CN114032529A - Chemical nickel plating solution and chemical nickel plating process for wafer-level packaging product - Google Patents
Chemical nickel plating solution and chemical nickel plating process for wafer-level packaging product Download PDFInfo
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- CN114032529A CN114032529A CN202111359701.0A CN202111359701A CN114032529A CN 114032529 A CN114032529 A CN 114032529A CN 202111359701 A CN202111359701 A CN 202111359701A CN 114032529 A CN114032529 A CN 114032529A
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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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
Abstract
The invention discloses a chemical nickel plating solution for wafer level packaging products and a chemical nickel plating process thereof, wherein the chemical nickel plating solution comprises the following components in mass concentration: 25-50g/L of nickel salt; 30-60g/L of reducing agent; 10-15g/L of anti-aging agent; 5-15g/L of composite complexing agent; reaction accelerator 50-80 mg/L; 5-10mg/L of surfactant; 0.2-5mg/L stabilizer and 20-40mg/L inhibitor; 60-120mg/L of antioxidant; 40-100mg/L carrier; the carrier is a compound of chloride ions and alum ions, and the mass concentration ratio is 1: (1-1.5), controlling the concentration of chloride ions to be between 20 and 40ppm/L and controlling the concentration of alum ions to be between 20 and 60ppm/L when the mixture is used; the mass concentration ratio of the antioxidant to the inhibitor in use is 3: 1. the solution ensures the bonding strength between the plating layer and the substrate, so that the nickel plating layer has good adhesiveness and uniform plating layer; the process not only ensures the uniformity of chemical plating, but also shortens the chemical plating time.
Description
Technical Field
The invention relates to the technical field of nickel plating, in particular to a chemical nickel plating solution for wafer-level packaging products and a chemical nickel plating process thereof.
Background
Traditionally, electrical connections between IC chips and the outside have been made by wire bonding I/O on the chip to a package carrier to form a leaded package. However, with I/O pitches shrinking below 70 μm, wire bonding techniques have not met the era. Wafer Level Packaging (WLP) technology is developed due to its advantages of small size, low cost, etc., and is currently used in many fields such as mobile phones, GPS, bluetooth devices, etc., and the production range is very wide. The chemical nickel plating technology has the excellent characteristics incomparable with the conventional chemical plating, such as uniform plating layer, high hardness, good wear resistance and corrosion resistance, convenient operation and the like, so the chemical nickel plating technology is more and more widely introduced to wafer-level packaging products.
The prior chemical nickel plating technology is mature, various types of chemical nickel plating solutions are commercialized and serialized, but the prior wafer-level packaging product has the following defects:
1) the temperature of the plating solution is high, the crystallinity and rigidity of the produced plated part are high easily in the chemical plating process, the roughened surface becomes brittle, and then the plating layer and the matrix almost have no binding force, and the plating layer is easy to fall off under the high-temperature circulation condition.
2) Along with the prolonging of the chemical plating time, the stability of the chemical nickel solution is poorer and poorer, and further, the phenomenon of cavities and cracks easily appears on the plating layer.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides the chemical nickel plating solution for the wafer level packaging product and the chemical nickel plating process thereof, the solution ensures the bonding strength between the coating and the substrate, so that the nickel-plated layer has good adhesiveness and uniform coating, and the process not only achieves the effect of filling the wafer packaging micropores without holes and gaps; and the chemical plating uniformity effect is good, and the arch rate is low.
In order to achieve the purpose, the invention provides an electroless nickel plating solution for wafer level packaging products, which comprises the following components in mass concentration:
the carrier is a compound of chloride ions and alum ions, and the mass concentration ratio is 1: (1-1.5), controlling the concentration of chloride ions to be between 20 and 40ppm/L and controlling the concentration of alum ions to be between 20 and 60ppm/L when the mixture is used;
the mass concentration ratio of the antioxidant to the inhibitor in use is 3: 1, the antioxidant and the inhibitor form a compound with a conjugate transmission bridge function when in use, so that the rapid deposition of pit parts is accelerated;
after the components are uniformly mixed according to the proportion, the pH value of the solution is adjusted to 4.3-4.6, and then a pH buffering agent with the mass concentration of 25% is added, and finally the preparation of the chemical nickel plating solution is completed.
The composite complexing agent comprises a component A and a component B, wherein the component A and the component B are mixed according to a mass concentration ratio of 2: (1-2); the component A comprises citric acid with the mass concentration of 1-5g/L and ammonium acetate with the mass concentration of 1-5 g/L;
the component B comprises polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide according to the mass concentration ratio of 1:1:1: 1; the component A and the component B are uniformly stirred and mixed according to the concentration ratio to form the composite complexing agent.
Wherein, the components of the nickel plating solution can also comprise a reaction antifouling agent with the mass concentration of 20-40mg/L, and the reaction antifouling agent is composed of 5-10mg/L ethylene glycol tertiary butyl ether and 15-30mg/L phosphate.
The specific process for preparing the chemical nickel solution comprises the following steps:
step a, preparing nickel salt, a composite complexing agent, a reducing agent, an anti-aging agent, a reaction accelerator, a surfactant, a stabilizer, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent according to a mass concentration ratio;
b, pouring a stabilizer, an anti-aging agent, a surfactant, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent into a nickel tank according to a proportion, carrying a stirring pump, stirring after pouring, wherein the stirring speed is 50-100r/min, and adding 1/2 composite complexing agent in the stirring process; stirring for 30 seconds to form a solution C;
step C, adding a reaction accelerator, a reducing agent and nickel salt into the solution C in sequence, stirring at a stirring speed of 100-200r/min, adding the remaining 1/2 composite complexing agent during stirring, and stirring uniformly for 30 seconds to form a solution D;
and D, adjusting the pH value of the solution D to 4.3-4.6, and then adding a pH buffer with the mass concentration of 25% to form the nickel plating solution.
Wherein the reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridine methanol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridine methanol is (1-2) to 1.
Wherein the nickel salt is nickel sulfate or nickel sulfamate, and the surfactant is sodium methallylsulfonate; the inhibitor is polyoxyethylene ether sulfate, the antioxidant is 1,2, 4-triazole, the chloride ions are provided by hydrochloric acid, and the alum ions are provided by alum sulfate; the anti-aging agent is a ketoamine anti-aging agent, and the stabilizer is benzotriazole.
In order to achieve the above object, the present invention further provides an electroless nickel plating process of an electroless nickel plating solution for wafer level packaging products, comprising the following steps,
step 1, bombarding the surface of a plated part by adopting vacuum plasma to remove various pollutants and oxidation layers on the surface of the plated part;
step 2, putting the processed plated piece into a nickel tank with the nickel plating solution to carry out chemical nickel plating treatment; the temperature of the chemical nickel plating is divided into two stages, the temperature of the first stage is 75-85 ℃, and the temperature of the second stage is 55-65 ℃; the flow is regulated by adopting a variable frequency regulator, and the plating solution flow rate of the introduced bath solution is changed by the variable frequency regulator, so that the balance force applied to the interior of the plating solution is broken;
step 3, after the chemical nickel plating is finished, taking out the nickel plated piece, and bombarding the surface of the nickel plated piece with the nickel plated layer by adopting vacuum plasma again;
and 4, carrying out the next process on the plated part subjected to the surface treatment.
Wherein, the specific conditions of the vacuum plasma bombardment in the step 4 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3; the distance of the plasma bombardment is controlled to be 3-5 cm; the treatment temperature is 30-40 ℃; the treatment time is 15-25 s.
Wherein, the specific conditions of the vacuum plasma bombardment in the step 1 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3, controlling the bombardment distance to be 20-25 mm; the treatment temperature is 90-110 ℃; the treatment time is 15-25 s.
Wherein, the flow rate of the copper plating is adjusted to 10-30L/min by the variable frequency regulator in the step 2.
The invention has the beneficial effects that: compared with the prior art, the chemical nickel plating solution and the chemical nickel plating process for the wafer level packaging product have the following advantages:
1) a reaction accelerator, a composite complexing agent, an inhibitor, an antioxidant and a carrying agent are added on the basis of the original components of the nickel plating solution, and the alum ions and the chloride ions of the carrying agent are matched according to the proportion of 1: (1-1.5) the proportion range is mixed, so that the deposition effect of nickel is better, the reduction rate is accelerated, and the continuous nucleation rate is improved, so that the compactness of the integral nickel layer is greatly improved; the surface crystal compactness of the obtained chemical nickel plating layer is higher;
2) the solution is added with an inhibitor and an antioxidant on the original basis, and when the solution is used, the mass concentration ratio of the antioxidant to the inhibitor is 3: the purpose of the inhibitor is to inhibit the salient points on the surface of the substrate and accelerate the rapid deposition of the concave points, but the common single inhibitor has larger molecular compound and is difficult to be adsorbed to the salient points firstly, so that a compound with the function of conjugate transmission bridges is needed as the connection, and the selected antioxidant has the effect, and the effect is optimal according to the proportion.
3) The nickel plating solution of the invention adopts a specially-made composite complexing agent, because the complexing capacity of the prior complexing agent is small, the phenomenon of instability is easily caused by small capacity in the complexing process, and nickel ions can be deposited on the wall of a tank all the time along with the lengthening of chemical plating time, in order to solve the problems, polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide are taken as a part of the complexing agent, and the macromolecular substances have the characteristic of high macromolecular viscosity while complexing; during chemical plating, the composite complexing agent promotes reaction and simultaneously can avoid metal ion deposition, so that the bonding strength between a plating layer and a substrate is very stable, the plated part cannot fall off even in subsequent high-temperature recycling, and the service life of the plated part is further prolonged; the stability of the composite complexing agent and the stability of the stabilizer are the same, and perfect chemical plating can be realized by using the solution in a double stable way; the double stability is favorable for adjusting the plating speed and the quality of the plating layer, and the plating piece is easy to spread on the surface of the electrode to achieve the purpose of uniform plating while the bonding strength between the plating layer and the matrix is ensured, so that the effect of filling the wafer packaging micropores without holes and gaps is further achieved, and the arch rate is low;
4) in the chemical plating process, the surface of the plated part is bombarded by vacuum plasma before and after the plated part, so that various pollutants and oxide layers on the surface of the plated part are removed, the surface of the plated part can be guaranteed to be compact and smooth after being cleaned, the surface cleaning degree is high, the close combination of a plating layer and a base material is facilitated, and the bonding strength between the plating layer and a base body is further guaranteed;
5) the flow is adjusted by adopting the variable frequency regulator in the chemical plating process, because the proton transmission of the solution is still difficult to ensure that the subsequent nickel ions and additives continuously enter the holes in the chemical plating process, and meanwhile, the bubbles generated in the chemical plating process easily form concave holes on the plating layer.
Detailed Description
In order to more clearly describe the present invention, the present invention is further described below in terms of words.
The invention provides a chemical nickel plating solution for wafer level packaging products, which comprises the following components in mass concentration:
the carrier is a compound of chloride ions and alum ions, and the mass concentration ratio is 1: (1-1.5), controlling the concentration of chloride ions to be between 20 and 40ppm/L and controlling the concentration of alum ions to be between 20 and 60ppm/L when the mixture is used;
the mass concentration ratio of the antioxidant to the inhibitor in use is 3: 1, the antioxidant and the inhibitor form a compound with a conjugate transmission bridge function when in use, so that the rapid deposition of pit parts is accelerated;
after the components are uniformly mixed according to the proportion, the pH value of the solution is adjusted to 4.3-4.6, and then a pH buffering agent with the mass concentration of 25% is added, and finally the preparation of the chemical nickel plating solution is completed.
In this embodiment, the complex complexing agent includes a component a and a component B, and the mass concentration ratio of the component a to the component B is 2: (1-2); the component A comprises citric acid with the mass concentration of 1-5g/L and ammonium acetate with the mass concentration of 1-5 g/L;
the component B comprises polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide according to the mass concentration ratio of 1:1:1: 1; the component A and the component B are uniformly stirred and mixed according to the concentration ratio to form the composite complexing agent.
In the embodiment, the components of the nickel plating solution can also comprise a reaction antifouling agent with the mass concentration of 20-40mg/L, and the reaction antifouling agent is composed of 5-10mg/L of ethylene glycol tertiary butyl ether and 15-30mg/L of phosphate. In the production process, the material numbers enter the cylinder and exit the plate cylinder, and are different, so that impurities are easily polluted, the chemical plating effect is uneven, and the like. Therefore, the reactive antifouling agent is added into the copper plating solution to keep the surface of the plated part clean in the chemical plating process, thereby ensuring the uniformity of chemical plating. The antioxidant is matched with the antifouling agent, so that not only can an oil pollution source be prevented, but also the corrosion of chemical trace ions can be prevented, and the optimal effect can be achieved by the proportion.
In this embodiment, the specific process for preparing the chemical nickel solution is as follows:
step a, preparing nickel salt, a composite complexing agent, a reducing agent, an anti-aging agent, a reaction accelerator, a surfactant, a stabilizer, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent according to a mass concentration ratio;
b, pouring a stabilizer, an anti-aging agent, a surfactant, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent into a nickel tank according to a proportion, carrying a stirring pump, stirring after pouring, wherein the stirring speed is 50-100r/min, and adding 1/2 composite complexing agent in the stirring process; stirring for 30 seconds to form a solution C;
step C, adding a reaction accelerator, a reducing agent and nickel salt into the solution C in sequence, stirring at a stirring speed of 100-200r/min, adding the remaining 1/2 composite complexing agent during stirring, and stirring uniformly for 30 seconds to form a solution D;
and D, adjusting the pH value of the solution D to 4.3-4.6, and then adding a pH buffer with the mass concentration of 25% to form the nickel plating solution.
The composite complexing agent is added in a separate mode in the using process, and is not poured into the plating solution at one time, because the composite complexing agent mainly plays a promoting role in the above steps to promote the uniform mixing of all components, the nickel salt is added in the last step in the configuration process, and the composite complexing agent mainly plays a complexing role in the following process, so that the stability of the plating solution is improved; the nickel salt is added in the last step, so that the oxidation of the nickel salt is reduced, and the deposition speed of the nickel liquid is improved; particularly, the composite complexing agent increases certain stability on the basis of the original complexing action, so that the stability of the plating solution is kept lasting for a long time.
In the embodiment, the reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridinol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridinol is (1-2): 1; the stabilizer is benzotriazole; benzotriazole is a high molecular stabilizer, and by adopting the high molecular stabilizer, the stability of the chemical nickel plating solution is ensured, and simultaneously, the formation of metal oxide generated by dissolution in the chemical plating process between a matrix and a nickel layer can be avoided, so that the obtained nickel layer is ensured to be fine in crystallization and compact; and further improve the binding force between the nickel layer and the substrate. A reaction accelerator is added into the solution, the reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridine methanol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridine methanol is (1-2) to 1; the accelerator adopts a composite mode, so that the phenomenon that the operation range of a single reaction accelerator is narrow is avoided; and the setting of accurate concentration accelerates the activation reaction speed, reduces the activation time, and can quickly realize the void-free and seamless filling of the wafer level packaging product.
In this embodiment, the nickel salt is nickel sulfate or nickel sulfamate, and the surfactant is sodium methallylsulfonate; the inhibitor is polyoxyethylene ether sulfate, the antioxidant is 1,2, 4-triazole, the chloride ions are provided by hydrochloric acid, and the alum ions are provided by alum sulfate; the most commonly used today is 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, known under the trade name anti-aging agent AW.
In order to achieve the above object, the present invention further provides an electroless nickel plating process of an electroless nickel plating solution for wafer level packaging products, comprising the following steps,
step 1, bombarding the surface of a plated part by adopting vacuum plasma to remove various pollutants and oxidation layers on the surface of the plated part;
step 2, putting the processed plated piece into a nickel tank with the nickel plating solution to carry out chemical nickel plating treatment; the temperature of the chemical nickel plating is divided into two stages, the temperature of the first stage is 75-85 ℃, and the temperature of the second stage is 55-65 ℃; the flow is regulated by adopting a variable frequency regulator, and the plating solution flow rate of the introduced bath solution is changed by the variable frequency regulator, so that the balance force applied to the interior of the plating solution is broken;
step 3, after the chemical nickel plating is finished, taking out the nickel plated piece, and bombarding the surface of the nickel plated piece with the nickel plated layer by adopting vacuum plasma again;
and 4, carrying out the next process on the plated part subjected to the surface treatment.
In this embodiment, the specific conditions of the vacuum plasma bombardment in the step 4 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3; the distance of the plasma bombardment is controlled to be 3-5 cm; the treatment temperature is 30-40 ℃; the treatment time is 15-25 s. The specific conditions of the vacuum plasma bombardment in the step 1 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3, controlling the bombardment distance to be 20-25 mm; the treatment temperature is 90-110 ℃; the treatment time is 15-25 s. The step 1 and the step 4 both adopt the mixed gas of hydrogen and nitrogen as the working medium for bombarding the surface of the plated part, the cleaning degree of the method is much better than that of the existing method adopting ultrapure water cleaning, the method is more favorable for the tight combination of the nickel plating layer and the base material, and the bonding strength between the plating layer and the base material is further improved. The bombardment is mainly different in distance; the closer the distance is, the greater the bombardment strength is, because the plated piece before nickel plating can be cleaned more deeply, so the bombardment distance is controlled to be 3-5 cm; step 4, nickel plating is finished, the surface of the nickel plated part has certain brittleness along with the time, the bombardment distance is lengthened, the surface of the plated part can become compact and smooth while cleaning, and the void ratio is reduced; and the bonding degree of the coating and the base material can be further enhanced in the bombardment process.
In the embodiment, the flow rate of the copper plating is regulated to 10-30L/min by the variable frequency regulator in the step 2.
The invention has the beneficial effects that: compared with the prior art, the chemical nickel plating solution and the chemical nickel plating process for the wafer level packaging product have the following advantages:
1) a reaction accelerator, a stabilizer, a composite complexing agent, an inhibitor, an antioxidant and a carrier are added on the basis of the original components of the nickel plating solution, and the alum ions and the chloride ions of the carrier are matched according to the proportion of 1: (1-1.5) the proportion range is mixed, so that the deposition effect of nickel is better, the reduction rate is accelerated, and the continuous nucleation rate is improved, so that the compactness of the integral nickel layer is greatly improved; the surface crystal compactness of the obtained chemical nickel plating layer is higher;
2) the solution is added with an inhibitor and an antioxidant on the original basis, and when the solution is used, the mass concentration ratio of the antioxidant to the inhibitor is 3: the purpose of the inhibitor is to inhibit the salient points on the surface of the substrate and accelerate the rapid deposition of the concave points, but the common single inhibitor has larger molecular compound and is difficult to be adsorbed to the salient points firstly, so that a compound with the function of conjugate transmission bridges is needed as the connection, and the selected antioxidant has the effect, and the effect is optimal according to the proportion.
3) The nickel plating solution adopts a specially-made stabilizer and a specially-made composite complexing agent, because the complexing capacity of the existing complexing agent is small, the phenomenon of instability is easily caused by small capacity in the complexing process, and nickel ions can be deposited on the wall of a tank all the time along with the lengthening of chemical plating time, in order to solve the problems, polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide are used as a part of the complexing agent, and the high molecular substances have the characteristic of high macromolecular viscosity while complexing; during chemical plating, the composite complexing agent promotes reaction and simultaneously can avoid metal ion deposition, so that the bonding strength between a plating layer and a substrate is very stable, the plated part cannot fall off even in subsequent high-temperature recycling, and the service life of the plated part is further prolonged; the stability of the composite complexing agent and the stability of the stabilizer are the same, and perfect chemical plating can be realized by using the solution in a double stable way; the double stability is favorable for adjusting the plating speed and the quality of the plating layer, and the plating piece is easy to spread on the surface of the electrode to achieve the purpose of uniform plating while the bonding strength between the plating layer and the matrix is ensured, so that the effect of filling the wafer packaging micropores without holes and gaps is further achieved, and the arch rate is low;
4) in the chemical plating process, the surface of the plated part is bombarded by vacuum plasma before and after the plated part, so that various pollutants and oxide layers on the surface of the plated part are removed, the surface of the plated part can be guaranteed to be compact and smooth after being cleaned, the surface cleaning degree is high, the close combination of a plating layer and a base material is facilitated, and the bonding strength between the plating layer and a base body is further guaranteed;
5) the flow is adjusted by adopting the variable frequency regulator in the chemical plating process, because the proton transmission of the solution is still difficult to ensure that the subsequent nickel ions and additives continuously enter the holes in the chemical plating process, and meanwhile, the bubbles generated in the chemical plating process easily form concave holes on the plating layer.
Compared with the prior art, the invention also has the following advantages:
1) the specially-made composite complexing agent consists of a specially-made component A and a component B, wherein the component A is used as a main complexing agent, and polyacrylamide in the component B has good scale inhibition performance, has a function of adsorbing impurities, and has good colloid characteristics and a dispersing function; but because of small complexing capacity, the phenomenon of instability is easily caused by small capacity in the complexing process, and nickel ions can be deposited on the wall of the tank all the time along with the lengthening of chemical plating time, in order to solve the problems, polyacrylamide, amino carboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide are used as a part of a complexing agent, and the macromolecular substances have the characteristic of high macromolecular viscosity while being complexed; when the chemical plating is carried out, the composite complexing agent promotes the reaction and simultaneously can avoid the deposition of metal ions, so that the bonding strength between the plating layer and the matrix is very stable, the plated part can not fall off even in subsequent high-temperature recycling, and the service life of the plated part is further prolonged.
2) Generally, the plating layer is easy to fall off due to the overhigh temperature during the chemical nickel plating; when the nickel plating solution is used for chemical plating, the temperature is divided into two chemical plating stages for treatment; the first stage can be completed in a short time by adopting the conventional high temperature of 75-85 ℃ due to the very good stability and the good complexation property at the beginning of use, and the nickel precipitation in the process is fast under the action of the composite complexing agent, so that most procedures of chemical nickel plating can be completed fast; along with the proceeding of chemical plating, the stability is reduced, the temperature is reduced, the chemical plating time is prolonged, even under the condition of 55-65 ℃, the dispersion capability and the covering capability of the plating solution ensure the continuation of the chemical plating due to the action of the composite complexing agent, and finally the proper thickness of a nickel plating layer is achieved; the temperature is divided by stages according to the thickness of the nickel plating layer, and the first-stage temperature is adopted when the thickness of the nickel plating layer reaches about 1/2; the second stage temperature is used when the thickness of the nickel plating layer reaches above 1/2. The technology adopts a mode of two stages with different temperatures and different time to carry out chemical plating, thereby avoiding the phenomenon that a plating layer is easy to fall off at high temperature; the bonding strength between the plating layer and the substrate is further ensured, so that the nickel plating layer has good adhesiveness and uniform plating layer; the process not only ensures the uniformity of chemical plating, but also shortens the chemical plating time.
The following are several specific examples of the invention
Example 1
An electroless nickel plating solution for wafer level packaging products comprises the following components in mass concentration:
the composite complexing agent comprises a component A and a component B, wherein the mass concentration ratio of the component A to the component B is 2: 1; the component A comprises citric acid with the mass concentration of 2g/L and ammonium acetate with the mass concentration of 2 g/L; the component B is a mixture of polyacrylamide, amino carboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide, and the mass concentration of the mixture is 2 g/L. The pH value of the solution is adjusted to be between 4.5, and then the solution is buffered by a pH buffering agent with the mass concentration of 25 percent to form the nickel plating solution.
The reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridine methanol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridine methanol is 1: 1.
The nickel plating solution prepared by the components is adopted, and the chemical nickel plating process is adopted to carry out nickel plating treatment on a plated part, wherein the temperature of the first stage is 80 ℃; the temperature of the second stage is 55 ℃, the chemical plating time of the two stages is 21 minutes, and the thickness of the finally obtained nickel layer is 12 microns; the obtained nickel-plated layer has consistent crystal size, smooth surface and no any cavity or crack; the nickel-plated layer is tested by a 180-degree bending test, and then a bent part is inspected by a magnifying glass which is amplified by 100 times, so that obvious cracks are not observed, and the peeling and falling phenomena are not generated; the bonding force of the nickel plating layer is good. In addition, the microscopic observation clearly shows that the nickel-plated layer has high structural compactness, uniform crystals and no any hollow and crack on the surface.
Example 2
An electroless nickel plating solution for wafer level packaging products comprises the following components in mass concentration:
the composite complexing agent comprises a component A and a component B, wherein the mass concentration ratio of the component A to the component B is 1: 1; the component A comprises citric acid with the mass concentration of 3.75g/L and ammonium acetate with the mass concentration of 3.75 g/L; the component B is a mixture of polyacrylamide, amino carboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide, and the mass concentration of the mixture is 7 g/L. The pH value of the solution is adjusted to be between 4.5, and then the solution is buffered by a pH buffering agent with the mass concentration of 25 percent to form the nickel plating solution.
The reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridine methanol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridine methanol is 2:1.
The nickel plating solution prepared by the components is adopted, and the chemical nickel plating process is adopted to carry out nickel plating treatment on a plated part, wherein the temperature of the first stage is 85 ℃; the temperature of the second stage is 60 ℃, the chemical plating time of the two stages is 20 minutes, and the thickness of the finally obtained nickel layer is 14 microns; the obtained nickel-plated layer has consistent crystal size, smooth surface and no any cavity or crack; the nickel-plated layer is tested by a 180-degree bending test, and then a bent part is inspected by a magnifying glass which is amplified by 100 times, so that obvious cracks are not observed, and the peeling and falling phenomena are not generated; the bonding force of the nickel plating layer is good. In addition, the microscopic observation clearly shows that the nickel-plated layer has high structural compactness, uniform crystals and no any hollow and crack on the surface.
Example 3
An electroless nickel plating solution for wafer level packaging products comprises the following components in mass concentration:
the balance of water, wherein the composite complexing agent comprises a component A and a component B, and the mass concentration ratio of the component A to the component B is 2: 1.5; the component A comprises citric acid with the mass concentration of 3g/L and ammonium acetate with the mass concentration of 3 g/L; the component B is a mixture of polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide, and the mass concentration is 4.5 g/L. The pH value of the solution is adjusted to be between 4.5, and then the solution is buffered by a pH buffering agent with the mass concentration of 25 percent to form the nickel plating solution.
The reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridine methanol, and the mass concentration ratio of the 2, 6-diaminopyridine to the 3-pyridine methanol is 2:1.
The nickel plating solution prepared by the components is adopted, and the chemical nickel plating process is adopted to carry out nickel plating treatment on a plated part, wherein the temperature of the first stage is 75 ℃; the temperature of the second stage is 65 ℃, the chemical plating time of the two stages is 20 minutes, and the thickness of the finally obtained nickel layer is 15 micrometers; the obtained nickel-plated layer has consistent crystal size, smooth surface and no any cavity or crack; the nickel-plated layer is tested by a 180-degree bending test, and then a bent part is inspected by a magnifying glass which is amplified by 100 times, so that obvious cracks are not observed, and the peeling and falling phenomena are not generated; the bonding force of the nickel plating layer is good. In addition, the microscopic observation clearly shows that the nickel-plated layer has high structural compactness, uniform crystals and no any hollow and crack on the surface.
Comparative example 1
The nickel plating solution prepared by the components is adopted to carry out chemical plating by adopting a conventional chemical plating mode, the chemical plating temperature is more than 80 ℃, the finally obtained nickel plating layer is 20 microns, and the chemical plating time is 35 minutes; the nickel plating layer is subjected to 180-degree bending test, then a bent part is inspected by a magnifying glass which is amplified by 100 times, cracks are obviously observed, and peeling and falling are generated; the bonding force between the nickel-plated layer and the base material does not reach the effect of market demand; in addition, it is clear from microscopic observation that the crystals of the nickel plating layer are not uniform in size and that some voids and cracks appear on part of the surface.
The test results for examples 1-3 and comparative example 1 are given in the following table:
1) coating appearance: visual inspection; 2) apparent morphology: tested by 180 degree bending test.
Through the three specific examples of the invention and the comparative example 1, the comparative example 1 adopts a conventional chemical plating method because a composite complexing agent, an accelerating reagent and a stabilizing agent are not adopted, the chemical plating time is long, the thickness of a nickel plating layer is large, the expected requirements cannot be met, and the product yield is low; the binding force between the plating layer and the base material is not high; the nickel layer of the plated part obtained by the invention has smooth appearance and uniform crystal lattice size of the plating layer; the microscopic observation shows that the structure of the plating layer is very compact, the crystallization of the plating layer is fine and uniform, and no crack exists; the 180-degree bending test shows that the bonding force of the plating layer is good, no obvious crack is observed when the plating layer is amplified by 100 times, which shows that the bonding force of the nickel plating layer obtained by the invention and the base material is very good, thereby perfectly ensuring the compactness of the plating layer structure.
The above disclosure is only an example of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (10)
1. The chemical nickel plating solution for the wafer level packaging product is characterized by comprising the following components in mass concentration:
the carrier is a compound of chloride ions and alum ions, and the mass concentration ratio is 1: (1-1.5), controlling the concentration of chloride ions to be between 20 and 40ppm/L and controlling the concentration of alum ions to be between 20 and 60ppm/L when the mixture is used;
the mass concentration ratio of the antioxidant to the inhibitor in use is 3: 1, the antioxidant and the inhibitor form a compound with a conjugate transmission bridge function when in use, so that the rapid deposition of pit parts is accelerated;
after the components are uniformly mixed according to the proportion, the pH value of the solution is adjusted to 4.3-4.6, and then a pH buffering agent with the mass concentration of 25% is added, and finally the preparation of the chemical nickel plating solution is completed.
2. The electroless nickel plating solution for wafer-level packaging products according to claim 1, wherein the composite complexing agent comprises a component A and a component B, and the mass concentration ratio of the component A to the component B is 2: (1-2); the component A comprises citric acid with the mass concentration of 1-5g/L and ammonium acetate with the mass concentration of 1-5 g/L;
the component B comprises polyacrylamide, aminocarboxylic acid resin, hyperbranched polyurethane sulfonate and beta-nicotinamide adenine dinucleotide according to the mass concentration ratio of 1:1:1: 1; the component A and the component B are uniformly stirred and mixed according to the concentration ratio to form the composite complexing agent.
3. An electroless nickel plating solution for wafer level packaging products as claimed in claim 1, wherein the composition of the nickel plating solution further comprises a reactive anti-fouling agent with a mass concentration of 20-40mg/L, wherein the reactive anti-fouling agent is composed of 5-10mg/L ethylene glycol tertiary butyl ether and 15-30mg/L phosphate ester.
4. An electroless nickel plating solution for wafer level package products as claimed in claim 3, wherein the specific process of the electroless nickel solution configuration is as follows:
step a, preparing nickel salt, a composite complexing agent, a reducing agent, an anti-aging agent, a reaction accelerator, a surfactant, a stabilizer, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent according to a mass concentration ratio;
b, pouring a stabilizer, an anti-aging agent, a surfactant, an inhibitor, an antioxidant, a carrier and a reaction antifouling agent into a nickel tank according to a proportion, carrying a stirring pump, stirring after pouring, wherein the stirring speed is 50-100r/min, and adding 1/2 composite complexing agent in the stirring process; stirring for 30 seconds to form a solution C;
step C, adding a reaction accelerator, a reducing agent and nickel salt into the solution C in sequence, stirring at a stirring speed of 100-200r/min, adding the remaining 1/2 composite complexing agent during stirring, and stirring uniformly for 30 seconds to form a solution D;
and D, adjusting the pH value of the solution D to 4.3-4.6, and then adding a pH buffer with the mass concentration of 25% to form the nickel plating solution.
5. An electroless nickel plating solution for wafer level packaging products as claimed in claim 1, wherein said reaction accelerator is a compound of 2, 6-diaminopyridine and 3-pyridinemethanol, and the mass concentration ratio of 2, 6-diaminopyridine to 3-pyridinemethanol is (1-2): 1.
6. An electroless nickel plating solution for wafer level packaging products according to claim 1, wherein said nickel salt is nickel sulfate or nickel sulfamate, said surfactant is sodium methallylsulfonate; the inhibitor is polyoxyethylene ether sulfate, the antioxidant is 1,2, 4-triazole, the chloride ions are provided by hydrochloric acid, and the alum ions are provided by alum sulfate; the anti-aging agent is a ketoamine anti-aging agent; the stabilizer is benzotriazole.
7. A chemical nickel plating process of chemical nickel plating solution for wafer level packaging products is characterized by comprising the following specific steps,
step 1, bombarding the surface of a plated part by adopting vacuum plasma to remove various pollutants and oxidation layers on the surface of the plated part;
step 2, placing the treated plated piece into a nickel tank with the nickel plating solution of any one of claims 1 to 6 for chemical nickel plating treatment; the temperature of the chemical nickel plating is divided into two stages, the temperature of the first stage is 75-85 ℃, and the temperature of the second stage is 55-65 ℃; the flow is regulated by adopting a variable frequency regulator, and the plating solution flow rate of the introduced bath solution is changed by the variable frequency regulator, so that the balance force applied to the interior of the plating solution is broken;
step 3, after the chemical nickel plating is finished, taking out the nickel plated piece, and bombarding the surface of the nickel plated piece with the nickel plated layer by adopting vacuum plasma again;
and 4, carrying out the next process on the plated part subjected to the surface treatment.
8. An electroless nickel plating process of an electroless nickel plating solution for wafer level packaging products as claimed in claim 7, wherein the specific conditions of the vacuum plasma bombardment of the step 4 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3; the distance of the plasma bombardment is controlled to be 3-5 cm; the treatment temperature is 30-40 ℃; the treatment time is 15-25 s.
9. An electroless nickel plating process of an electroless nickel plating solution for wafer level packaging products as claimed in claim 7, wherein the specific conditions of the vacuum plasma bombardment in the step 1 are as follows: the working medium adopted by the vacuum plasma bombardment is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen to the nitrogen is (1-2): 3, controlling the bombardment distance to be 20-25 mm; the treatment temperature is 90-110 ℃; the treatment time is 15-25 s.
10. The electroless nickel plating process of the electroless nickel plating solution for the wafer level package products as claimed in claim 7, wherein the flow rate of the copper plating is adjusted to 10-30L/min by a variable frequency regulator in the step 2.
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