or prepared from the prior published literature.
One embodiment of the invention provides an application of dithiocarbamate compounds in chemical palladium plating, wherein the dithiocarbamate compounds have a structure shown in a general formula (I):
wherein R is 1 、R 2 Independently selected from hydrogen, phenyl, substituted or unsubstituted amine groups, or substituted or unsubstituted C1-C8 alkyl groups; r 3 Selected from hydrogen, metal ions, ammonium ions, cyano groups, or substituted or unsubstituted C1-C8 alkyl groups.
In the embodiment, a dithiocarbamic acid compound with a structure shown in a general formula (I) is used as a raw material to prepare the chemical palladium plating composition, and then the chemical palladium plating composition is used for carrying out palladium plating treatment on a palladium part to be plated. The inventor of the invention finds in experiments that the application of the dithiocarbamate compound to the chemical palladium plating can effectively improve the deposition speed of palladium ions, shorten the treatment time of the chemical palladium plating and improve the productivity. In addition, the dithiocarbamate compound can stabilize the chemical palladium plating composition and reduce the risk of palladium ion precipitation in the composition, thereby improving the stability of the chemical palladium plating composition, ensuring the palladium plating effect, prolonging the service life of the chemical palladium plating composition and reducing the production cost of the chemical palladium plating.
In one specific example, R 1 、R 2 Independently selected from substituted amino, wherein the substituent on the amino is C1-C4 alkyl. For example, the substituents on the amine group may be, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl.
In one specific example, R 1 、R 2 Independently selected from substituted C1-C8 alkyl, wherein, the substituent on the C1-C8 alkyl is hydroxyl, carboxyl, sulfonic group, amino, C1-C4 alkoxy or C1-C4 alkyl substituted amino. For example, the substituent on the substituted C1-C8 alkyl group may be, but is not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methoxy, ethoxy, propoxy, butoxy, methylamino, ethylamino, propylamino, butylamino.
In one specific example, R 3 Is selected from substituted C1-C8 alkyl, wherein, the substituent on the alkyl is hydroxyl, carboxyl, sulfonic group, amido, nitryl or C1-C4 ester group. For example, the C1-C4 ester group may be, but is not limited to, a carbomethoxy group, an carbethoxy group, a propisocarbonyl group, or a carbomethoxy group.
In one specific example, R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted C1-C4 alkyl.
In one specific example, R 1 、R 2 、R 3 Independently selected from substituted C1-C4 alkyl, wherein the substituent on the alkyl is hydroxyl, carboxyl, sulfonic group or amino.
In another embodiment of the present invention, an electroless palladium plating composition is provided, wherein the raw material of the electroless palladium plating composition comprises a dithiocarbamate compound having a structure represented by general formula (i).
Preferably, the concentration of the dithiocarbamate in the electroless palladium plating composition is 0.1mg/L to 20 mg/L. For example, in the electroless palladium plating composition, the concentration of the dithiocarbamate compound may be, but is not limited to, 0.1mg/L, 0.2mg/L, 0.3mg/L, 0.4mg/L, 0.5mg/L, 0.6mg/L, 0.7mg/L, 0.8mg/L, 0.9mg/L, 1mg/L, 1.5mg/L, 2mg/L, 2.5mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L, 8mg/L, 9mg/L, 10mg/L, 11mg/L, 12mg/L, 13mg/L, 14mg/L, 15mg/L, 16mg/L, 17mg/L, 18mg/L, 19 mg/L.
In one particular example, the raw materials of the electroless palladium composition further include a palladium source, a complexing agent, a reducing agent, and a solvent.
Preferably, the solvent is water. Further preferably, the solvent is at least one of pure water, ultrapure water, and deionized water.
In a specific example, the raw materials of the electroless palladium plating composition are a palladium source, a complexing agent, a reducing agent, a solvent and a dithiocarbamate compound having a structure shown by a general formula (I).
Specifically, the palladium source is a soluble palladium-containing compound. Preferably, the palladium source is a water-soluble palladium-containing compound, further preferably, the palladium source is a water-soluble palladium salt. For example, the palladium source may be, but is not limited to, palladium chloride, tetraamminepalladium dichloride, palladium nitrate, palladium sulfate. Specifically, the palladium source is at least one of palladium chloride, tetraamminepalladium dichloride, palladium nitrate and palladium sulfate.
Preferably, the complexing agent is at least one of a fatty amine, a fatty acid salt, a nitrogen-containing fatty acid, and a nitrogen-containing fatty acid salt. Specifically, the aliphatic amine may be, but is not limited to, methylamine, dimethylamine, ethylenediamine, 1, 3-diaminopropane, 1, 2-diaminopropylamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine. The fatty acid is preferably a carboxylic acid, for example the fatty acid may be, but is not limited to, citric acid, malic acid, malonic acid, succinic acid, glutaric acid, tartaric acid, glycolic acid, lactic acid. The cation in the fatty acid salt that forms a salt with the fatty acid may be, but is not limited to, sodium ion, potassium ion, and ammonium ion. The fatty acid salt is preferably a carboxylate. For example, the fatty acid salt may be, but is not limited to, sodium citrate, sodium malate, sodium malonate, sodium succinate, sodium glutarate, sodium tartrate, sodium glycolate, sodium lactate. The nitrogen-containing fatty acid is preferably a nitrogen-containing carboxylic acid. For example, the nitrogen-containing fatty acid may be, but is not limited to, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, glycine, glycyl-glycine, dihydroxyethylglycine, iminodiacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid. The cation forming a salt with the nitrogen-containing fatty acid in the nitrogen-containing fatty acid salt may be, but is not limited to, sodium ion, potassium ion, and ammonium ion. The nitrogen-containing fatty acid salt is preferably a nitrogen-containing carboxylic acid salt. For example, the nitrogen-containing fatty acid salt may be, but is not limited to, sodium ethylenediaminetetraacetate, sodium hydroxyethylethylenediaminetriacetate, sodium dihydroxyethylethylenediaminediacetate, sodium propylenediaminetetraacetate, sodium diethylenetriaminepentaacetate, sodium triethylenetetraminehexaacetate, sodium glycinate, sodium glycyl-glycinate, sodium dihydroxyethylglycinate, sodium iminodiacetate, sodium hydroxyethyliminodiacetate, sodium nitrilotriacetate.
In a specific example, the reducing agent is at least one of a hypophosphorous acid-based compound and a formic acid-based compound. Specifically, the hypophosphorous acid-based compound is preferably at least one of hypophosphorous acid and hypophosphites. In some specific examples, the hypophosphorous acid-based compound may be hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, or the like. The formic acid compound is preferably at least one of formic acid, formate ester, and formamide. In some specific examples, the formate compound can be formic acid, sodium formate, potassium formate, ammonium formate, lithium formate, methyl formate, ethyl formate, propyl formate, formamide, N-dimethylformamide, and the like.
In a specific example, in the electroless palladium plating composition, the concentration of the dithiocarbamate compound is 0.1mg/L to 20mg/L, the concentration of palladium ions provided by a palladium source is 100mg/L to 1500mg/L, the concentration of a complexing agent is 5g/L to 200g/L, and the concentration of a reducing agent is 1g/L to 30 g/L.
In a specific example, the raw materials of the electroless palladium plating composition are a palladium source, a complexing agent, a reducing agent, a solvent and a dithiocarbamate compound having a structure shown by a general formula (I). In the chemical palladium plating composition, the concentration of the dithiocarbamate compound is 0.1 mg/L-20 mg/L, the concentration of palladium ions provided by a palladium source is 100 mg/L-1500 mg/L, the concentration of a complexing agent is 5 g/L-200 g/L, the concentration of a reducing agent is 1 g/L-30 g/L, and the balance is a solvent. Preferably, in the chemical palladium plating composition, the concentration of the dithiocarbamate compound is 0.1 mg/L-20 mg/L, the concentration of palladium ions provided by a palladium source is 100 mg/L-1500 mg/L, the concentration of a complexing agent is 5 g/L-200 g/L, the concentration of a reducing agent is 1 g/L-30 g/L, and the balance is water.
In some specific examples, the palladium source provides palladium ions at a concentration of 100mg/L, 150mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L, 1000mg/L, 1100mg/L, 1200mg/L, 1300mg/L, 1400mg/L, 1500mg/L in the electroless palladium composition. In some specific examples, the concentration of the complexing agent in the electroless palladium composition is 5g/L, 10g/L, 20g/L, 30g/L, 50g/L, 70g/L, 80g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, 200 g/L. In some specific examples, the concentration of the reducing agent in the electroless palladium plating composition is 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 10g/L, 15g/L, 18g/L, 20g/L, 22g/L, 25g/L, 28g/L, 30 g/L.
The invention also provides a chemical palladium plating method, which adopts the chemical palladium plating composition to carry out chemical palladium plating treatment on a palladium piece to be plated.
In a specific example, the pH value of the electroless palladium plating composition is adjusted to 4-9 before the electroless palladium plating treatment. When the electroless palladium plating composition requires adjustment of the pH during use, conventional acids or bases may be used for the adjustment. For example, the acid may be hydrochloric acid, sulfuric acid; the alkali can be ammonia water, sodium hydroxide, potassium hydroxide, etc. In the electroless palladium plating process, the pH of the electroless palladium plating composition may be adjusted to 4, 5, 6, 7, 8, etc.
In a specific example, the member to be plated with palladium is a printed circuit board, an integrated circuit board, or a wafer.
In one specific example, the electroless palladium plating composition is prepared by a method comprising the steps of: calculating the dosage of each raw material of the composition according to a preset volume; adding a palladium source into a solvent for dissolving; then adding a complexing agent, a reducing agent and a dithiocarbamic acid compound with a structure shown in a general formula (I); adjusting the pH value of the composition to 4-9.
Preferably, the preparation method of the electroless palladium plating composition comprises the following steps: calculating the dosage of each raw material of the composition according to a preset volume; adding a palladium source into a solvent for dissolving; then adding a complexing agent, a reducing agent and a dithiocarbamic acid compound with a structure shown in a general formula (I); adjusting the pH value of the composition to 4-9.
As a specific example, the electroless palladium plating composition is prepared by the following method: the predetermined volume of the composition was 2L using pure water as the solvent. Calculating the dosage of each raw material in the composition according to the volume of 2L; adding a palladium source into pure water for dissolving; then adding a complexing agent, a reducing agent and a dithiocarbamic acid compound with a structure shown in a general formula (I), and adjusting the pH value of the composition to a required value.
In one particular example, the member to be plated with palladium may be, but is not limited to, a ceramic, a plastic, a resin, a silicon material, or the like. Before the part to be plated with palladium is subjected to chemical palladium plating treatment, the part to be plated with palladium is covered with a metal layer. The metal layer may be, but is not limited to, a copper layer, a nickel layer, a gold layer, a silver layer, a palladium layer, or the like. Namely, metal layers such as a copper layer, a nickel layer, a gold layer, a silver layer or a palladium layer are formed on the part to be plated with palladium, and then the part to be plated with the metal layers is subjected to chemical palladium plating treatment. It is understood that the metal layer can be formed on the palladium member to be plated partially or completely.
In one particular example, the palladium article to be plated is pre-treated prior to the electroless palladium plating treatment. The pretreatment steps are as follows: degreasing → water washing → microetching → water washing → presoaking → activation → water washing → nickel deposition → water washing, wherein the water washing is to rinse the substrate with deionized water for 1 minute.
Specifically, the pretreatment comprises the following steps:
(1) oil removal: the oil removal agent TS-acid clean 6189 from Guangdong Shuo science and technology Limited is used, the operation temperature is 35 ℃, and the treatment time is 5 minutes.
(2) Micro-etching: the microetching agent consists of 100g/L sodium persulfate and 2% (v/v) concentrated sulfuric acid, the operation temperature is 30 ℃, and the treatment time is 2 minutes.
(3) Pre-dipping: the treatment was carried out with 1% sulfuric acid for 2 minutes.
(4) And (3) activation: the TS-Activator LA Activator from Guangdong Shuo science and technology Limited is used, the operating temperature is 24 ℃, and the processing time is 1 minute.
(5) Depositing nickel: the nickel deposition is carried out by chemical nickel plating 5183LMP series of chemical liquid of Guangdong Shuoji company, the operation temperature is 82 ℃, and the treatment time is 25 minutes.
And after the pretreatment, performing chemical palladium plating treatment on the part to be plated after the pretreatment. The chemical palladium plating treatment method comprises the following steps: immersing the pretreated part to be plated with palladium into the chemical palladium plating composition of the following embodiment, wherein the temperature of the chemical palladium plating composition is 55-65 ℃ (preferably 60 ℃), the pH value of the chemical palladium plating composition is 4-9, and the time of chemical palladium plating treatment is 8-15 min, preferably 10 min.
It can be understood that after the electroless palladium plating treatment, the part to be plated with palladium after the electroless palladium plating treatment is washed with water and dried, and subsequent steps can be performed as required, and the subsequent steps can be, but are not limited to, gold plating, and the like.
The following are specific examples.
In the following examples and comparative examples, the CAS number refers to a registration number assigned to a chemical substance by chemical abstracts.
Example 1
In this embodiment, the dithiocarbamate compound is S- (N, N-dimethylthiocarbamoyl) mercaptoacetic acid (CAS number: 4007-01-6). The predetermined volume of the electroless palladium plating composition in this example was 2L. Based on 2L, the raw materials in the composition are 100mg/L palladium chloride, 5g/L ethylenediamine, 1g/L sodium hypophosphite and 0.1mg/L S- (N, N-dimethylthiocarbamoyl) thioglycolic acid, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: adding pure water into a beaker, dissolving palladium chloride into the pure water, sequentially adding ethylenediamine, sodium hypophosphite and S- (N, N-dimethylthiocarbamoyl) thioglycolic acid, adjusting the pH of the solution to 4 by hydrochloric acid, and keeping the volume of the electroless palladium plating composition to be 2L for later use.
Example 2
In this embodiment, the dithiocarbamate is butyl ethyldithiocarbamate (CAS number: 83962-20-3). The predetermined volume of the electroless palladium plating composition in this example was 2L. Based on 2L, the raw materials of the composition are 700mg/L palladium sulfate, 30g/L ethylene diamine tetraacetic acid, 15g/L sodium formate and 10mg/L butyl ethyl dithiocarbamate, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: adding pure water into a beaker, dissolving palladium sulfate into the pure water, sequentially adding ethylene diamine tetraacetic acid, sodium formate and butyl ethyl dithiocarbamate, adjusting the pH of the solution to 6.5 by using sulfuric acid, and keeping the volume of the chemical palladium plating composition to be 2L for later use.
Example 3
In this embodiment, the dithiocarbamate compound is N- [2- (dimethylamino) ethyl ] -N-methyldithiocarbamate (CAS number: 18997-75-6). The predetermined volume of the electroless palladium plating composition in this example was 2L. Based on 2L, the raw materials in the composition are 100mg/L palladium nitrate, 5g/L nitrilotriacetic acid, 5g/L methyl formate and 0.1mg/L N- [2- (dimethylamino) ethyl ] -N-methyldithiocarbamic acid, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: pure water was added to a beaker, palladium nitrate was dissolved in the pure water, nitrilotriacetic acid, methyl formate and N- [2- (dimethylamino) ethyl ] -N-methyldithiocarbamic acid were sequentially added thereto, the pH of the solution was adjusted to 8 with aqueous ammonia, and the volume of the electroless palladium plating composition was 2L.
Example 4
In this embodiment, the dithiocarbamate is butylisopropyldithiocarbamate (CAS number: 85938-58-5). The predetermined volume of the electroless palladium plating composition in this example was 2L. Based on 2L, the raw materials in the composition are 1500mg/L tetraamminepalladium dichloride, 100g/L citric acid, 30g/L ammonium formate and 20mg/L butyl isopropyl dithiocarbamate, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: adding pure water into a beaker, dissolving palladium tetraammine dichloride in the pure water, sequentially adding citric acid, ammonium formate and butyl isopropyl dithiocarbamate, adjusting the pH of the solution to 9 by using ammonia water, and keeping the volume of the chemical palladium plating composition to be 2L for later use.
Example 5
In this embodiment, the dithiocarbamate compound is ethyl dithiocarbamate (CAS number: 625-61-6). The predetermined volume of the electroless palladium plating composition in this example was 2L. Based on 2L, the raw materials of the composition are 700mg/L palladium acetate, 200g/L lactic acid, 10g/L sodium hypophosphite and 10mg/L ethyl dithiocarbamate, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: adding pure water into a beaker, dissolving palladium acetate into the pure water, sequentially adding lactic acid, sodium hypophosphite and ethyl dithiocarbamate, adjusting the pH of the solution to 5 by using sulfuric acid, and keeping the volume of the chemical palladium plating composition to be 2L for later use.
Example 6
In this embodiment, the dithiocarbamate is sodium diphenyldithiocarbamate (CAS number: 2801-05-0). The predetermined volume of the electroless palladium plating composition in this example was 2L. 2L is taken as a reference, the raw materials in the composition are 1500mg/L palladium chloride, 50g/L tartaric acid, 30g/L sodium formate and 5mg/L sodium diphenyldithiocarbamate, and the solvent is pure water.
The preparation method of the electroless palladium plating composition in the embodiment comprises the following steps: adding pure water into a beaker, dissolving palladium chloride into the pure water, sequentially adding tartaric acid, sodium formate and sodium diphenyldithiocarbamate, adjusting the pH of the solution to be 8 by using ammonia water, and keeping the volume of the chemical palladium plating composition to be 2L for later use.
Comparative example 1
Comparative example 1 is different from example 1 in that N, N-dimethyldithiocarbamoylenepropionic acid (CAS No: 89798-57-2) was used in place of S- (N, N-dimethylthiocarbamoyl) mercaptoacetic acid.
Comparative example 2
Comparative example 2 differs from example 1 in that the electroless palladium plating composition does not contain S- (N, N-dimethylthiocarbamoyl) mercaptoacetic acid.
Comparative example 3
Comparative example 3 differs from example 1 in that acetaldehyde is used instead of S- (N, N-dimethylthiocarbamoyl) mercaptoacetic acid.
Test example
1. Stability testing of electroless Palladium compositions
The test method comprises the following steps: 50ml of each of the electroless palladium plating compositions prepared in examples 1 to 6 and comparative examples 1 to 3 was taken, and then heated in a water bath at 70 ℃ to observe the time until precipitation of the palladium simple substance began, and the stability of each composition was measured, and the results are shown in Table 1.
2. Palladium deposition rate test
The part to be plated with palladium is a printed circuit board, the specification of the printed circuit board is 13.5cm multiplied by 10cm, and the FR4 material is a copper-clad circuit board.
Firstly, respectively pretreating palladium parts to be plated, wherein the pretreatment comprises the following steps:
(1) oil removal: the oil removal agent TS-acid clean 6189 product of Guangdong Shuo science and technology Limited is used, the operation temperature is 35 ℃, and the treatment time is 5 minutes.
(2) Micro-etching: the microetching agent consists of 100g/L sodium persulfate and 2% (v/v) concentrated sulfuric acid, the operation temperature is 30 ℃, and the treatment time is 2 minutes.
(3) Pre-dipping: the treatment was carried out with 1% sulfuric acid for 2 minutes.
(4) And (3) activation: the TS-Activator LA Activator, a product of Guangdong Shuo science and technology Limited, is used, the operation temperature is 24 ℃, and the processing time is 1 minute.
(5) Depositing nickel: the nickel deposition is carried out by chemical nickel plating 5183LMP series of chemical liquid of Guangdong Shuoji company, the operation temperature is 82 ℃, and the treatment time is 25 minutes.
And then, respectively carrying out chemical palladium plating treatment on the parts to be plated with palladium after pretreatment. The chemical palladium plating treatment method comprises the following steps: and respectively soaking the pretreated parts to be plated with palladium into the chemical palladium plating compositions of the examples 1-6 and the comparative examples 1-3, wherein the temperature of the chemical palladium plating composition is preferably 60 ℃, and the time of chemical palladium plating treatment is 10 min.
The test method for testing the palladium deposition speed comprises the following steps: the thickness of the palladium layer was measured by X-RAY fluorescence (XRF) using a device known as fischerchope X-RAY XDV- μ coating thickness gauge, germany, and the coating thickness was measured and divided by the time of electroless palladium plating for 10min to obtain the palladium deposition rate, with specific results as shown in table 1.
TABLE 1
| Electroless palladium plating composition | Stability test | Palladium deposition rate (μm/min) |
| Example 1 | Heating for 72 hours without palladium precipitation | 0.005 |
| Example 2 | Heating for 72 hours without palladium precipitation | 0.02 |
| Example 3 | Heating for 72 hours without palladium precipitation | 0.006 |
| Example 4 | Heating for 72 hours without palladium precipitation | 0.03 |
| Example 5 | Heating for 72 hours without palladium precipitation | 0.022 |
| Example 6 | Heating for 72 hours without palladium precipitation | 0.035 |
| Comparative example 1 | Heating for 45 hours to precipitate | 0.0035 |
| Comparative example 2 | Heating for 24 hours to cause precipitation | 0.002 |
| Comparative example 3 | Heating for 24 hours to cause precipitation | 0.021 |
As is clear from the results shown in Table 1, the palladium plating compositions of examples 1 to 6 were free from palladium precipitates after heating at 70 ℃ or more for 72 hours in the stability test of the electroless palladium plating compositions. In comparative example 1, the stability test results were inferior to those of examples 1 to 6, although N, N-dimethyldithiocarbamimidoyl allyl acid had the same parent nucleus as that of the compound having the structure represented by general formula (I). Comparative example 2 no dithiocarbamate compound of the structure shown in formula (I) was added, and the composition of comparative example 2 was inferior in thermal stability. Comparative example 3 a technical solution using acetaldehyde existing in the prior art as an accelerator was used, and the test results showed that the solution could not satisfy the stability required for the electroless palladium plating composition.
In terms of the deposition rate of palladium, the deposition rates of palladium in examples 1 to 6 were all 0.005 μm/min or more. The plating speed of the composition of comparative example 1 is 0.0035 μm/min, and the plating speed of the composition of comparative example 2 is 0.002 μm/min, which are lower than the palladium deposition speed in examples 1-6.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The application of dithiocarbamic acid compounds in chemical palladium plating is characterized in that: the dithiocarbamate compound has a structure shown in a general formula (I):
wherein R is 1 、R 2 Independently selected from hydrogen, phenyl, substituted or unsubstituted amine groups, or substituted or unsubstituted C1-C8 alkyl groups; when R is 1 、R 2 When the substituent is independently selected from substituted amino, the substituent on the amino is C1-C4 alkyl; when R is 1 、R 2 Independently selected from substituted C1-C8 alkyl, the substituent on the C1-C8 alkyl is hydroxyl, carboxyl, sulfonic group, amino, C1-C4 alkoxy or C1-C4 alkyl substituted amino;
R 3 selected from cyano, or substituted or unsubstituted C1-C8 alkyl; when R is 3 When the substituent is selected from substituted C1-C8 alkyl, the substituent on the C1-C8 alkyl is hydroxyl, carboxyl, sulfonic acid group, amino, nitro or C1-C4 ester group.
2. The use of claim 1, wherein: r 1 、R 2 Independently selected from hydrogen, phenyl, substituted or unsubstituted C1-C4 alkyl; when R is 1 、R 2 Independently selected from substituted C1-C4 alkyl, the substituent on the C1-C4 alkyl is hydroxyl, carboxyl, sulfonic group or amino;
R 3 selected from substituted or unsubstituted C1-C4 alkyl; when R is 3 When the substituent is selected from substituted C1-C4 alkyl, the substituent on the C1-C4 alkyl is hydroxyl, carboxyl, sulfonic group or amino.
3. An electroless palladium plating composition, characterized by: the raw material of the electroless palladium plating composition comprises a dithiocarbamate compound with a structure shown in a general formula (I).
4. The electroless palladium plating composition according to claim 3, wherein: the raw materials of the chemical palladium plating composition also comprise a palladium source, a complexing agent, a reducing agent and a solvent.
5. The electroless palladium plating composition according to claim 4, wherein: in the chemical palladium plating composition, the concentration of the dithiocarbamate compound is 0.1-20 mg/L, the concentration of palladium ions provided by a palladium source is 100-1500 mg/L, the concentration of a complexing agent is 5-200 g/L, and the concentration of a reducing agent is 1-30 g/L.
6. The electroless palladium plating composition according to any one of claims 4 to 5, wherein: the complexing agent is at least one of fatty amine, fatty acid salt, nitrogen-containing fatty acid and nitrogen-containing fatty acid salt.
7. The electroless palladium plating composition according to any one of claims 4 to 5, wherein: the reducing agent is at least one of hypophosphorous acid compounds and formic acid compounds.
8. An electroless palladium plating method is characterized in that: the method comprises the following steps:
an electroless palladium plating treatment of a palladium to be plated by using the electroless palladium plating composition according to any one of claims 3 to 7.
9. The electroless palladium plating method according to claim 8, wherein: also comprises the following steps: and before the chemical palladium plating treatment, adjusting the pH value of the chemical palladium plating composition to 4-9.
10. The electroless palladium plating method according to any one of claims 8 to 9, wherein: the part to be plated with palladium is a printed circuit board, an integrated circuit board or a wafer.
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| GB1184123A (en) * | 1968-04-22 | 1970-03-11 | Elektrogeraetewerk Gornsdorf V | Process for Currentless Deposition of Copper Coatings |
| GB1603471A (en) * | 1977-03-19 | 1981-11-25 | Tokuyama Soda Kk | Electrolytic process |
| SU1102820A1 (en) * | 1981-07-23 | 1984-07-15 | Уральский ордена Трудового Красного Знамени политехнический институт им.С.М.Кирова | Aqueous solution for chemical deposition of copper-containing coatings |
| US4617205A (en) * | 1984-12-21 | 1986-10-14 | Omi International Corporation | Formaldehyde-free autocatalytic electroless copper plating |
| JPS6280279A (en) * | 1985-10-03 | 1987-04-13 | Taiyo Yuden Co Ltd | Chemical copper plating solution |
| JP4474605B2 (en) * | 2000-01-11 | 2010-06-09 | 奥野製薬工業株式会社 | Electroless nickel plating solution |
| KR100859259B1 (en) * | 2005-12-29 | 2008-09-18 | 주식회사 엘지화학 | Cobalt-base alloy electroless-plating solution and electroless-plating by using the same |
| JP2011094192A (en) * | 2009-10-29 | 2011-05-12 | Fujifilm Corp | Composition for forming layer to be plated, method for producing metal pattern material, and metal pattern material |
| CN101709462B (en) * | 2009-12-23 | 2012-01-11 | 长沙理工大学 | Chemical palladium plating solution |
| CN103898490B (en) * | 2014-04-11 | 2017-03-22 | 深圳市荣伟业电子有限公司 | High-reliability type chemical palladium plating liquor and cyanide-free chemical nickel-palladium-gold processing method |
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